Composition and method for treating plants with exogenous chemicals

Information

  • Patent Grant
  • 6475953
  • Patent Number
    6,475,953
  • Date Filed
    Friday, March 24, 2000
    24 years ago
  • Date Issued
    Tuesday, November 5, 2002
    21 years ago
Abstract
A composition is disclosed for application to a plant that comprises glyphosate, an aqueous diluent, and an excipient substance that is amphiphilic. The weight/weight ratio of the excipient substance to the exogenous chemical is between about 1:3 and about 1:100. The aqueous composition forms anisotropic aggregates on a wax layer, and the presence of the anisotropic aggregates can be detected by a test described herein. Compositions of the present invention, when applied to plants, provide enhanced biological activity per unit amount of glyphosate, as compared to otherwise similar compositions containing surfactants that do not form anisotropic aggregates. Without being bound by theory, it is presently believed that this enhanced biological activity results from the formation or enlargement of hydrophilic channels through the epicuticular wax of the plant.
Description




BACKGROUND OF THE INVENTION




This invention relates to formulations and methods for enhancing the efficacy of exogenous chemicals used in treating plants. An exogenous chemical, as defined herein, is any chemical substance, whether naturally or synthetically derived, which (a) has biological activity or is capable of releasing in a plant an ion, moiety or derivative which has biological activity, and (b) is applied to a plant with the intent or result that the chemical substance or its biologically active ion, moiety or derivative enter living cells or tissues of the plant and elicit a stimulatory, inhibitory, regulatory, therapeutic, toxic or lethal response in the plant itself or in a pathogen, parasite or feeding organism present in or on the plant. Examples of exogenous chemical substances include, but are not limited to, chemical pesticides (such as herbicides, algicides, fungicides, bactericides, viricides, insecticides, aphicides, miticides, nematicides, molluscicides, and the like), plant growth regulators, fertilizers and nutrients, gametocides, defoliants, desiccants, mixtures thereof, and the like.




Exogenous chemicals, including foliar-applied herbicides, have at times been formulated with surfactants, so that when water is added, the resulting sprayable composition is more easily and effectively retained on the foliage (e.g., the leaves or other photosynthesizing organs) of plants. Surfactants can also bring other benefits, including improved contact of spray droplets with a waxy leaf surface and, in some cases, improved penetration of the accompanying exogenous chemical into the interior of leaves. Through these and perhaps other effects, surfactants have long been known to increase the biological effectiveness of herbicide compositions, or other compositions of exogenous chemicals, when added to or included in such compositions. Thus, for example, the herbicide glyphosate (N-phosphonomethylglycine) has been formulated with surfactants such as polyoxyalkylene-type surfactants including, among other surfactants, polyoxyalkylene alkylamines. Commercial formulations of glyphosate herbicide marketed under the trademark ROUNDUP® have been formulated with a surfactant composition based on such a polyoxyalkylene alkylamine, in particular a polyethoxylated tallowamine, this surfactant composition being identified as MON 0818. Surfactants have generally been combined with glyphosate or other exogenous chemicals either in a commercial concentrate (herein referred to as a “coformulation”), or in a diluted mixture that is prepared from separate compositions, one comprising an exogenous chemical (e.g. glyphosate) and another comprising surfactant, prior to use in the field (i.e., a tank mix).




Various combinations of exogenous chemicals and surfactants or other adjuvants have been tested in the past. In some instances, the addition of a particular surfactant has not produced uniformly positive or negative changes in the effect of the exogenous chemical on the plant (e.g., a surfactant that may enhance the activity of a particular herbicide on certain weeds may interfere with, or antagonize, the herbicidal efficacy on another weed species).




Some surfactants tend to degrade fairly rapidly in aqueous solutions. As a result, surfactants that exhibit this property can only be used effectively in tank mixes (i.e., mixed with the other ingredients in solution or dispersion in the tank soon before spraying is to occur), rather than being coformulated in an aqueous composition with the other ingredients in the first instance. This lack of stability, or inadequate shelf-life, has hindered the use of certain surfactants in some exogenous chemical formulations.




Other surfactants, though chemically stable, are physically incompatible with certain exogenous chemicals, particularly in concentrate coformulations. For example, most classes of nonionic surfactant, including polyoxyethylene alkylether surfactants, do not tolerate solutions of high ionic strength, as for example in a concentrated aqueous solution of a salt of glyphosate. Physical incompatibility can also lead to inadequate shelf-life. Other problems that can arise from such incompatibility include the formation of aggregates large enough to interfere with commercial handling and application, for example by blocking spray nozzles.




Another problem that has been observed in the past is the effect of environmental conditions on uptake of an exogenous chemical composition into foliage of a plant. For example, conditions such as temperature, relative humidity, presence or absence of sunlight, and health of the plant to be treated, can affect the uptake of a herbicide into the plant. As a result, spraying exactly the same herbicidal composition in two different situations can result in different herbicidal control of the sprayed plants.




One consequence of the above-described variability is that often a higher rate of herbicide per unit area is applied than might actually be required in that situation, in order to be certain that adequate control of undesired plants will be achieved. For similar reasons, other foliar-applied exogenous chemicals are also typically applied at significantly higher rates than needed to give the desired biological effect in the particular situation where they are used, to allow for the natural variability that exists in efficiency of foliar uptake. A need therefore exists for compositions of exogenous chemicals that, through more efficient uptake into plant foliage, allow reduced use rates.




Many exogenous chemicals are commercially packaged as a liquid concentrate that contains a significant amount of water. The packaged concentrate is shipped to distributors or retailers. Ultimately the packaged concentrate ends up in the hands of an end user, who further dilutes the concentrate by adding water in accordance with label instructions on the package. The dilute composition thus prepared is then sprayed on plants.




A significant portion of the cost of such packaged concentrates is the cost of transporting the concentrate from the manufacturing site to the location where the end user purchases it. Any liquid concentrate formulation that contained relatively less water and thus more exogenous chemical would reduce the cost per unit amount of exogenous chemical. However, one important limit on the ability of the manufacturer to increase the loading of the exogenous chemical in the concentrate is the stability of that formulation. With some combinations of ingredients, a limit will be reached at which any further reduction of water content in the concentrate will cause it to become unstable (e.g., to separate into discrete layers), which may make it commercially unacceptable.




Accordingly, a need exists for improved formulations of exogenous chemicals, particularly herbicides, that are stable, effective, less sensitive to environmental conditions, and permit the use of reduced amounts of exogenous chemical to achieve the desired biological effect in or on plants. A need also exists for stable liquid concentrate formulations of exogenous chemicals that contain less water and more exogenous chemical than prior art concentrates.




SUMMARY OF THE INVENTION




The present invention relates to novel methods and compositions wherein exogenous chemicals are applied to plants to generate a desired biological response.




One embodiment of the present invention is a method of applying an exogenous chemical to a plant, comprising the steps of (a) contacting foliage of the plant with a biologically effective amount of the exogenous chemical, and (b) contacting the same foliage with an aqueous composition that comprises a first excipient substance that is amphiphilic. The weight/weight ratio of said first excipient substance to the exogenous chemical is between about 1:3 and about 1:100. Further, the aqueous composition forms anisotropic aggregates in or on a wax layer as explained below. “Contacting” in this context means placing the substance or composition on the foliage. “Amphiphilic” means having at least one polar, water-soluble head group which is hydrophilic and at least one water-insoluble organic tail which is hydrophobic, contained within the same molecule.




In this method, step (b) can occur simultaneously with or within about 96 hours before or after step (a). In embodiments of the method in which the two steps occur simultaneously, either the exogenous chemical and the aqueous composition can be applied to the plant separately, for example by two spray nozzles directed at the same foliage, or the exogenous chemical can be contained within the aqueous composition, for example in a tank mix or coformulation.




Formation of anisotropic aggregates in or on a wax layer is determined by a test described in detail subsequently herein. In general, the test, as it applies to a composition comprising an exogenous chemical, comprises the steps of (1) providing a glass microscope slide coated with a thin, uniform layer of wax, such that the wax layer on the slide exhibits a dark field when illuminated by transmitted polarized light and examined through a microscope, (2) preparing a sample of an aqueous solution or dispersion of the composition to be tested, diluted or concentrated if necessary such that the concentration of exogenous chemical is about 15% to about 20% by weight of the composition, (3) positioning the wax-coated slide on the stage of a microscope that transmits polarized light through the slide, (4) placing a drop of the sample on the wax on the slide to form an assay slide, (5) maintaining the assay slide at approximately ambient temperature for a period of about 5 to about 20 minutes, and (6) determining, at the end of that period, whether when transmitting polarized light the locus of the drop on the slide displays birefringence. Birefringence at 5-20 minutes indicates the presence of anisotropic aggregates in or on the wax layer, while the absence of birefringence at that time indicates the absence of anisotropic aggregates as defined herein.




The test, as it applies to an aqueous composition of one or more excipient substances, not itself containing an exogenous chemical but intended for application to foliage of a plant in conjunction with an exogenous chemical, is as just described, except that in step (2) the composition is diluted or concentrated so that the concentration of the first excipient substance is approximately 5% to 7% by weight.




An “excipient substance” as that term is used in this patent is any substance other than an exogenous chemical and water that is added to the composition. “Excipient substances” include inert ingredients, although an excipient substance useful in the present invention does not have to be devoid of biological activity.




Another embodiment of the present invention is a plant treatment composition comprising (a) an exogenous chemical, and (b) a first excipient substance that is amphiphilic. As described above, the weight/weight ratio of said first excipient substance to the exogenous chemical is between about 1:3 and about 1:100, and in presence of water said composition forms anisotropic aggregates in or on a wax layer. This composition can be used in a method of treating plants, in which foliage of the plant is contacted with a biologically effective amount of a composition as described above and further comprising an aqueous diluent.




A wide variety of exogenous chemicals can be used in the compositions and methods of the present invention. A preferred class is foliar-applied exogenous chemicals, i.e. exogenous chemicals that are normally applied post-emergence to foliage of plants. A preferred subclass of foliar-applied exogenous chemicals is those that are water-soluble. By “water-soluble” in this context is meant having a solubility in distilled water at 25° C. greater than about 1% by weight. Especially preferred water-soluble exogenous chemicals are salts that have an anion portion and a cation portion. In one embodiment of the invention, at least one of the anion and cation portions is biologically active and has a molecular weight of less than about 300. Particular examples of such exogenous chemicals where the cation portion is biologically active are paraquat, diquat and chlormequat. More commonly it is the anion portion that is biologically active.




Another preferred subclass of exogenous chemicals is those that exhibit systemic biological activity in the plant. Within this subclass, an especially preferred group of exogenous chemicals is N-phosphonomethylglycine and its herbicidal derivatives. N-phosphonomethylglycine, often referred to by its common name glyphosate, can be used in its acid form, but is more preferably used in the form of a salt. Any water-soluble salt of glyphosate can be used in the practice of this invention. Some preferred salts include the sodium, potassium, ammonium, mono-, di-, tri- and tetra-C


1-4


-alkylammonium, mono-, di- and tri-C


1-4


-alkanolammonium, mono-, di- and tri-C


1-4


-alkylsulfonium and sulfoxonium salts. The ammonium, monoisopropylammonium and trimethylsulfonium salts of glyphosate are especially preferred. Mixtures of salts can also be useful in certain situations.




A composition of the present invention comprising an exogenous chemical and a first excipient substance as described above can have a number of different physical forms. For example, the composition can further comprise water in an amount effective to make the composition a dilute aqueous composition ready for application to foliage of a plant. Such a composition typically contains about 0.02 to about 2 percent by weight of the exogenous chemical, but for some purposes can contain up to about 10 percent by weight or even more of the exogenous chemical.




Alternatively, the composition can be a shelf-stable concentrate composition comprising the exogenous chemical substance in an amount of about 10 to about 90 percent by weight. By “shelf-stable” in this context it is meant that the composition does not exhibit phase separation when stored at ambient temperature for a period of time dependent on the particular circumstances. Such shelf-stable concentrates can be, for example, (1) a solid composition comprising the exogenous chemical substance in an amount of about 30 to about 90 percent by weight, such as a water-soluble or water-dispersible granular formulation, or (2) a composition that further comprises a liquid diluent, wherein the composition comprises the exogenous chemical substance in an amount of about 10 to about 60 percent by weight. In this latter embodiment, it is especially preferred for the exogenous chemical substance to be water-soluble and present in an aqueous phase of the composition in an amount of about 15 to about 45 percent by weight of the composition. In particular, such a composition can be, for example, an aqueous solution concentrate or an emulsion having an oil phase. If it is an emulsion, it can more specifically be, for example, an oil-in-water emulsion, a water-in-oil emulsion, or a water-in-oil-in-water multiple emulsion. In one particular embodiment of the invention, the solid or aqueous composition further comprises a solid inorganic particulate colloidal material.




As described above, one embodiment of the invention is a sprayable composition having the property that it forms anisotropic aggregates in or on a wax layer. This composition comprises an exogenous chemical, an aqueous diluent, and a first excipient substance which is amphiphilic. In the sprayable composition, the weight/weight ratio of the first excipient substance to the exogenous chemical is between about 1:3 and about 1:100. A sprayable composition conforms to this embodiment of the invention even if the formation of anisotropic aggregates in or on a wax layer occurs only following concentration of the composition on the wax layer by evaporation of water. The term “spray composition” is sometimes used herein to mean a sprayable composition.




In a related embodiment of the invention, a concentrate composition is provided which, upon dilution, dispersion or dissolution in water forms the sprayable composition just described. The concentrate composition contains a reduced amount of the aqueous diluent, or, in a particular embodiment, is a dry composition having less than about 5% water by weight. Typically a concentrate composition of the invention contains at least about 10% by weight of the exogenous chemical, preferably at least about 15%.




An alternative embodiment is a composition that does not itself comprise an exogenous chemical, but is intended for application to a plant in conjunction with or as a carrier for the application of an exogenous chemical. This composition comprises a first excipient substance as described above. Such a composition may be sprayable, in which case it also comprises an aqueous diluent, or it may be a concentrate, requiring dilution. dispersion or dissolution in water to provide a sprayable composition. Thus, this embodiment of the invention can be provided as a stand-alone product and applied to a plant, diluted as appropriate with water, simultaneously with the application of an exogenous chemical, or before or after the application of the exogenous chemical.




In all embodiments, it is believed that the first excipient substance forms supramolecular aggregates in aqueous solution or dispersion. In particular it is believed that aqueous compositions of the present invention form aggregates in aqueous solution or dispersion the majority of which are not simple micelles. “Majority” means that more than 50% by weight of the first excipient substance present is in the form of complex aggregates other than simple micelles, e.g. as bilayers or multilamellar structures. Preferably, more than 75% by weight is in the form of complex aggregates other than simple micelles.




Whether or not an amphiphilic substance forms such aggregates depends on its molecular architecture. The effects of molecular architecture on supramolecular self-assembly of amphiphilic molecules, as set forth for example by J. N. Israelachvili, D. J. Mitchell and B. W. Ninham in


Faraday Transactions II


, Volume 72, pp. 1525-1568 (1976) and in numerous later articles and monographs, are well known and understood. An important aspect is “critical packing parameter” (P) which is defined in the literature by the following equation:








P=V/lA








where V is the volume of the hydrophobic tail of the molecule, l is the effective length of the hydrophobic tail, and A is the area occupied by the hydrophilic headgroup. These dimensions can be calculated from physical measurements as described in the literature and have been published for numerous amphiphilic compounds.




It is believed that amphiphilic substances useful as the first excipient substance herein have a critical packing parameter greater than ⅓. The first excipient substance forms aggregates in aqueous solution or dispersion which preferably have at least one dimension that is greater than two times the molecular length of the first excipient substance.




In one embodiment of the invention, an aqueous composition comprises supramolecular aggregates of the first excipient substance which have an average diameter of at least 20 nm, preferably at least 30 nm.




These supramolecular aggregates can take a number of forms. In one preferred embodiment, the first excipient substance is a vesicle-forming amphiphilic substance, such as a vesicle-forming lipid, and when the substance is dispersed in water the majority (greater than 50% by weight, preferably greater than 75% by weight) of the first excipient substance is present as vesicles or liposomes. In another preferred embodiment the first excipient substance is present as bilayers or multilamellar structures which are not organized as vesicles or liposomes. Compositions of the present invention can also include, without limitation, colloidal systems such as emulsions (water/oil, oil/water, or multiple, e.g., water/oil/water), foams, microemulsions, and suspensions or dispersions of microparticulates, nanoparticulates, or microcapsules. Compositions of the invention can include more than one type of aggregate or colloidal system; examples include liposomes or vesicles dispersed in a microemulsion, and compositions having characteristics of both emulsions and suspensions, e.g. suspo-emulsions. The present invention also encompasses any formulation, which may or may not contain a significant amount of water, that on dilution in an aqueous medium forms such colloidal systems, and/or systems comprising vesicles, liposomes, bilayers or multilamellar structures, so long as the other requirements stipulated herein are met.




The weight ratio of the first excipient substance to the exogenous chemical is between about 1:3 and about 1:100. We have been surprised by the high level of biological effectiveness, specifically herbicidal effectiveness of a glyphosate composition, exhibited at such low ratios of excipient substance to exogenous chemical. Higher ratios can also be effective but are likely to be uneconomic in most situations and increase the risk of producing an antagonistic effect on effectiveness of the exogenous chemical.




Prior art exogenous chemical compositions that have included liposome-forming excipient substances have typically contained a higher percentage of the liposome-forming excipient substance than of the exogenous chemical. Compositions of the present invention, in contrast, contain less of the excipient substance than the exogenous chemical, and in some embodiments much less. This makes the compositions of the present invention much less expensive than the above-described prior art compositions. It is surprising that the enhancement of biological activity that has been observed when using the present invention can be achieved with the addition of relatively small amounts of such excipient substances.




In one embodiment of the invention the first excipient substance is a liposome-forming material that comprises an amphiphilic compound or mixture of such compounds having two hydrophobic moieties, each of which is a saturated alkyl or acyl chain having from about 8 to about 22 carbon atoms. The amphiphilic compound or mixture of such compounds having said two hydrophobic moieties with about 8 to about 22 carbon atoms constitutes from about 40 to 100 percent by weight of all amphiphilic compounds having two hydrophobic moieties present in the liposome-forming material. Preferably the liposome-forming material has a hydrophilic head group comprising a cationic group. More preferably, the cationic group is an amine or ammonium group.




In a preferred embodiment of the invention, the first excipient substance comprises a liposome-forming compound having a hydrophobic moiety comprising two saturated or unsaturated hydrocarbyl groups R


1


and R


2


each having about 7 to about 21 carbon atoms. A number of subclasses of such liposome-forming compounds are known.




One subclass has the formula






N


+


(CH


2


R


1


)(CH


2


R


2


)(R


3


)(R


4


) Z





  I






wherein R


3


and R


4


are independently hydrogen, C


1-4


alkyl or C


1-4


hydroxyalkyl and Z is a suitable anion.




A second subclass has the formula






N


+


(R


5


)(R


6


)(R


7


)CH


2


CH(OCH


2


R


1


)CH


2


(OCH


2


R


2


) Z





  II






wherein R


5


, R


6


and R


7


are independently hydrogen, C


1-4


alkyl or C


1-4


hydroxyalkyl and Z is a suitable anion.




A third subclass has the formula






N


+


(R


5


)(R


6


)(R


7


)CH


2


CH(OCOR


1


)CH


2


(OCOR


2


) Z





  III






wherein R


5


, R


6


, R


7


and Z are as defined above.




A fourth subclass has the formula






N


+


(R


5


)(R


6


)(R


7


)CH


2


CH


2


-PO


4







CH


2


CH(OCOR


1


)CH


2


(OCOR


2


)  IV






wherein R


5


, R


6


, and R


7


are as defined above.




Compounds of formulas I-IV will have the indicated formulas at a pH of 4 and may have the same formulas at other pH's as well. It should be understood, however, that compositions of the present invention are not limited to use at a pH of 4.




R


1


and R


2


preferably are independently saturated straight-chain alkyl groups each having about 7 to about 21 carbon atoms. Examples of suitable agriculturally acceptable anions Z include hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate.




In all of the above subclasses of liposome-forming substances, the hydrophilic moiety comprises a cationic group, specifically an amine or ammonium group. The compound as a whole is in some cases cationic (as in I, II and III) and in some cases neutral (as in IV). Where the amine group is quaternary, it behaves as a cationic group independently of pH. Where the amine group is secondary or tertiary, it behaves as a cationic group when protonated, i.e. in an acid medium, for example at a pH of 4.




In a preferred embodiment, the first excipient substance is a phospholipid selected from the group consisting of di-C


8-22


-alkanoylphosphatidylcholines and di-C


8-22


-alkanoylphosphatidylethanolamines. In a particularly preferred embodiment, the first excipient substance is a dipalmitoyl or distearoyl ester of phosphatidylcholine or a mixture thereof.




Other subclasses of liposome-forming substances having two hydrophobic chains each comprising a C


7-21


hydrocarbyl group can also be used as the first excipient substance in compositions of the invention. While substances having a cationic group in the hydrophilic moiety are preferred, nonionic or anionic substances can be used if desired.




In another embodiment of the invention. the first excipient substance is an amphiphilic quaternary ammonium compound or mixture of such compounds. The hydrophobic moiety of the quaternary ammonium compound is a saturated alkyl or haloalkyl group having about 6 to about 22 carbon atoms. In this embodiment, the first excipient substance is not necessarily a liposome-forming substance, but it is believed to form aggregates in aqueous solution or dispersion as described above.




Preferred quaternary ammonium compounds (other than those which are liposome-forming and have two hydrocarbyl chains) for use as the first excipient substance in compositions of the invention have the formula






R


8


—W


a


—X—Y


b


—(CH


2


)


n


—N


+


(R


9


)(R


10


)(R


11


) T





  V






wherein R


8


represents the hydrophobic moiety and is a hydrocarbyl or haloalkyl group having from about 6 to about 22 carbon atoms, W and Y are independently O or NH, a and b are independently 0 or 1 but at least one of a and b is 1, X is CO, SO or SO


2


, n is 2 to 4, R


9


, R


10


and R


11


are independently C


1-4


alkyl, and T is a suitable anion. R


8


in one particular embodiment is hydrocarbyl having about 12 to about 18 carbon atoms. R


8


can also be fluorinated. In one specific embodiment, R


8


is perfluorinated, and preferably has about 6 to about 12 carbon atoms. Suitable anions T include hydroxide, chloride, bromide, iodide, sulfate, phosphate and acetate. In one particularly preferred embodiment, R


8


is saturated perfluoroalkyl having about 6 to about 12 carbon atoms, X is CO or SO


2


, Y is NH, a is 0, b is 1, n is 3, R


9


, R


10


and R


11


are methyl, and T is selected from the group consisting of chloride, bromide and iodide.




In a further embodiment of the invention, the first excipient substance is an alkylether surfactant or mixture of such surfactants having the formula






R


12


—O—(CH


2


CH


2


O)


n


(CH(CH


3


)CH


2


O)


m


—R


13


  VI






wherein R


12


is an alkyl or alkenyl group having about 16 to about 22 carbon atoms, n is an average number of about 10 to about 100, m is an average number of 0 to about 5 and R


13


is hydrogen or C


1-4


alkyl. Preferably R


12


is a saturated straight-chain alkyl group, R


13


is hydrogen, m is 0 and n is from about 10 to about 40, more preferably from about 20 to about 40. Most preferably the alkylether surfactant is a polyoxyethylene cetyl or stearyl ether or mixture thereof having 20-40 moles of ethylene oxide (EO). The term “alkylether” as used herein should be understood to include alkenylether surfactants.




Compositions of the present invention can optionally further comprise a second excipient substance having at least one hydrophobic moiety, wherein if the second excipient substance has one hydrophobic moiety, the hydrophobic moiety is a hydrocarbyl or haloalkyl group having about 6 to about 22 carbon atoms, and wherein if the second excipient substance has a plurality of hydrophobic moieties, each such hydrophobic moiety is a hydrocarbyl or haloalkyl group having more than 2 carbon atoms, said plurality of hydrophobic moieties having a total of about 12 to about 40 carbon atoms. The second excipient substance, if present, may or may not itself be one that forms supramolecular aggregates as described above. In a particular embodiment of the invention where the first excipient substance is a liposome-forming substance of formula I, II, III or IV above, a second excipient substance is present and is a quaternary ammonium compound or mixture of such compounds. Among preferred quaternary ammonium compounds for use as the second excipient substance in this embodiment are compounds of formula V above.




In another particular embodiment of the invention where the first excipient substance is a liposome-forming substance of formula I, II, III or IV above, a second excipient substance is present and is a compound or mixture of compounds of formula






R


14


—CO—A—R


15


  VII






wherein R


14


is a hydrocarbyl group having about 5 to about 21 carbon atoms, R


15


is a hydrocarbyl group having 1 to about 14 carbon atoms, the total number of carbon atoms in R


14


and R


15


is about 11 to about 27, and A is O or NH.




R


14


preferably has about 11 to about 21 carbon atoms, R


15


preferably has 1 to about 6 carbon atoms and A is preferably O. More preferably, the second excipient substance is a C


1-4


alkyl ester of a C


12-18


fatty acid, for example a propyl, isopropyl or butyl ester of a C


12-18


fatty acid. Butyl stearate is an especially preferred example. The aqueous composition in embodiments comprising a compound of formula VII preferably is an emulsion comprising an oil phase that comprises said second excipient substance, for example a water-in-oil-in-water multiple emulsion or an oil-in-water emulsion. Alternatively, a second excipient substance of formula VII is associated in some way with a liposome-forming first excipient substance.




In yet another particular embodiment of the invention, the first excipient substance is an alkylether surfactant of formula VI and a second excipient substance is present and is a compound or mixture of compounds of formula VII.




In any of the above particular embodiments. the exogenous chemical and/or second excipient substance can be encapsulated within or associated with aggregates (e.g., liposomes) formed by the first excipient substance, but do not necessarily have to be so encapsulated or associated. “Associated” in this context means bound to or at least partly intercalated in some fashion in a vesicle wall, as opposed to being encapsulated. In yet another embodiment of the invention where the first excipient substance forms liposomes, the exogenous chemical and/or second excipient substance is not encapsulated in or associated with the liposomes at all. Although the present invention does not exclude the possibility of so encapsulating or associating the exogenous chemical, a presently preferred dilute sprayable liposomal composition encapsulates less than 5% by weight of the exogenous chemical that is present in the overall composition. Another dilute sprayable liposomal embodiment of the present invention has no substantial amount (i.e., less than 1% by weight) of the exogenous chemical encapsulated in the liposomes. As a droplet of such a liposomal composition dries on foliage of a plant, the proportion of the exogenous chemical that is encapsulated in the liposomes may change. Compositions of the present invention that include an exogenous chemical can be applied to foliage of plants in an amount that is effective to achieve the desired biological effect of the exogenous chemical. For example. when the exogenous chemical is a post-emergence herbicide, the composition can be applied to a plant in a herbicidally effective amount.




Without being bound by theory, it is believed that that the method and compositions of the present invention create or enlarge hydrophilic channels through the epicuticular wax of the plant cuticle, these channels being capable of accommodating the mass transfer of a water-soluble exogenous chemical into the plant, and thus transporting the exogenous chemical into the plant more rapidly or more completely than an epicuticular wax layer lacking such formation or enlargement of hydrophilic channels. Of course, certain compositions of the present invention can also enter a plant through stomata, but this generally requires a very low surface tension which is not an essential feature of the present compositions. The enhanced cuticular penetration believed to be achieved by the compositions of the present invention enhances the overall delivery and effectiveness of the exogenous chemical. Whereas an exogenous chemical such as glyphosate, formulated as an aqueous solution or dispersion with surfactants which do not have the property of forming anisotropic aggregates in or on a wax layer, normally penetrates through the epicuticular wax very slowly (e.g., in 1-4 days), a substantial portion of the exogenous chemical in compositions of the present invention penetrates much more quickly (e.g., in from about 10 minutes to a few hours, preferably in less than about 30 minutes).




Thus, methods and compositions of the invention are believed to owe their superior effectiveness at least in part to accelerated uptake into plant foliage. In conventional methods of treating plants with exogenous chemicals, in particular polar exogenous chemicals, the epicuticular wax layer presents an almost continuous barrier through which such exogenous chemicals diffuse with difficulty, even in the presence of surfactants which increase diffusive mobility but do not introduce the possibility of rapid mass transfer through hydrophilic channels.




Again without being bound by theory. it is believed that the hydrophilic channels are created within the epicuticular wax layer by the self-assembly of molecules of the first excipient substance which has a hydrophobic moiety that associates with the wax and a hydrophilic moiety that attracts water to form an aqueous continuum across the epicuticular wax layer linking up with hydrophilic pathways in the cuticle proper. A polar exogenous chemical can move by mass transfer along such an aqueous continuum to enter the plant.




Again without being bound by theory, it is believed that when the composition is present on the leaf of a plant as a droplet of aqueous solution or dispersion, in an aqueous microdomain on the cuticular surface (i.e., the aqueous region at the interface between the water droplet and the epicuticular wax). the majority (i.e., more than 50% by weight) of the aggregate-forming substance is present in a form other than a monolayer, for example as a bilayer or multilamellar (liquid crystal) structure. The aggregate-forming substances employed have several preferred characteristics that are believed to contribute to the formation of transcuticular hydrophilic channels. For instance, they have a tendency to form extended self-assembled structures in the presence of water and the kinds of waxes encountered in cuticles. Generally, materials that form non-simple (i.e., not small spherical micellar structures) aggregates in solution, such as vesicles or cylindrical, discotic, or ribbon-like micellar structures are preferred. These tend to form more complex adsorbed and absorbed layers with hydrophobic substrates than those simple micellar systems that tend to produce simple adsorbed monolayers. These substances also tend to produce lyotropic mesophases such as lamellar, hexagonal or reversed hexagonal phases in the compositions established in the aqueous microdomains in or on the cuticle.




In one embodiment of the invention, a cationic headgroup on the first excipient substance is also preferred. The cationic group is believed to enhance initial adhesion to the leaf surface, since the majority of such surfaces carry an overall negative charge. The cationic group is also believed to contribute to the hydrophilicity of channels in the epicuticular wax formed or enlarged by the method and compositions of the invention. Cationic groups, in particular amine or ammonium groups, attract water molecules which further enlarge the hydrophilic channels and thereby provide an improved pathway of entry for exogenous chemicals that are polar or water-soluble.




It is further believed that the creation or enlargement of hydrophilic channels in epicuticular wax results in the wax becoming plasticized. A further embodiment of the invention is thus a method for applying an exogenous chemical to a plant having an epicuticular wax layer, comprising (a) plasticizing the epicuticular wax layer in conjunction with (b) contacting the epicuticular wax layer with the exogenrous chemical. In this embodiment the step of plasticizing the epicuticular wax layer is accomplished by contacting the layer with an aqueous composition comprising a first excipient substance as defined above and optionally a second excipient substance as defined above. The weight ratio of the first excipient substance to the exogenous chemical is between about 1:3 and about 1:100.




Herbicidal compositions in accordance with the present invention are also useful in methods for enhancing the yield of a field crop. Such a method can comprise the steps of (a) planting a crop in a field, (b) substantially freeing the field of one or more weed species that would diminish the yield of the crop by applying to the weed species a herbicidally effective amount of a composition as described above, (c) allowing the crop to mature, and (d) harvesting the crop. Alternatively, the method can comprise the steps of (a) substantially freeing the field of one or more weed species that would diminish the yield of the crop by applying to the weed species a herbicidally effective amount of the composition, (b) planting the crop in the field, (c) allowing the crop to mature, and (d) harvesting the crop.




In one particular method in accordance with the present invention, a herbicidal composition as described above can be applied to a complex of weeds that are present in a single field, the weeds being, for example, velvetleaf, morningglory, and prickly sida. The composition is applied in a herbicidally effective amount, and provides herbicidal control of each of the weed species in the complex.




Another embodiment of the present invention is a herbicidal method, comprising contacting the foliage of a plant with a herbicidally effective amount of a composition as described above, whereby the herbicidal effectiveness of the composition on the plant to which it is applied is visibly better than the herbicidal effectiveness on that same species of plant, under substantially the same conditions, of a composition-containing a similar amount of surfactant but that does not form anisotropic aggregates. “Visibly better” in this context means that the difference in herbicidal effect of the two compositions on the plants is readily noticeable to the eye of an experienced weed scientist.




Another embodiment of the present invention is a herbicidal method which can be used in a field that contains both weed and crop plants, where the crop plants are resistant to the effects of a particular herbicide at the rate that herbicide is used. The method comprises contacting the foliage of both the weeds and the crops in the field with a composition as described above. The composition will have a herbicidal effect on the weeds (i.e., it will partially or entirely kill the weeds) but it will not harm the crops. This herbicidal method applies to any combination of a selective post-emergence herbicide (e.g. 2,4-D) and a crop on which that herbicide can be used selectively to kill weeds (e.g., in the case of 2,4-D, wheat). This herbicidal method also applies to any combination of a normally non-selective post-emergence herbicide and a crop bred or genetically modified to be resistant to that herbicide. An example of a suitable combination of herbicide and herbicide-resistant crop is ROUNDUP® herbicide and ROUNDUP READY® crops, developed by Monsanto Company.




The compositions and methods of the present invention have a number of advantages. They provide enhanced biological activity of exogenous chemicals in or on plants in comparison with prior formulations, either in terms of greater ultimate biological effect. or obtaining an equivalent biological effect while using a reduced application rate of exogenous chemical. Certain herbicide formulations of the present invention can avoid antagonism that has been observed in some prior art herbicide formulations, and can minimize quick production of necrotic lesions on leaves that in some situations hinder overall translocation of herbicide in the plant. Certain herbicide compositions of the invention modify the spectrum of activity of the herbicide across a range of plant species. For example, certain formulations of the present invention containing glyphosate can provide good herbicidal activity against broadleaf weeds while not losing any herbicidal effectiveness on narrowleaf weeds. Others can enhance herbicidal effectiveness on narrowleaf weeds to a greater extent than on broadleaf weeds. Still others can have enhanced effectiveness which is specific to a narrow range of species or even a single species.




Another advantage of the present invention is that it employs relatively small amounts of the first and second excipient substances in relation to the amount of exogenous chemical employed. This makes the compositions and methods of the present invention relatively inexpensive, and also tends to reduce instability problems in specific compositions where one or both excipient substances are physically incompatible with the exogenous chemical (e.g., alkylether surfactants in solutions of high ionic strength, such as concentrated glyphosate salt solutions).




Even at the low concentrations of the excipient substances used in the present invention, there may be limits on the maximum concentration of exogenous chemical that can be used without causing compatibility problems (e.g., separation of the composition into discrete layers). In some preferred embodiments of the invention, composition stability at high loadings of exogenous chemical is maintained by adding other ingredients such as, for example, colloidal particulates. Some compositions of the present invention exhibit enhanced biological activity and have a higher loading of exogenous chemical than possible in prior art compositions.




Further, compositions of the present invention are less sensitive in some instances to environmental conditions such as relative humidity at the time of application to the plant. Also, the present invention allows the use of smaller amounts of herbicides or other pesticides, while still obtaining the required degree of control of weeds or other undesired organisms.




DESCRIPTION OF SPECIFIC EMBODIMENTS




When the phrase “anisotropic aggregates in or on a wax layer” is used herein, it relates to determinations made by the following test procedure. We have found this test to predict with a high degree of reliability whether a composition comprising water and an exogenous chemical, or a composition comprising water which is to be used in conjunction with an exogenous chemical, will show enhanced biological effectiveness when applied to foliage of plants. Modifications can be made to the test; however a procedure modified in some major respect will not necessarily give the same results and will not necessarily predict enhanced effectiveness as reliably as the procedure described here.




The first stage in the procedure is to prepare a wax-coated slide. We have found a preferred wax for the purpose to be a blend of carnauba wax and beeswax in a weight/weight ratio of approximately 10:1. A clear wax mixture is prepared consisting of 5% carnauba wax and 0.5% beeswax in isopropanol, and is maintained at a temperature of approximately 82° C. The end of a glass 2.4 cm×7.2 cm microscope slide is immersed perpendicularly in the wax mixture to a depth of approximately one-third of the length of the slide. After 10 to 15 seconds, the slide is very slowly and steadily withdrawn from the wax mixture and allowed to cool. leaving a wax layer deposited on both faces of the slide.




Visual examination of the slide can give a preliminary indication of the thickness and uniformity of the wax coating. If imperfections are evident the slide is rejected. If the slide shows no obvious imperfections, the wax coating is carefully removed from one face of the slide by wiping with acetone. Further evaluation of the acceptability of the wax-coated slide for the test is done by examining the slide under a microscope. The slide is selected for use in the test if, on microscopic examination using a 4.9× objective, the wax coating is uniformly thick and there is uniform density of wax particles across the slide. Preference is for a coating that has few observable wax particles and exhibits a very dark field when examined under polarized light.




The next stage in the procedure is to conduct the test. For this purpose, samples of an exogenous chemical composition to be tested are diluted, if necessary, to 15% to 20% by weight of the exogenous chemical. In the case of glyphosate, the desired concentration in a composition sample is 15% to 20% acid equivalent (a.e.). Samples of reference compositions are also prepared; in the case of glyphosate, Formulations B and J as defined in the Examples herein are appropriate.




For a composition of a first excipient substance not containing an exogenous chemical but to be applied in conjunction with an exogenous chemical, the desired concentration is approximately 5% to 7% by weight of the first excipient substance.




The following instrumentation, or equivalent, items are required or useful:




Nikon SMZ-10A stereoscopic microscope equipped for polarized light observation, photomicrography, and video observation and recording.




3CCD MTI camera.




Diagnostic Instruments 150 IL-PS power supply.




Sony Trinitron color video monitor, model PVM-1353MD.




Mitsubishi time-lapse video cassette recorder, model HS-S5600.




Hewlett Packard Pavillion 7270 computer, with Windows 95 and Image-Pro Plus version 2.0 electronic imaging program installed.




Hewlett Packard Deskjet 870Cse printer.




A wax-coated slide, prepared and selected as described above, is positioned on the microscope stage, with the system set-to provide transmitted light, both straight and polarized. A 1 μl drop of the sample to be tested is applied to the wax surface using a thoroughly cleaned 1 μl Hamilton syringe. This and subsequent operations are followed through the microscope at 4.9× objective. Duplicate or triplicate tests are done for each composition. Numerous tests can be conducted simultaneously on a single slide. Progression of change in the microscopic appearance of the sample is observed through the microscope and recorded at designated time intervals. We have found useful intervals to be 1 minute, 10 minutes, 2 hours and >24 hours after application of the drop to the wax surface. Observations can also be made at intermediate times to capture possible significant transitions occurring at such times.




The temperature of the wax layer tends to increase with prolonged exposure to the microscope light. In many cases we have found this does not significantly interfere with the results obtained. However, in some cases temperature does affect the outcome of the test and in such cases it is preferred to illuminate the sample only for the short periods necessary to make observations, so that the temperature of the wax layer remains close to ambient temperature. An example of a composition of the invention where it is believed to be important to keep temperature close to ambient is one containing a fatty acid ester such as butyl stearate.




At dark field (polarized light) the wax layer is observed for birefringence, and at light field the character of the drop surface is observed, at each time interval. The following records are made:




birefringence (yes/no);




time of initial appearance of birefringence;




character of the birefringence,




appearance of drop surface as composition “dries”;




degree of spread of the drop;




effects of temperature (warming of the slide) if any;




other noticeable changes.




Optionally, images are recorded at significant times using the 3CCD MTI camera and the Image-Pro Plus program as documentation of observed changes. Tests may if desired also be recorded on video, especially during the first 15 minutes. In addition to images captured using 4.9× objective, overall-field views using 0.75× objective can be recorded to provide clear comparisons of different samples tested on the same slide.




A particularly useful parameter for predicting enhanced effectiveness is the observation of birefringence (yes/no) 5-20 minutes after deposition of the test drop on the wax-coated slide. We have found 10-15 minutes after deposition to be an especially suitable time for observation of this parameter. The following results for oil-in-water emulsion compositions comprising glyphosate IPA salt, butyl stearate and alkylether surfactants are typical of those obtained. Each of compositions WCS-1 to WCS-5 contained 15% w/w glyphosate a.e., 0.5% w/w butyl stearate and 5% w/w alkylether surfactant. Formulations B and J are commercial standard compositions of glyphosate defined in the Examples section later herein, and were diluted to 15% glyphosate a.e. for the test.



















Birefringence at






Composition




Alkylether




10 min.











WCS-1




Brij 78 (steareth-20)




yes






WCS-2




Plurafac A-38 (ceteareth-27)




yes






WCS-3




Brij 98 (oleth-20)




yes






WCS-4




Brij 35 (laureth-23)




no






WCS-5




Neodol 1-9 (C


11


linear alcohol 9EO)




no






Formulation B





no






Formulation J





no














It will be noted that where the hydrophobic moiety of the alkylether was a C


11


(WCS-5) or C


12


(WCS-4) hydrocarbyl group, the composition did not show anisotropic properties in the form of birefringence 10 minutes after application to the wax-coated slide. However, where the hydrophobic moiety had a carbon chain length of 16 to 18 (WCS-1 to WCS-3), birefringence was evident, indicating the presence of anisotropic aggregates in or on the wax layer. The intensity of birefringence was greatest with WCS-1 (containing steareth-20), followed by WCS-2 (containing ceteareth-27) and then WCS-3 (oleth-20).




Tests of alkylether compositions, as evidenced in Examples herein, have shown that in general those containing alkylethers of hydrophobe carbon chain length 16 or greater show greater biological effectiveness than those having a shorter hydrophobe. In general greater biological effectiveness has been obtained where the hydrophobe is saturated (as, for example, in steareth-20 and ceteareth-27) than where it is unsaturated 8 (as, for example, in oleth-20).




The following compositions were made containing 15% glyphosate a.e. and 5% alkylether surfactant, but no butyl stearate. In WCS-10 the surfactant was steareth-10, in 11 WCS-1 1 oleth-10 and in WCS-12 steareth-8 (laboratory sample from Sigma).




















Composition




Alkylether




Birefringence at 15 min.













WCS-10




Brij 76 (steareth-10)




yes







WCS-11




Brij 97 (oleth-10)




no







WCS-12




steareth-8




yes















The property of forming anisotropic aggregates as determined by this test appears to require, on a C


16-18


straight-chain alcohol, a minimum of about 10 moles of ethylene oxide (EO). Where the alcohol is oleyl, an EO chain of 10 units is already too short, but where the alcohol is stearyl, even as short an EO chain as 8 units appears to suffice. It should be noted, however, that the steareth-8 used in composition WCS-12 was obtained as a laboratory sample and is likely chemically purer than the commercial surfactants used in other compositions. Commercial grade steareth-8 will not necessarily give the same result.




As further evidence of the usefulness of the present anisotropy test in predicting biological effectiveness of exogenous chemical compositions, compositions WCS-6, WCS-7 and WCS-8 were prepared, each containing 30% glyphosate a.e. by weight, and were then diluted to 15% glyphosate a.e. for the test. All contained soybean lecithin (45% phospholipid, Avanti) and were prepared by process (v) as detailed in the Examples herein. Composition WCS-6, before dilution, contained 5% lecithin, 5% Fluorad FC-754 and 0.75% Ethomeen T/25. Composition WCS-7, before dilution, contained 2% lecithin and 2% Fluorad FC-754. Composition WCS-8, before dilution, contained 2% lecithin and 0.75% Ethomeen T/25. In addition. Composition WCS-9 was prepared containing 15% glyphosate a.e. and 5% soybean lecithin (45% phospholipid, Avanti). The following results were obtained.



















Birefringence at






Composition




Excipient ingredients




10 min.











WCS-6




lecithin + FC-754 + Ethomeen T/25




yes






WCS-7




lecithin + FC-754




yes






WCS-8




lecithin + Ethomeen T/25




no






WCS-9




lecithin




no














As evidenced in the Examples herein, enhanced biological effectiveness is a feature of compositions containing lecithin as the first excipient substance and Fluorad FC-754 as the second excipient substance. In the absence of Fluorad FC-754 or like material, lecithin, either alone or together with a tertiary alkylamine surfactant such as Ethomeen T/25 or MON 0818, does not consistently generate the desired enhancement.




In a further demonstration of the usefulness of the present anisotropy test, compositions WCS-13 and WCS-14 were prepared, each containing 20% glyphosate a.e. by weight, and were then diluted to 15% glyphosate a.e. for the test. Both contained soybean lecithin (45% phospholipid, Avanti). Composition WCS-13 was made by process (x) as described in the Examples herein and, before dilution, contained 6% lecithin, 6% Ethomeen T/25 and 1.5% butyl stearate. Composition WCS-14 was identical except that it contained no butyl stearate. Particular care was taken in this study to avoid excessive warming of the wax-coated slide by prolonged illumination. The following results were obtained.



















Birefringence








at






Composition




Excipient ingredients




15 min.











WCS-13




lecithin + Ethomeen T/25 + butyl stearate




yes






WCS-14




lecithin + Ethomeen T/25




no














The addition of a small quantity of butyl stearate was thus sufficient to confer, on a glyphosate+lecithin+Ethomeen T/25 composition, the property of forming anisotropic aggregates in or on a wax layer. The Examples herein illustrate the unexpected enhancement of biological effectiveness observed when an exogenous chemical is formulated with lecithin and a fatty acid ester such as butyl stearate.




Thus where, for reasons of economy, compatibility with the exogenous chemical, or other. considerations it is desired to provide an exogenous chemical composition having a relatively low content of excipient substances (for example a weight ratio of each excipient substance to exogenous chemical of about 1:3 or less), the anisotropy test provided here is an in vitro assay method which can be used to identify biologically effective compositions in advance of extensive testing in vivo.




The in vitro assay method just described, together with modifications thereof that will be readily apparent to those of skill in the art, is a further embodiment of the present invention.




Examples of exogenous chemical substances that can be included in compositions of the present invention include, but are not limited to, chemical pesticides (such as herbicides, algicides, fungicides, bactericides, viricides, insecticides, aphicides, miticides, nematicides, molluscicides and the like), plant growth regulators, fertilizers and nutrients, gametocides, defoliants, desiccants, mixtures thereof and the like. In one embodiment of the invention, the exogenous chemical is polar.




A preferred group of exogenous chemicals are those that are normally applied post-emergence to the foliage of plants, i.e. foliar-applied exogenous chemicals.




Some exogenous chemicals useful in the present invention are water-soluble, for example salts that comprise biologically active ions, and also comprise counterions, which may be biologically inert or relatively inactive. A particularly preferred group of these water-soluble exogenous chemicals or their biologically active ions or moieties are systemic in plants, that is, they are to some extent translocated from the point of entry in the foliage to other parts of the plant where they can exert their desired biological effect. Especially preferred among these are herbicides, plant growth regulators and nematicides, particularly those that have a molecular weight, excluding counterions, of less than about 300. More especially preferred among these are exogenous chemical compounds having one or more functional groups selected from amine, carboxylate, phosphonate and phosphinate groups.




Among such compounds, an even more preferred group are herbicidal or plant growth regulating exogenous chemical compounds having at least one of each of amine, carboxylate, and either phosphonate or phosphinate functional groups. Salts of N-phosphonomethylglycine are examples of this group of exogenous chemicals. Further examples include salts of glufosinate. for instance the ammonium salt (ammonium DL-homoalanin-4-yl (methyl) phosphinate).




Another preferred group of exogenous chemicals which can be applied by the method of the invention are nematicides such as those disclosed in U.S. Pat. No. 5,389,680, the disclosure of which is incorporated herein by reference. Preferred nematicides of this group are salts of 3,4,4-trifluoro-3-butenoic acid or of N-(3,4,4-trifluoro-1-oxo-3-butenyl) glycine.




Exogenous chemicals which can usefully be applied by the method of the present invention are normally, but not exclusively, those which are expected to have a beneficial effect on the overall growth or yield of desired plants such as crops, or a deleterious or lethal effect on the growth of undesirable plants such as weeds. The method of the present invention is particularly useful for herbicides, especially those that are normally applied post-emergence to the foliage of unwanted vegetation.




Herbicides which can be applied by the method of the present invention include but are not limited to any listed in standard reference works such as the “Herbicide Handbook,”


Weed Science Society of America,


1994, 7th Edition, or the “Farm Chemicals Handbook,” Meister Publishing Company, 1997 Edition. Illustratively these herbicides include acetanilides such as acetochlor, alachlor and metolachlor, aminotriazole, asulam, bentazon, bialaphos, bipyridyls such as paraquat, bromacil, cyclohexenones such as clethodim and sethoxydim, dicamba, diflufenican, dinitroanilines such as pendimethalin, diphenylethers such as acifluorfen, fomesafen and oxyfluorfen, fatty acids such as C


9-10


fatty acids, fosamine, flupoxam, glufosinate, glyphosate, hydroxybenzonitriles such as bromoxynil, imidazolinones such as imazaquin and imazethapyr, isoxaben, norflurazon, phenoxies such as 2,4-D, phenoxypropionates such as diclofop, fluazifop and quizalofop, picloram, propanil, substituted ureas such as fluometuron and isoproturon, sulfonylureas such as chlorimuron, chlorsulfuron, halosulfuron, metsulfuron, primisulfuron, sulfometuron and sulfosulfuron, thiocarbamates such as triallate. triazines such as atrazine and metribuzin, and triclopyr. Herbicidally active derivatives of any known herbicide are also within the scope of the present invention. A herbicidally active derivative is any compound which is a minor structural modification, most commonly but not restrictively a salt or ester, of a known herbicide. These compounds retain the essential activity of the parent herbicide, but may not necessarily have a potency equal to that of the parent herbicide. These compounds may convert to the parent herbicide before or after they enter the treated plant. Mixtures or coformulations of a herbicide with other ingredients. or of more than one herbicide, may likewise be employed.




An especially preferred herbicide is N-phosphonomethylglycine (glyphosate), a salt, adduct or ester thereof, or a compound which is converted to glyphosate in plant tissues or which otherwise provides glyphosate ion. Glyphosate salts that can be used according to this invention include but are not restricted to alkali metal, for example sodium and potassium, salts; ammonium salt; alkylamine, for example dimethylamine and isopropylamine, salts; alkanolamine, for example ethanolamine, salts; alkylsulfonium, for example trimethylsulfonium, salts; sulfoxonium salts; and mixtures thereof. The herbicidal compositions sold by Monsanto Company as ROUNDUP® and ACCORD® contain the monoisopropylamine (IPA) salt of N-phosphonomethylglycine. The herbicidal compositions sold by Monsanto Company as ROUNDUP® Dry and RIVAL® (contain the monoammonium salt of N-phosphonomethylglycine. The herbicidal composition sold by Monsanto Company as ROUNDUP® Geoforce contains the monosodium salt of N-phosphonomethylglycine. The herbicidal composition sold by Zeneca as TOUCHDOWN® contains the trimethylsulfonium salt of N-phosphonomethylglycine. The herbicidal properties of N-phosphonomethylglycine and its derivatives were first discovered by Franz, then disclosed and patented in U.S. Pat. No. 3,799,758, issued Mar. 26, 1974. A number of herbicidal salts of N-phosphonomethylglycine were patented by Franz in U.S. Pat. No. 4,405,531, issued Sep. 20, 1983. The disclosures of both of these patents are hereby incorporated by reference.




Because the commercially most important herbicidal derivatives of N-phosphonomethylglycine are certain salts thereof, the glyphosate compositions useful in the present invention will be described in more detail with respect to such salts. These salts are. well known and include ammonium, IPA, alkali metal (such as the mono-, di-, and trisodium salts, and the mono-, di-, and tripotassium salts), and trimethylsulfonium salts. Salts of N-phosphonomethylglycine are commercially significant in part because they are water soluble. The salts listed immediately above are highly water soluble, thereby allowing for highly concentrated solutions that can be diluted at the site of use. In accordance with the method of this invention as it pertains to glyphosate herbicide, an aqueous solution containing a herbicidally effective amount of glyphosate and other components in accordance with the invention is applied to foliage of plants. Such an aqueous solution can be obtained by dilution of a concentrated glyphosate salt solution with water, or dissolution or dispersion in water of a dry (e.g. granular, powder, tablet or briquette) glyphosate formulation.




Exogenous chemicals should be applied to plants at a rate sufficient to give the desired biological effect. These application rates are usually expressed as amount of exogenous chemical per unit area treated, e.g. grams per hectare (g/ha). What constitutes a “desired effect” varies according to the standards and practice of those who investigate, develop, market and use a specific class of exogenous chemicals. For example, in the case of a herbicide, the amount applied per unit area to give 85% control of a plant species as measured by growth reduction or mortality is often used to define a commercially effective rate.




Herbicidal effectiveness is one of the biological effects that can be enhanced through this invention. “Herbicidal effectiveness,” as used herein, refers to any observable measure of control of plant growth, which can include one or more of the actions of (1) killing, (2) inhibiting growth, reproduction or proliferation, and (3) removing, destroying, or otherwise diminishing the occurrence and activity of plants.




The herbicidal effectiveness data set forth herein report “inhibition” as a percentage following a standard procedure in the art which reflects a visual assessment of plant mortality and growth reduction by comparison with untreated plants, made by technicians specially trained to make and record such observations. In all cases. a single technician makes all assessments of percent inhibition within any one experiment or trial. Such measurements are relied upon and regularly reported by Monsanto Company in the course of its herbicide business.




The selection of application rates that are biologically effective for a specific exogenous chemical is within the skill of the ordinary agricultural scientist. Those of skill in the art will likewise recognize that individual plant conditions, weather and growing conditions, as well as the specific exogenous chemical and formulation thereof selected, will affect the efficacy achieved in practicing this invention. Useful application rates for exogenous chemicals employed can depend upon all of the above conditions. With respect to the use of the method of this invention for glyphosate herbicide, much information is known about appropriate application rates. Over two decades of glyphosate use and published studies relating to such use have provided abundant information from which a weed control practitioner can select glyphosate application rates that are herbicidally effective on particular species at particular growth stages in particular environmental conditions.




Herbicidal compositions of glyphosate or derivatives thereof are used to control a very wide variety of plants worldwide. Such compositions can be applied to a plant in a herbicidally effective amount, and can effectively control one or more plant species of one or more of the following genera without restriction: Abutilon, Amaranthus, Artemisia, Asclepias, Avena, Axonopus, Borreria, Brachiaria, Brassica, Bromus, Chenopodium, Cirsium, Conmmelina, Convolvulus, Cynodon, Cyperus, Digitaria, Echinochloa, Eleusine, Elymus, Equisetum, Erodium, Helianthus, Imperata, Ipomoea, Kochia, Lolium, Malva, Oryza, Ottochloa, Panicum, Paspalum, Phalaris, Phragmites, Polygonum, Portulaca, Pteridium, Pueraria, Rubus, Salsola, Setaria, Sida, Sinapis, Sorghum, Triticum, Typha, Ulex, Xanthium, and Zea.




Particularly important species for which glyphosate compositions are used are exemplified without limitation by the following:




Annual broadleaves:




velvetleaf (


Abutilon theophrasti


)




pigweed (Amaranthus spp.)




buttonweed (Borreria spp.)




oilseed rape, canola, indian mustard, etc. (Brassica spp.)




comrelina (Commelina spp.)




filaree (Erodium spp.)




sunflower (Helianthus spp.)




momingglory (Ipomoea spp.)




kochia (


Kochia scoparia


)




mallow (Malva spp.)




wild buckwheat, smartweed, etc. (Polygonum spp.)




purslane (Portulaca spp.)




russian thistle (Salsola spp.)




sida (Sida spp.)




wild mustard (


Sinapis arvensis


)




cocklebur (Xanthium spp.)




Annual narrowleaves:




wild oat (


Avena fatua


)




carpetgrass (Axonopus spp.)




downy brome (


Bromus tectorurn


)




crabgrass (Digitaria spp.)




barnyardgrass (


Echinochloa crus


-


galli


)




goosegrass (


Eleusine indica


)




annual ryegrass (


Lolium multiflorum


)




rice (


Oryza sativa


)




ottochloa (


Ottochloa nodosa


)




bahiagrass (


Paspalum notatum


)




canarygrass (Phalaris spp.)




foxtail (Setaria spp.)




wheat (


Triticurn aestivum


)




corn (


Zea mays


)




Perennial broadleaves:




mugwort (Artemisia spp.)




milkweed (Asclepias spp.)




canada thistle (


Cirsium arvense


)




field bindweed (


Convolvulus arvensis


)




kudzu (Pueraria spp.)




Perennial narrowleaves:




brachiaria (Brachiaria spp.)




bermudagrass (


Cynodon dactylon


)




yellow nutsedge (


Cyperus esculentus


)




purple nutsedge (


C. rotundus


)




quackgrass (


Elymus repens


)




lalang (


Imperata cylindrica


)




perennial ryegrass (


Lolium perenne


)




guineagrass (


Panicum maximum


)




dallisgrass (


Paspalum dilatatum


)




reed (Phragmites spp.)




johnsongrass (


Sorghum halepense


)




cattail (Typha spp.)




Other perennials:




horsetail (


Equisetum spp.


)




bracken (


Pteridium aquilinum


)




blackberry (Rubus spp.)




gorse (


Ulex europaeus


)




Thus, the method of the present invention, as it pertains to glyphosate herbicide, can be useful on any of the above species.




Effectiveness in greenhouse tests, usually at exogenous chemical rates lower than those normally effective in the field, is a proven indicator of consistency of field performance at normal use rates. However, even the most promising composition sometimes fails to exhibit enhanced performance in individual greenhouse tests. As illustrated in the Examples herein, a pattern of enhancement emerges over a series of greenhouse tests; when such a pattern is identified this is strong evidence of biological enhancement that will be useful in the field.




Aggregate-forming substances useful as the first excipient substance in compositions of the present invention include a wide variety of amphiphilic materials, of which three classes are preferred.




The first preferred class of aggregate-forming substances can be defined as amphiphilic liposome-forming substances. These include various lipids of synthetic, animal, or plant origin, including phospholipids, ceramides, sphingolipids, dialkyl surfactants, and polymeric surfactants. A variety of these materials are known to those skilled in the art, and are commercially available. Lecithins are particularly rich in phospholipids and can be derived from a number of plant and animal sources. Soybean lecithin is one particular example of a relatively inexpensive commercially available material that includes such substances.




Many other substances have been described which can be used to form liposomes; the present invention includes compositions comprising any such liposome-forming substances, so long as other requirements set out above are met, and use of such compositions for enhancing biological effectiveness of exogenous chemicals applied to foliage of plants. For example, U.S. Pat. No. 5,580,859, incorporated here by reference, discloses liposome-forming substances having a cationic group, including N-(2,3-di-(9-(Z)-octadecenyloxy))-prop-1-yl-N,N,N-trimethylammonium chloride (DOTMA) and 1,2-bis(oleoyloxy)-3-(trimethylammonio)propane (DOTAP). Liposome-forming substances which are not themselves cationic, but do contain a cationic group as part of the hydrophilic moiety, include for example dioleoylphosphatidylcholine (DOPC) and dioleoylphosphatidylethanolamine (DOPE). Liposome-forming substances that do not contain a cationic group include dioleoylphosphatidylglycerol (DOPG). Any of these liposome-forming substances can be used with or without the addition of cholesterol.




These substances contain portions that are hydrophilic and hydrophobic within the same molecule. They have the ability to self-assemble in aqueous solution or dispersion into structures that are more complex than simple micelles. The nature of the aggregate that will be formed can be related to the critical packing parameter P by the following equation:








P=V/lA








where V is the volume of the hydrophobic tail of the molecule, l is the effective length of the hydrophobic tail, and A is the area occupied by the hydrophilic headgroup in the surface of the aggregate. The most probable self-assembled structures are spherical micelles when P is less than ⅓, rodlike micelles when P is between ⅓ and ½, lamellar when P is between 1 and ½, and inverse structures when P is greater than 1. The preferred materials in the present invention have P greater than ⅓.




Cationic liposome-forming substances having a hydrophobic moiety comprising two hydrocarbyl chains are accompanied by a counterion (anion), identified as Z in formulas I, II and III above. Any suitable anion can be used, including agriculturally acceptable anions such as hydroxide. chloride, bromide, iodide, sulfate, phosphate and acetate. In a specific embodiment where the exogenous chemical has a biologically active anion, that anion can serve as the counterion for the liposome-forming substance. For example, glyphosate can be used in its acid form together with the hydroxide of a cationic liposome-forming substance such as a compound of formula I.




Compounds of formula I known in the art to be liposome-forming include distearyldimethylammonium chloride and bromide (also known in the art as DODAC and DODAB respectively). Compounds of formula II known in the art to be liposome-forming include DOTMA referenced above and dimyristooxypropyldimethylhydroxyethylammonium bromide (DMRIE). Compounds of formula III known in the art to be liposome-forming include dioleoyloxy-3-(dimethylammonio)propane (DODAP) and DOTAP referenced above. Compounds of formula IV known in the art to be liposome-forming include DOPC and DOPE, both referenced above.




In many liposome-forming substances known in the art, the hydrophobic hydrocarbyl chains are unsaturated, having one or more double bonds. Particularly commonly used in the pharmaceutical art are dioleyl or dioleoyl compounds. A potential problem with these is that in an oxidizing environment they become oxidized at the site of the double bond. This can be inhibited by including in the formulation an antioxidant such as ascorbic acid. Alternatively the problem can be avoided by use of liposome-forming substances wherein a high proportion of the hydrophobic hydrocarbyl chains are fully saturated. Thus in a preferred embodiment of the invention, R


1


and R


2


in formulas I-IV are independently saturated straight-chain alkyl groups. Particularly preferred compositions use liposome-forming substances in which R


1


and R


2


are both palmityl (cetyl) or palmitoyl or, alternatively, are both stearyl or stearoyl groups.




Phospholipids, because of their low cost and favorable environmental properties, are particularly favored among liposome-forming substances in the method and compositions of the invention. Vegetable lecithins, such as soybean lecithin, have successfully been used in accordance with the invention. The phospholipid content of the lecithin product can range from about 10% to close to 100%. While acceptable results have been obtained with crude lecithin (10-20% phospholipid), it is generally preferred to use lecithin that is at least partially de-oiled, so that the phospholipid content is in the region of about 45% or more. Higher grades. such as 95%, provide excellent results but the much higher cost is unlikely to be justified for most applications.




The phospholipid component of lecithin, or any phospholipid composition used in the present invention, may comprise one or more phosphatides of natural or synthetic origin. Each of these phosphatides is generally a phosphoric ester that on hydrolysis yields phosphoric acid, fatty acid(s), polyhydric alcohol and, typically, a nitrogenous base. A phosphatide component may be present in a partially hydrolyzed form, e.g. as phosphatidic acid. Suitable phosphatides include, without limitation, phosphatidylcholine, hydrogenated phosphatidylcholine, phosphatidylinositol, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylethanolamine, N-acyl phosphatidylethanolamine, and mixtures of any of these.




In vegetable lecithins a high proportion of the hydrophobic hydrocarbyl chains of the phospholipid compounds are typically unsaturated. One preferred embodiment of compositions in accordance with the present invention comprises both saturated phospholipid and unsaturated phospholipid, with the weight ratio of saturated phospholipid to unsaturated phospholipid being greater than about 1:2. In various particularly preferred embodiments, (1) at least 50% by weight of the phospholipids are di-C


12-22


-saturated alkanoyl phospholipid, (2) at least 50% by weight of the phospholipids are di-C


16-18


-saturated alkanoyl phospholipid, (3) at least 50% by weight of the phospholipids are distearoyl phospholipid, (4) at least 50% by weight of the phospholipids are dipalmitoyl phospholipid, or (5) at least 50% by weight of the phospholipids are distearoyl phosphatidylcholine. dipalmitoyl phosphatidylcholine, or a mixture thereof. Higher proportions of saturated alkanoyl phospholipids are generally found in lecithins of animal origin, such as for example egg yolk lecithin, than in vegetable lecithins.




Phospholipids are known to be chemically unstable, at least in acid media, where they tend to degrade to their lyso-counterparts. Thus where phospholipids rather than more stable liposome-forming substances are used, it is usually preferable to adjust the pH of the composition upward. In the case of glyphosate compositions, the pH of a composition based on a mono-salt such as the monoisopropylammonium (IPA) salt is typically around 5 or lower. When phospholipids are used as the first excipient substance in a glyphosate composition of the invention, it will therefore be preferable to raise the pH of the composition, for example to around 7. Any convenient base can be used for this purpose; it will often be most convenient to use the same base as used in the glyphosate salt, for example isopropylamine in the case of glyphosate IPA salt.




Amphiphilic compounds useful as the first excipient substance herein are not limited to those having two hydrophobic hydrocarbyl groups such as the compounds of formulas I to IV. The second preferred class of aggregate-forming substances useful in the invention are cationic surfactant compounds having formula V above. In compounds of formula V, R


8


unless perfluorinated preferably has from about 12 to about 18 carbon atoms. R


8


is preferably perfluorinated, in which case it preferably has from about 6 to about 12 carbon atoms. Preferably n is 3. R


9


groups are preferably methyl.




Sulfonylamino compounds of formula V are especially preferred. Suitable examples include 3-(((heptadecafluorooctyl)sulfonyl)amino)-N,N,N-trimethyl-1-propaminium iodide, available for example as Fluorad FC-135 from 3M Company, and the corresponding chloride. It is believed that Fluorad FC-754 of 3M Company is the corresponding chloride.




Fluoro-organic surfactants such as the cationic types falling within formula V belong to a functional category of surfactants known in the art as “superspreaders” or “superwetters”. As a class “superspreaders” or “superwetters” are very effective in reducing surface tension of aqueous compositions containing relatively low concentrations of these surfactants. In many applications fluoro-organic surfactants can substitute for organosilicone surfactants which are likewise “superspreaders” or “superwetters”. An example is found in European patent application 0 394 211 which discloses that either organosilicone or fluoro-organic surfactants can be used interchangeably in solid granular formulations of pesticides to improve dissolution rate.




Two major problems have limited interest in “superspreaders” and “superwetters” by formulators of exogenous chemicals such as pesticides. The first is high unit cost. The second is that although surfactants of this functional category can enhance performance of an exogenous chemical on some species, for example by assisting penetration of the exogenous chemical into the interior of leaves via stomata, they can be antagonistic, sometimes severely so, to performance of the same exogenous chemical on other species.




Surprisingly, a subclass of fluoro-organic surfactants has now been found to be essentially non-antagonistic at concentrations which nevertheless provide useful adjuvant effects. This subclass comprises cationic fluoro-organic surfactants of formula V and others having a property profile in common with those of formula V. The lack of antagonism makes this subclass very different from other fluoro-organic “superspreaders” or “superwetters”. Further, it has been found that these non-antagonistic fluoro-organic surfactants can be useful at concentrations low enough to be cost-effective. Data in the Examples herein for compositions comprising Fluorad FC-135 or Fluorad FC-754 illustrate the unexpected properties of this subclass.




Derivatives of Fluorad FC-754, herein described as “FC-acetate” and “FC-salicylate,” have been prepared by the following procedure. (1) The solvent in a sample of Fluorad FC-754 is gently evaporated off by heating in a glass beaker at 70-80° C., to leave a solid residue. (2) The solid residue is allowed to cool to room temperature. (3) A 1 g aliquot of the residue is placed in a centrifuge tube and dissolved in 5 ml isopropanol. (4) A saturated solution of potassium hydroxide (KOH) is prepared in isopropanol. (5) This solution is added drop by drop to the solution of FC-754 residue; this results in formation of a precipitate and addition of KOH solution continues until no further precipitate forms. (6) The tube is centrifuged at 4000 rpm for 5 minutes. (7) More KOH solution is added to check if precipitation is complete; if not, the tube is centrifuged again. (8) The supernatant is decanted into another glass tube. (9) A saturated solution of acetic acid (or salicylic acid) is prepared in isopropanol. (10) This solution is added to the supernatant in an amount sufficient to lower pH to 7. (11) Isopropanol is evaporated from this neutralized solution by heating at 60° C. until completely dry. (12) The residue (either the acetate or salicylate salt) is dissolved in a suitable amount of water and is then ready for use.




The third preferred class of aggregate-forming substance useful as the first excipient substance according to the present invention is a long-chain alkylether surfactant having the formula VI above. R


12


can be branched or unbranched, saturated or unsaturated. R


12


is preferably straight chain saturated C


16


alkyl (cetyl) or straight chain saturated C


18


alkyl (stearyl). In preferred alkylethers m is 0, n is an average number from about 20 to about 40 and R


13


is preferably hydrogen. Among especially preferred alkylether surfactants are those identified in the International Cosmetic Ingredient Directory as ceteth-20, ceteareth-20, ceteareth-27, steareth-20 and steareth-30.




Of the classes of aggregate-forming substance useful as the first excipient substance, not all give rise to anisotropic aggregates in or on a wax layer, as required by the present invention, when used as the sole excipient substance in the composition at a weight ratio of 1:3 to 1:100 with the exogenous chemical. Many compounds of formulas V and VI are sufficient in the absence of a second excipient substance, but in general the liposome-forming substances of formulas I to IV require the presence of a second excipient substance to exhibit the required anisotropic behavior. However, even in the presence of a first excipient substance of formulas V or VI, there may be advantages in also including a second excipient substance as herein defined.




The second excipient substance has one or more hydrophobic moieties. If there is only one hydrophobic moiety, it is a hydrocarbyl or haloalkyl group having about 6 to about 22 carbon atoms. If there is more than one hydrophobic moiety, each such moiety is a hydrocarbyl or haloalkyl group having more than 2 carbon atoms, and the total number of carbon atoms in the hydrophobic moieties is about 12 to about 40.




One class of second excipient substance useful in the present invention is quaternary ammonium compounds. Among quaternary ammonium compounds that may be used are compounds of formula






N


+


(R


16


)(R


17


)(R


18


)(R


19


) Q





  VIII






where R


16


, R


17


, R


18


and R


19


are independently C


3-6


alkyl groups and Q is a suitable anion, such as for example hydroxide, chloride, bromide, iodide, sulfate, phosphate or acetate. In preferred compounds of formula VIII all R groups are the same. Particularly preferred compounds of formula VIII are tetrabutylammonium salts. Where the exogenous chemical comprises a biologically active anion, a salt of formula VIII where Q is that anion is an option providing both the exogenous chemical and second excipient substance. An example is the tetrabutylammonium salt of glyphosate.




Other quaternary ammonium compounds that may be useful include compounds having a single C


12-22


hydrocarbyl group and three C


1-4


alkyl groups attached to the quaternary nitrogen atom. One or more of the C


1-4


alkyl groups in such compounds can be replaced by a benzyl group. Specific examples include cetyltrimethylammonium bromide and benzalkonium chloride. Yet other quaternary ammonium compounds useful as the second excipient substance include compounds of formula I, where the first excipient substance is not of formula I.




Preferred quaternary ammonium compounds useful as the second excipient substance are compounds of formula V. where the first excipient substance is not of formula V. The same specific compounds of formula V are especially preferred whether a compound of formula V is the first or the second excipient substance. Particularly good results have been obtained where the first excipient substance is lecithin and the second excipient substance is Fluorad FC-135 or FC-754 or chemical equivalents thereof




Another class of compound useful as the second excipient substance is an amide or ester of formula VII above.




R


14


in formula VII is preferably aliphatic and has about 7 to about 21 carbon atoms, more preferably about 13 to about 21 carbon atoms. It is especially preferred that R


14


be a saturated straight-chain alkyl group. R


15


is preferably an aliphatic group having 1-6 carbon atoms, more preferably alkyl or alkenyl having 2-4 carbon atoms. An especially preferred compound of formula VII for use as the second excipient substance is butyl stearate.




As compounds of formula VII, including butyl stearate, are generally oily liquids, aqueous compositions containing them are typically emulsions having at least one aqueous phase and at least one oil phase. with the compound of formula VII being present predominantly in the oil phase. Such emulsions may be water-in-oil, oil-in-water or water-in-oil-in-water (W/O/W) multiple emulsions.




Aqueous concentrate compositions where the first excipient substance is an alkylether of formula VI and the second excipient substance, if present, is a fatty acid ester of formula VII are limited in the degree to which an exogenous chemical such as glyphosate can be loaded. At some point, as the loading of exogenous chemical is increased, the composition will not remain suitably stable. Addition of a small amount of colloidal particulate to such compositions has surprisingly been found to greatly increase loading ability while retaining desired stability. Oxides of silicon, aluminum and titanium are preferred colloidal particulate materials. Particle size is preferably such that specific surface area is in the range from about 50 to about 400 m


2


/g. Where the exogenous chemical is glyphosate, the use of colloidal particulate enables loadings of at least 30% by weight for compositions containing sufficient alkylether and fatty acid ester to show enhanced herbicidal effectiveness, or at least 40% for compositions containing alkylether but no fatty acid ester and showing herbicidal effectiveness at least equal to current commercial products loaded at about 30%. We have found especially useful improvement in storage stability can be obtained using colloidal particulates having specific surface area between about 180 and about 400 m


2


/g.




Other means of improving stability of highly loaded compositions comprising an alkylether of formula VI, with or without a fatty acid ester, may also be possible and are within the scope of the present invention.




Compositions in accordance with the present invention are typically prepared by combining water. the exogenous chemical (unless it is a formulation which will not contain an exogenous chemical) and the aggregate-forming substance. Where the aggregate-forming substance is one that disperses readily in water, as is the case for example with Fluorad FC-135 or Fluorad FC-754, simple mixing with mild agitation may be sufficient. However, where the aggregate-forming substance requires high shear to disperse in water, as is the case for example with most forms of lecithin, it is presently preferred to sonicate or microfluidize the aggregate-forming substance in water. This can be done before or after a surfactant and/or the exogenous chemical is added. The sonication or microfluidization will generally produce liposomes or other aggregate structures other than simple micelles. The precise nature, including average size, of liposomes or other aggregates depends among other things on the energy input during sonication or microfluidization. Higher energy input generally results in smaller liposomes. Although it is possible to entrap or otherwise bind loosely or tightly the exogenous chemical in or on liposomes or with other supramolecular aggregates, the exogenous chemical does not need to be so entrapped or bound, and in fact the present invention is effective when the exogenous chemical is not entrapped or bound in the aggregates at all.




In a particular embodiment of the invention, the liposomes or other aggregates have an average diameter of at least 20 nm, more preferably at least 30 nm. We have determined by light scattering that certain liposomal compositions of the invention have average liposome diameters ranging from 54 to 468 nm as calculated using linear fit and from 38 to 390 nm as calculated using quadratic fit.




The concentrations of the various components will vary, in part depending on whether a concentrate is being prepared that will be further diluted before spraying onto a plant, or whether a solution or dispersion is being prepared that can be sprayed without further dilution.




In an aqueous glyphosate formulation that includes a dialkyl surfactant, for example a cationic dialkyl surfactant of formula I, suitable concentration ranges are: glyphosate 0.1-400 grams acid equivalent (a.e.)/liter, and dialkyl surfactant 0.001-10% by weight. In an aqueous glyphosate formulation using a cationic fluoro-organic surfactant and lecithin, suitable concentrations can be: glyphosate 0.1-400 g a.e./l, fluoro-organic surfactant 0.001-10% by weight, and soybean lecithin 0.001-10% by weight.




In an aqueous glyphosate formulation that includes a C


16-18


alkylether surfactant and butyl stearate, suitable concentrations can be: glyphosate 0.1-400 g a.e./l, alkylether surfactant 0.001-10% by weight, and butyl stearate 0.001-10% by weight. To achieve the higher concentrations in these ranges, it is often beneficial to add other ingredients to provide acceptable storage stability, for example colloidal particulate silica or aluminum oxide at 0.5-2.5% by weight. In an aqueous glyphosate formulation that includes a C


16-18


alkylether surfactant but no butyl stearate, glyphosate concentration can suitably be increased to 500 g a.e./l or more, in the presence of a colloidal particulate at 0.5-2.5% by weight.




In solid glyphosate formulations, higher concentrations of ingredients are possible because of the elimination of most of the water.




Weight/weight ratios of ingredients may be more important than absolute concentrations. For example, in a glyphosate formulation containing lecithin and a cationic fluoro-organic surfactant, the ratio of lecithin to glyphosate a.e. is in the range from about 1:3 to about 1:100. It is generally preferred to use a ratio of lecithin to glyphosate a.e. close to as high as can be incorporated in the formulation while maintaining stability, in the presence of an amount of the fluoro-organic surfactant sufficient to give the desired enhancement of herbicidal effectiveness. For example, a lecithin/glyphosate a.e. ratio in the range from about 1:3 to about 1:10 will generally be found useful, although lower ratios, from about 1:10 to about 1:100 can have benefits on particular weed species in particular situations. The ratio of fluoro-organic surfactant, when present, to glyphosate a.e. is likewise preferably in the range from about 1:3 to about 1:100. Because fluoro-organic surfactants tend to have relatively high cost, it will generally be desirable to keep this ratio as low as possible consistent with achieving the desired herbicidal effectiveness.




The ratio of fluoro-organic surfactant, where present, to lecithin is preferably in the range from about 1:10 to about 10:1, more preferably in the range from about 1:3 to about 3:1 and most preferably around 1:1. The ranges disclosed herein can be used by one of skill in the art to prepare compositions of the invention having suitable concentrations and ratios of ingredients. Preferred or optimum concentrations and ratios of ingredients for any particular use or situation can be determined by routine experimentation.




Although the combination of the components might be done in a tank mix, it is preferred in the present invention that the combination be made further in advance of the application to the plant, in order to simplify the tasks required of the person who applies the material to plants. We have found, however, that in some cases the biological effectiveness of a liposome-containing composition prepared from scratch as a dilute spray composition is superior to that of a composition having the same ingredients at the same concentrations but diluted from a previously prepared concentrate formulation.




Although various compositions of the present invention are described herein as comprising certain listed materials, in some preferred embodiments of the invention the compositions consist essentially of the indicated materials.




Optionally, other agriculturally acceptable materials can be included in the compositions. For example, more than one exogenous chemical can be included. Also, various agriculturally acceptable adjuvants can be included, whether or not their purpose is to directly contribute to the effect of the exogenous chemical on a plant. For example, when the exogenous chemical is a herbicide, liquid nitrogen fertilizer or ammonium sulfate might be included in the composition. As another example, stabilizers can be added to the composition. In some instances it might be desirable to include microencapsulated acid in the composition, to lower the pH of a spray solution on contact with a leaf. One or more surfactants can also be included. Surfactants mentioned here by trade name, and other surfactants that can be useful in the method of the invention, are indexed in standard reference works such as McCutcheon's Emulsifiers and Detergents, 1997 edition, Handbook of Industrial Surfactants, 2nd Edition, 1997, published by Gower, and International Cosmetic Ingredient Dictionary, 6th Edition, 1995.




The compositions of the present invention can be applied to plants by spraying, using any conventional means for spraying liquids, such as spray nozzles, atomizers, or the like. Compositions of the present invention can be used in precision farming techniques, in which apparatus is employed to vary the amount of exogenous chemical applied to different parts of a field, depending on variables such as the particular plant species present, soil composition, and the like. In one embodiment of such techniques, a global positioning system operated with the spraying apparatus can be used to apply the desired amount of the composition to different parts of a field.




The composition at the time of application to plants is preferably dilute enough to be readily sprayed using standard agricultural spray equipment. Preferred application rates for the present invention vary depending upon a number of factors, including the type and concentration of active ingredient and the plant species involved. Useful rates for applying an aqueous composition to a field of foliage can range from about 25 to about 1,000 liters per hectare (l/ha) by spray application. The preferred application rates for aqueous solutions are in the range from about 50 to about 300 l/ha.




Many exogenous chemicals (including glyphosate herbicide) must be taken up by living tissues of the plant and translocated within the plant in order to produce the desired biological (e.g., herbicidal) effect. Thus, it is important that a herbicidal composition not be applied in such a manner as to excessively injure and interrupt the normal functioning of the local tissue of the plant so quickly that translocation is reduced. However, some limited degree of local injury can be insignificant, or even beneficial, in its impact on the biological effectiveness of certain exogenous chemicals.




A large number of compositions of the invention are illustrated in the Examples that follow. Many concentrate compositions of glyphosate have provided sufficient herbicidal effectiveness in greenhouse tests to warrant field testing on a wide variety of weed species under a variety of application conditions. Water-in-oil-in-water multiple emulsion compositions tested in the field have included:




















% w/w





Type of



















Field




Glyphosate




Fatty




Emulsifier




Emulsifier




% in inner aq. phase




Emulsifier




Emulsifier




fatty acid




















composition




g a.e./l




acid ester




#1




#2




Water




Glyphosate




#1




#2




ester























F-1




100




18.0




3.0




5.0




13.8




20




Span 80




Tween 20




Bu stearate






F-2




100




7.5




3.0




5.0




5.6




20




Span 80




Tween 20




Bu stearate






F-3




100




7.5




3.0




5.0




5.6




 0




Span 80




Tween 20




Bu stearate






F-4




160




7.5




3.0




5.0




5.6




 0




Span 80




Tween 20




Bu stearate














The above compositions were prepared by process (vi) as described in the Examples.




Aqueous compositions tested in the field having an alkylether surfactant as the first excipient substance and/or containing a fatty acid ester have included:



















% w/w

















Field




Glypho-




Fatty






Type of






compo-




sate




acid




Surfac-




Type of




fatty acid






sition




g a.e./l




ester




tant




surfactant




ester



















F-5




163




1.0




10.0




oleth-20




Bu stearate






F-6




163




1.0




10.0




Tween 80




Bu stearate






F-7




163




1.0




10.0




Neodol 25-20




Bu stearate






F-8




163




1.0




10.0




steareth-20




Bu stearate






F-9




163




1.0




10.0




Neodol 25-12




Bu stearate






F-10




163




7.5




10.0




Tween 80




Bu stearate






F-11




163




0.5




5.0




oleth-20




Bu stearate






F-12




163




0.3




5.0




oleth-20




Bu stearate






F-13




163




0.3




2.5




oleth-20




Bu stearate






F-14




163




1.0




10.0




Neodol 25-12




Bu stearate






F-15




163




0.3




5.0




Genapol UD-110




Bu stearate






F-16




163




0.5




5.0




steareth-20




Bu stearate






F-17




163




0.5




5.0




ceteth-20




Bu stearate






F-18




163




0.5




5.0




laureth-23




Bu stearate






F-19




163




0.5




5.0




ceteareth-27




Bu stearate






F-20




163




0.5




5.0




Neodol 25-12




Bu stearate






F-21




163




0.5




5.0




Neodol 25-20




Bu stearate






F-22




163





5.0




steareth-20






F-23




163





5.0




ceteth-20






F-24




163





5.0




laureth-23






F-25




163




0.3




5.0




ceteareth-27




Bu stearate






F-26




163




0.3




2.5




ceteareth-27




Bu stearate






F-27




163





5.0




ceteareth-27






F-28




163




0.5




5.0




ceteareth-27




Me stearate






F-29




163




0.5




5.0




steareth-20




Me stearate






F-30




163




0.5




5.0




oleth-20






F-31




163




0.5




5.0




Neodol 45-13




Bu stearate






F-32




163





5.0




Neodol 45-13






F-33




163




0.5




5.0




ceteareth-15




Bu stearate






F-34




163





5.0




ceteareth-15






F-35




163




0.5




5.0




steareth-30




Bu stearate














The above compositions were prepared by process (vii) if they contain fatty acid ester and by process (viii) if they do not. Both processes are described in the Examples.




Aqueous compositions tested in the field containing colloidal particulates have included:



















% w/w





















Field




Glyphosate




Fatty





Coll.






Type of colloidal




Type of fatty




Other






composition




g a.e./l




acid ester




Surfactant




partic.




Other




Type of surfactant




particulate




acid ester




ingredients























F-36




360




1.0




10.0




1.3





steareth-20




Aerosil 380




Bu stearate







F-37




360




1.0




10.0




1.3





oleth-20




Aerosil 380




Bu stearate






F-38




360




1.0




10.0




1.3





steareth-30




Aerosil 380




Bu stearate






F-39




360





10.0




1.3





steareth-30




Aerosil 380






F-40




360






0.8






Aerosil 90






F-41




350






0.8






Al oxide C






F-42




360





3.0




0.8





Ethomeen T/25




Al oxide C






F-43




360





3.0




0.1





Ethomeen T/25




Al oxide C






F-44




360






0.3






Al oxide C






F-45




360





3.0




0.3





Ethomeen T/25




Al oxide C






F-46




360





6.0




0.8





Agrimul PG-2069




Al oxide C






F-47




360





3.0




0.8





Tween 20




Al oxide C






F-48




480





1.0




0.4





Neodol 1-7




Aerosil 90






F-49




480





2.0




0.4





Agrimul PG-2069




Aerosil 90






F-50




360




1.0




10.0




1.3





ceteareth-15




Aerosil 380




Bu stearate






F-51




360




1.0




10.0




1.3





ceteth-20




Aerosil 380




Bu stearate






F-52




360




1.0




10.0




1.3





steareth-20




Aerosil 380




Bu stearate






F-53




360




1.0




10.0




1.3





oleth-20




Aerosil 380




Bu stearate






F-54




360




1.0




10.0




1.3





ceteareth-27




Aerosil 380




Bu stearate






F-55




360




1.0




10.0




1.3





steareth-30




Aerosil 380




Bu stearate






F-56




360





10.0




1.3





steareth-30




Aerosil 380






F-57




360





10.0




1.3





ceteareth-27




Aerosil 380






F-58




360





10.0




1.3





steareth-20




Aerosil 380






F-59




360





10.0




1.3





oleth-20




Aerosil 380






F-60




360




1.0




10.0




1.3





ceteareth-27




Aerosil 380




Me stearate






F-61




360




1.0




10.0




1.3





ceteareth-27




Aerosil 380




Me palmitate






F-62




300





10.0




1.3





ceteareth-27




Aerosil 380






F-63




240





10.0




1.3





ceteareth-27




Aerosil 380






F-64




360





6.0




1.3





ceteareth-27




Aerosil 380






F-65




300





6.0




1.3





ceteareth-27




Aerosil 380






F-66




240





6.0




1.3





ceteareth-27




Aerosil 380






F-67




360






0.6






Aerosil 90






F-68




360






3.1






Aerosil 90






F-69




360






0.6






Al oxide C






F-70




360






3.1






Al oxide C






F-71




360






0.8






Aerosil 90






F-72




360






0.8






Al oxide C






F-73




360





3.0




0.8





Ethomeen T/25




Aerosil 90






F-74




360





3.0




0.8





Ethomeen T/25




Al oxide C






F-75




360





3.0




0.3





Ethomeen T/25




Al oxide C






F-76




360





3.0




0.8





Ethomeen T/25




Nalco 1056






F-77




360





3.0




0.8





Ethomeen T/25




Nalco 1056






F-78




480





3.0 + 1.0




0.4





Ethomeen T/25 +




Al oxide C












Agrimul PG-2069






F-79




480





3.0 + 3.0




0.4





Ethomeen T/25 +




Al oxide C












Agrimul PG-2069






F-80




360





3.0




0.8





Agrimul PG-2069




Aerosil 90






F-81




360





3.0




0.8





Tween 20




Aerosil 90






F-82




360





3.1 + 3.1




0.8




7.1




Ethomeen T/25 +




Aerosil 90





(Bu)


4


NOH












Tween 20






F-83




360






0.8




7.1





Aerosil 90





(Bu)


4


NOH






F-84




480





3.0




0.8





steareth-20




Aerosil 380






F-85




480





3.0




1.5





oleth-20




Aerosil 380






F-86




480





3.0




1.5





oleth-20




Aerosil MOX-170






F-87




480





3.0




1.5





oleth-20




Aerosil OX-50






F-88




480





3.0




1.5





Velvetex




Aerosil 380






F-89




480





3.0




1.5





steareth-20




Aerosil blend 2






F-90




480





3.0




1.5





oleth-20




Aerosil blend 2






F-91




480





4.5




1.5





oleth-20




Aerosil 380







F-92




480





4.5




1.5





steareth-20




Aerosil 380






F-93




480





3.0




1.5





steareth-20




Aerosil blend 1






F-94




480





1.0




1.5





steareth-20




Aerosil blend 1






F-95




480





6.0




1.5





steareth-20




Aerosil blend 1






F-96




480





4.5




1.5




0.5




steareth-20




Aerosil blend 2





propylene glycol






F-97




480





6.0




1.5




0.5




steareth-20




Aerosil blend 2





propylene glycol






F-98




480





6.0




1.5




0.5




oleth-20




Aerosil blend 2





propylene glycol






F-99




480





4.5 + 2.3




1.5




0.5




steareth-20 +




Aerosil blend 2





propylene glycol












Ethomeen T/25






F-100




480





6.0




1.5





steareth-20




Al oxide C






F-101




480





4.5 + 2.3




1.5




0.5




steareth-20 +




Al oxide C





propylene glycol












Ethomeen T/25






F-102




480





4.5 + 1.0




1.5




0.5




steareth-20 +




Al oxide C





propylene glycol












Ethomeen T/25






F-103




480





3.0




1.5





steareth-20




Aerosil 380






F-104




480





4.5




1.5





steareth-20




Al oxide C






F-105




480





6.0




1.5





steareth-20




Aerosil 380






F-106




480





4.5 + 1.0




1.5




0.5




steareth-20 +




Aerosil 380





propylene glycol












Ethomeen T/25






F-107




480





4.5




1.5




0.5




steareth-20 +




Aerosil 380





propylene glycol












Ethomeen T/25






F-108




480





4.5




1.5





steareth-20




Aerosil blend 2






F-109




480





6.0




1.5





steareth-20




Aerosil blend 2






F-110




480





4.5




1.5




0.5




steareth-20 +




Aerosil blend 2





propylene glycol












Ethomeen T/25






F-111




480





4.5




1.5





steareth-30




Aerosil blend 2






F-112




480





4.5 + 1.0




1.5




0.5




steareth-20 +




Aerosil blend 2





propylene glycol












Ethomeen T/25






F-113




480





6.0




1.5





steareth-30




Aerosil blend 2






F-114




480





4.5 + 2.3




1.5




0.5




steareth-20 +




Aerosil blend 2





propylene glycol












Ethomeen T/25






F-115




480





10.0




1.5





steareth-20




Aerosil blend 2






F-116




480





4.5




1.5





ceteareth-27




Aerosil 380






F-117




480





6.0




1.5





ceteareth-27




Aerosil 380






F-118




480





4.5




1.5





ceteareth-27




Aerosil blend 2






F-119




480





6.0




1.5





ceteareth-27




Aerosil blend 2






F-120




480





4.5




1.5





ceteareth-27




Al oxide C






F-121




480





6.0




1.5





ceteareth-27




Al oxide C











Aerosil blend 1: Aerosil MOX-80 + Aerosil MOX-170 (1:1)










Aerosil blend 2: Aerosil MOX-80 + Aerosil 380 (1:2)













Aqueous compositions tested in the field having soybean lecithin (45% phospholipid, Avanti) as the first excipient substance and a cationic fluoro-organic surfactant as the second excipient substance have included:


















% w/w
















Field




Glyphosate





Fluorad




Fluorad







composition




g a.e./l




Lecithin




FC-135




FC-754




MON 0818









F-122




167




6.0




8.3





4.0






F-123




168




6.0





8.3




4.0






F-124




228




2.0





2.0




0.5






F-125




347




3.0





3.0




0.5






F-126




344




1.0





1.0




0.5






F-127




111




8.0




8.0





0.5






F-128




228




6.0





3.0




6.0






F-129




228




6.0





6.0




6.0






F-130




228




3.3





5.0




0.5






F-131




228




5.0





5.0




0.8






F-132




372




3.0





3.0




0.8






F-133




372




3.0





5.0




0.8






F-134




372




3.0





12.0




0.8














The above compositions were prepared by process (v) as described in the Examples.




Aqueous compositions tested in the field having soybean lecithin (45% phospholipid, Avanti) as the first excipient substance and fatty acid ester as the second excipient substance have included:



















% w/w



















Field




Glyphosate





MON




Fatty acid






Type of fatty






composition




g a.e./l




Lecithin




0818




ester




Surfactant




Type of surfactant




acid ester









F-135




360




0.5




6.0




7.5




6.0




Ethomeen T/25




Bu stearate






F-136




360




6.0




4.5




1.5




3.0 + 4.5




ceteareth-27 +




Bu stearate












Ethomeen T/25






F-137




228




6.0




3.0




1.5




3.0




Ethomeen T/25




Bu stearate






F-138




228




0.8





3.8




3.0 + 3.0




ceteareth-27 +




Bustearate












Ethomeen T/25






F-139




228




1.5





1.5




3.0 + 3.0




ceteareth-27 +




Bu stearate












Ethomeen T/25






F-140




228




6.7




0.8




0.7




0.8




Ethomeen T/25




Bu stearate






F-141




228




6.7




1.7




0.7




1.7




Ethomeen T/25




Bu stearate






F-142




228




6.7




3.3




0.7




3.3




Ethomeen T/25




Bu stearate






F-143




228




3.3




0.8




0.7




0.8




Ethomeen T/25




Bu stearate






F-144




228




3.3




1.7




0.7




1.7




Ethomeen T/25




Bu stearate






F-145




228




3.3




2.5




0.7




2.5




Ethomeen T/25




Bu stearate






F-146




228




3.3




3.3




0.7




3.3




Ethomeen T/25




Bu stearate






F-147




228




6.7




2.5




0.7




2.5




Ethomeen T/25




Bu stearate






F-148




228





3.0




0.5




3.0




Ethomeen T/25




Bu stearate






F-149




228




2.0




2.5




0.5




2.5




Ethomeen T/25




Bu stearate






F-150




228




4.0




6.0




0.5






Bu stearate






F-151




228




4.0




6.0




2.0






Bu stearate






F-152




228




4.0




6.0




1.0






Bu stearate






F-153




228




2.0




2.0




0.5






Bu stearate






F-154




228




2.0




4.0




0.5






Bu stearate






F-155




228





6.0




0.5






Bu stearate














The above compositions were prepared by process (x) as described in the Examples.




Dry compositions tested in the field have included:



















% w/w





















Field




Glyphosate





Butyl





Coll.






Type of colloidal




Other






composition




a.e.




Lecithin




stearate




Surfactant




partic.




Other




Type of surfactant




particulate




ingredients























F-156




64






25.0




2.0





steareth-20




Aerosil blend 1







F-157




68






20.0




2.0





steareth-20




Aerosil blend 1






F-158




72






15.0




2.0





steareth-20




Aerosil blend 1






F-159




64






25.0




1.0





ceteth-20




Aerosil 380






F-160




65






25.0




1.0





steareth-20




Aerosil 380






F-161




65






25.0




1.0





oleth-20




Aerosil 380






F-162




67




10.0





10.0 + 1.5




1.0





Fluorad FC-754 +




Aerosil 380













Ethomeen T/25






F-163




73




7.0





 7.0 + 1.5




1.0





Fluorad FC-754 +




Aerosil 380













Ethomeen T/25






F-164




64




12.0




3.0




12.0






MON 0818






F-165




64




6.7




6.7




13.2






MON 0818






F-166




68






20.0




2.0





steareth-20




Aerosil blend 1






F-167




66





2.0




20.0




2.0





steareth-20




Aerosil blend 1






F-168




68






20.0




2.0





oleth-20




Aerosil blend 1






F-169




66





2.0




20.0




2.0





oleth-20




Aerosil blend 1






F-170




66





2.0




20.0




2.0





ceteareth-27




Aerosil blend 1






F-171




48






14.1





36.1




ceteareth-27





NH


4


phosphate






F-172




65






20.0





5.0




ceteareth-27





Na acetate






F-173




70






20.0






ceteareth-27











Aerosil blend 1: Aerosil MOX-80 + Aerosil MOX-170 (1:1)













The above compositions were prepared by the process described for dry granular compositions in the Examples.











EXAMPLES




In the following Examples illustrative of the invention, greenhouse tests were conducted to evaluate relative herbicidal effectiveness of glyphosate compositions. Compositions included for comparative purposes included the following:




Formulation B: which consists of 41% by weight of glyphosate IPA salt in aqueous solution. This formulation is sold in the USA by Monsanto Company under the ACCORD® trademark.




Formulation C: which consists of 41% by weight of glyphosate IPA salt in aqueous solution with a coformulant (15% by weight) of a surfactant (MON 0818 of Monsanto Company) based on polyoxyethylene (15) tallowamine. This formulation is sold in Canada by Monsanto Company under the ROUNDUP® trademark.




Formulation J: which consists of 41% by weight of glyphosate IPA salt in aqueous solution, together with surfactant. This formulation is sold in the USA by Monsanto Company under the ROUNDUP® ULTRA trademark.




Formulation K: which consists of 75% by weight of glyphosate ammonium salt together with surfactant, as a water-soluble dry granular formulation. This formulation is sold in Australia by Monsanto Company under the ROUNDUP® DRY trademark.




Formulations B, C and J contain 356 grams of glyphosate acid equivalent per liter (g a.e./l). Formulation K contains 680 grams of glyphosate acid equivalent per kilogram (g a.e./kg).




Various proprietary excipients were used in compositions of the Examples. They may be identified as follows:

















Trade name




Manufacturer




Chemical description











Aerosil 90




Degussa




amorphous silica, 90 m


2


/g






Aerosil 200




Degussa




amorphous silica, 200 m


2


/g






Aerosil 380




Degussa




amorphous silica, 380 m


2


/g






Aerosil MOX-80




Degussa




amorphous silica/aluminum oxide, 80 m


2


/gm






Aerosil MOX-170




Degussa




amorphous silica/aluminum oxide, 170 m


2


/g






Aerosil OX-50




Degussa




amorphous silica, 50 m


2


/g






Aerosil R-202




Degussa




amorphous hydrophobic silica (dimethylsiloxane surface group)






Aerosil R-805




Degussa




amorphous hydrophobic silica (octyl surface group)






Aerosil R-812




Degussa




amorphous hydrophobic silica (trimethylsilyl surface group)






Aerosol OS




Cytec




diisopropyl naphthalene sulfonate, Na salt






Aerosol OT




Cytec




dioctyl sulfosuccinate, Na salt






Agrimer AL-25




ISP




1-ethenyl hexadecyl-2-pyrrolidinone






Agrimer AL-30




ISP




1-ethenyl-2-pyrrolidinone polymer






Agrimul PG-2069




Henkel




C


9-11


alkylpolyglycoside






Alcodet 218




Rhone-Poulenc




isolauryl 10EO thioether






Aluminum oxide C




Degussa




aluminum oxide, 100 m


2


/g






Amidox L-5




Stepan




lauramide 5EO






Ammonyx CO




Stepan




palmitamine oxide






Ammonyx LO




Stepan




lauramine oxide






Arcosolve DPM




Arco




dipropyleneglycol monomethyl ether






Diacid 1550




Westvaco




cyclocarboxypropyl oleic acid






Dowanol PNB




Dow




propylene glycol n-butyl ether






Dowanol TPNB




Dow




tripropylene glycol n-butyl ether






Emerest 2421




Henkel




glyceryl oleate






Emerest 266l




Henkel




PEG-12 laurate






Emid 6545




Henkel




oleic diethanolamide






Emphos CS-12




Witco




alkylaryl ethoxylate phosphate ester






Emphos CS-131




Witco




alkylaryl ethoxylate phosphate ester






Emphos CS-141




Witco




nonylphenol 10EO phosphate






Emphos CS-330




Witco




alkylaryl ethoxylate phosphate ester






Emphos PS-21A




Witco




alcohol ethoxylate phosphate ester






Emphos PS-121




Witco




linear alcohol ethoxylate phosphate ester, acid form






Emphos PS-400




Witco




linear alcohol ethoxylate phosphate ester, acid form






Ethomeen C/12




Akzo




cocoamine 2EO






Ethomeen C/25




Akzo




cocoamine 15EO






Ethomeen T/12




Akzo




tallowamine 2EO






Ethomeen T/25




Akzo




tallowamine 15EO






Ethoquad T/20




Akzo




methyltallowammonium chloride 10EO






Exxate 700




Exxon




C


7


alkyl acetate






Exxate 1000




Exxon




C


10


alkyl acetate






Exxol D-130




Exxon




dearomatized aliphatic solvent






Fluorad FC-120




3M




C


9-10


perfluoroalkyl sulfonate, NH4 salt






Fluorad FC-129




3M




fluorinated alkyl carboxylate, K salt






Fluorad FC-135




3M




fluorinated alkyl quatemary ammonium iodide






Fluorad FC-170C




3M




fluorinated alkanol EO






Fluorad FC-171




3M




fluorinated alkanol EO






Fluorad FC-431




3M




fluorinated alkyl ester






Fluorad FC-750




3M




fluorinated alkyl quaternary ammonium iodide






Fluorad FC-751




3M




fluorinated amphoteric surfactant






Fluorad FC-754




3M




fluorinated alkyl quaternary ammonium chloride






Fluorad FC-760




3M




fluorinated alkanol EO






Genapol UD-030




Hoechst




C


11


oxo alcohol 3EO






Genapol UD-110




Hoechst




C


11


oxo alcohol 11EO






Isopar V




Exxon




isoparaffinic oil






Kelzan




Monsanto




xanthan gum






LI-700




Loveland




lecithin-based adjuvant






Makon 4




Stepan




nonylphenol 4EO






Makon 6




Stepan




nonylphenol 6EO






Makon 30




Stepan




nonylphenol 30EO






Makon NF-5




Stepan




polyalkoxylated aliphatic base






MON 0818




Monsanto




tallowamine 15EO-based surfactant






Myrj 52




ICI




PEG-40 stearate






Myrj 59




ICI




PEG-100 stearate






Nalco 1056




Nalco




silica (26%)/aluminum oxide (4%); average particle size 20 nm






Neodol 1-12




Shell




C


11


linear alcohol 12EO






Neodol 1-7




Shell




C


11


linear alcohol 7EO






Neodol 1-9




Shell




C


11


linear alcohol 9EO






Neodol 25-12




Shell




C


12-15


linear alcohol 12EO






Neodol 25-20




Shell




C


12-15


linear alcohol 20EO






Neodol 25-3




Shell




C


12-15


linear alcohol 3EO






Neodol 25-7




Shell




C


12-15


linear alcohol 7EO






Neodol 25-9




Shell




C


12-15


linear alcohol 9EO






Neodol 45-13




Shell




C


14-15


linear alcohol 13EO






Neodol 91-2.5




Shell




C


9-11


linear alcohol 2.5EO






Neodox 25-11




Shell




C


12-15


linear alcohol ethoxycarboxylate 11EO






Ninate 411




Stepan




amine dodecylbenezene sulfonate






Ninol 40-CO




Stepan




coco diethanolamide






Orchex 796




Exxon




paraffinic oil






Pluronic 31-R1




BASF




21PO-7EO-21PO block copolymer






Pluronic F-108




BASF




128EO-54PO-128EO block copolymer






Pluronic F-127




BASF




98EO-67PO-98EO block copolymer






Pluronic F-68




BASF




75EO-30PO-75EO block copolymer






Pluronic L-35




BASF




11EO-16PO-11EO block copolymer






Pluronic L-43




BASF




7EO-21PO-7EO block copolymer






Pluronic L-81




BASF




6EO-39PO-6EO block copolymer






Pluronic P-84




BASF




27EO-39PO-27EO block copolymer






Polystep B-25




Stepan




decyl sulfate, Na salt






Reax 88B




Westvaco




highly sulfonated lignin, Na salt






Sident 9




Degussa




abrasive silica, 50 m


2


/g






Silwet 800




Witco




heptamethyltrisiloxane EO






Silwet L-77




Witco




heptamethyltrisiloxane 7EO methyl ether






Simulsol SL-4




Seppic




alkyl polyglucoside






Simulsol SL-10




Seppic




alkyl polyglucoside






Simulsol SL-62




Seppic




alkyl polyglucoside






Sipernat 22




Degussa




hydrophilic precipitated silica, 190 m


2


/g, av. aggregate size 100 μm






Sipernat 225




Degussa




hydrophilic precipitated silica 190 m


2


/g. av. aggregate size <10 μm






Span 60




ICI




sorbitan monostearate






Span 65




ICI




sorbitan tristearate






Span 80




ICI




sorbitan monooleate






Span 85




ICI




sorbitan trioleate






Steol CS-370




Stepan




lauryl EO sulfate, Na salt






Stepanol WAC




Stepan




lauryl sulfate, Na salt






Stepfac 8170




Stepan




nonylphenol EO phosphate






Surfynol 104




Air Products




tetramethyldecyne diol






Surfynol 465




Air Products




tetramethyldecyne diol 10EO






Tergitol 15-S-15




Union Carbide




C


15


branched secondary alcohol 15EO






Tergitol 15-S-20




Union Carbide




C


15


branched secondary alcohol 20EO






Tergitol 15-S-30




Union Carbide




C


15


branched secondary alcohol 30EO






Tergitol 15-S-40




Union Carbide




C


15


branched secondary alcohol 40EO






Titanium dioxide P25




Degussa




titanium dioxide, average particle size 21 nm






Toximul 8240




Stepan




PEG-36 castor oil






Toximul 8302




Stepan




alcohol EO blend






Triton RW-20




Union Carbide




alkylamine 2EO






Triton RW-50




Union Carbide




alkylamine 5EO






Triton RW-75




Union Carbide




alkylamine 7.5EO






Triton RW-100




Union Carbide




alkylamine 10EO






Triton RW-150




Union Carbide




alkylamine 15EO






Tryfac 5552




Henkel




decyl EO phosphate, free acid






Tween 20




ICI




sorbitan monolaurate 20EO






Tween 40




ICI




sorbitan monopalmitate 20EO






Tween 80




ICI




sorbitan monooleate 20EO






Tween 85




ICI




sorbitan trioleate 20EO






Velvetex AB-45




Henkel




cocobetaine






Westvaco H-240




Westvaco




dicarboxylate surfactant, K salt














Fluorad FC-135, though defined only generically as above in 3M product literature and in standard directories. has been specifically identified as






C


8


F


17


SO


2


NH(CH


2


)


3


N


+


(CH


3


)


3


I






in a paper by J. Linert & J. N. Chasman of 3M, titled “The effects of fluorochemical surfactants on recoatability” in the Dec. 20, 1993 issue of American Paint & Coatings Journal, and reprinted as a trade brochure by 3M. Fluorad FC-750 is believed to be based on the same surfactant. Fluorad FC-754 is believed to have the structure






C


8


F


17


SO


2


NH(CH


2


)


3


N


+


(CH


3


)


3


Cl











that is, identical to Fluorad FC-135 but with a chloride anion replacing iodide.




The following surfactants, identified in the Examples as “Surf H1” to “Surf H5”, have hydrocarbyl groups as the hydrophobic moiety but otherwise bear some structural similarity to the above Fluorad surfactants. They were synthesized and characterized under contract to Monsanto Company.




Surf H1: C


12


H


25


SO


2


NH(CH


2


)


3


N


+


(CH


3


)


3


I









Surf H2: C


17


H


35


CONH(CH


2


)


3


N


+


(CH


3


)


3


I









Surf H3: C


11


H


23


CONH(CH


2


)


3


N


+


(CH


3


)


3


I









Surf H4: cis-C


8


H


17


CH=CH(CH


2


)


7


CONH(CH


2


)


3


N


+


(CH


3


)


3


I









Surf H5: C


7


H


15


CONH(CH


2


)


3


N


+


(CH


3


)


3


I









Fatty alcohol ethoxylate surfactants are referred to in the Examples by their generic names as given in the International Cosmetic Ingredient Dictionary, 6th Edition, 1995 (Cosmetic, Toiletry and Fragrance Association, Washington, DC). They were interchangeably sourced from various manufacturers, for example:




Laureth-23: Brij 35 (ICI), Trycol 5964 (Henkel).




Ceteth-10: Brij 56 (ICI).




Ceteth-20: Brij 58 (ICI).




Steareth-10: Brij 76 (ICI).




Steareth-20: Brij 78 (ICI), Emthox 5888-A (Henkel), STA-20 (Heterene).




Steareth-30: STA-30 (Heterene).




Steareth-100: Brij 700 (ICI).




Ceteareth-15: CS-15 (Heterene).




Ceteareth-20: CS-20 (Heterene).




Ceteareth-27: Plurafac A-38 (BASF).




Ceteareth-55: Plurafac A-39 (BASF).




Oleth-2: Brij 92 (ICI).




Oleth-10: Brij 97 (ICI).




Oleth-20: Brij 98 (ICI), Trycol 5971 (Henkel).




Where a proprietary excipient is a surfactant supplied as a solution in water or other solvent, the amount to be used was calculated on a true surfactant basis, not an “as is” basis. For example, Fluorad FC-135 is supplied as 50% true surfactant, together with 33% isopropanol and 17% water; thus to provide a composition containing 0.1% w/w Fluorad FC-135 as reported herein, 0.2 g of the product as supplied was included in 100 g of the composition.




Spray compositions of the Examples contained an exogenous chemical, such as glyphosate IPA salt, in addition to the excipient ingredients listed. The amount of exogenous chemical was selected to provide the desired rate in grams per hectare (g/ha) when applied in a spray volume of 93 l/ha. Several exogenous chemical rates were applied for each composition. Thus, except where otherwise indicated, when spray compositions were tested, the concentration of exogenous chemical varied in direct proportion to exogenous chemical rate, but the concentration of excipient ingredients was held constant across different exogenous chemical rates.




Concentrate compositions were tested by dilution, dissolution or dispersion in water to form spray compositions. In these spray compositions prepared from concentrates, the concentration of excipient ingredients varied with that of exogenous chemical.




Except where otherwise indicated, these aqueous spray compositions were prepared by one of the following processes (i), (ii) or (iii).




(i) For compositions not containing lecithin or phospholipids, aqueous compositions were prepared by simple mixing of ingredients under mild agitation.




(ii) A weighed quantity of lecithin in powder form was dissolved in 0.4 ml chloroform in a 100 ml bottle. The resulting solution was air-dried to leave a thin film of lecithin, to which was added 30 ml deionized water. The bottle and its contents were then sonicated in a Fisher Sonic Dismembrator, Model 550, fined with a 2.4 cm probe tip, set at output level 8, and operated continuously for 3 minutes. The resulting aqueous dispersion of lecithin was then allowed to cool to room temperature, and formed a lecithin stock which was later mixed in the required amounts with other ingredients under mild agitation. In some cases, as indicated in the Examples, certain ingredients were added to the lecithin in water before sonication, so that the lecithin and these ingredients were sonicated together. Without being bound by theory, it is believed that by sonicating a formulation ingredient together with lecithin, at least some of that ingredient becomes encapsulated within, or otherwise bound to or trapped by, vesicles or other aggregates formed by phospholipids present in the lecithin.




(iii) The procedure of process (ii) was followed except that, before sonication, the step of forming a lecithin solution in chloroform was omitted. Instead, lecithin in powder form was placed in a beaker, water was added and the beaker and its contents were then sonicated.




Except where otherwise indicated. aqueous concentrate compositions were prepared by one of the following processes (iv) to (x).




(iv) A weighed amount of lecithin powder of the type indicated was placed in a beaker and deionized water was added in no more than the amount required for the desired final composition. The beaker and its contents were then placed in a Fisher Sonic Dismembrator, Model 550, fitted with a 2.4 cm probe tip, set at output level 8, and operated for 5 minutes. The resulting lecithin dispersion formed the basis to which other ingredients were added with mild agitation to make the aqueous concentrate formulation. The order of addition of these ingredients was varied and was sometimes found to affect the physical stability of the concentrate formulation. Where a fluoro-organic surfactant such as Fluorad FC-135 or FC-754 was to be included, it was generally added first, followed by other surfactants if required and then by the exogenous chemical. Where the exogenous chemical used was glyphosate IPA salt. this was added in the form of a 62% (45% a.e.) solution by weight, at a pH of 4.4 to 4.6. A final adjustment with water took place if necessary as the last step. In some cases certain ingredients of the concentrate formulation were added before rather than after sonication, so that they were sonicated with the lecithin.




(v) A weighed amount of lecithin powder of the type indicated was placed in a beaker and deionized water was added in sufficient quantity to provide, after sonication as detailed below, a lecithin stock at a convenient concentration, normally in the range from 10% to 20% w/w and typically 15% w/w. The beaker and its contents were then placed in a Fisher Sonic Dismembrator, Model 550, fitted with a 2.4 cm probe tip with the pulse period set at 15 seconds with 1 minute intervals between pulses to allow cooling. Power output was set at level 8. After a total of 3 minutes of sonication (12 pulse periods) the resulting lecithin stock was finally adjusted to the desired concentration if necessary with deionized water. To prepare an aqueous concentrate formulation, the following ingredients were mixed in the appropriate proportions with mild agitation, normally in the order given although this was sometimes varied and was found in some cases to affect the physical stability of the concentrate formulation: (a) exogenous chemical, for example glyphosate IPA salt as a 62% w/w solution at pH 4.4-4.6; (b) lecithin stock; (c) other ingredients if required; and (d) water.




(vi) Water-in-oil-in-water (W/O/W) multiple emulsions were prepared as follows. First a water-in-oil emulsion was prepared. To do this, the required amounts of the selected oil and a first emulsifier (referred to in the Examples as “emulsifier #1”) were mixed thoroughly. If it was desired to prepare the formulation with glyphosate in the inner aqueous phase, a measured amount of concentrated (62% w/w) aqueous solution of glyphosate IPA salt was added to the mixture of oil and first emulsifier with agitation to ensure homogeneity. The amount of water required in the inner aqueous phase was then added to complete the water-in-oil emulsion, which was finally subjected to high-shear mixing, typically using a Silverson L4RT-A mixer fitted with a fine emulsor screen operated for 3 minutes at 10,000 rpm. The required amount of a second emulsifier (referred to in the Examples as “emulsifier #2”) was next added to the water-in-oil emulsion with agitation to ensure homogeneity. If it was desired to prepare the formulation with glyphosate in the outer aqueous phase, a measured amount of concentrated (62% w/w) aqueous solution of glyphosate IPA salt was added to the blend of the water-in-oil emulsion and the second emulsifier with further agitation. To complete the water-in-oil-in-water multiple emulsion composition, the amount of water required in the outer aqueous phase was added. The composition was finally subjected to high-shear mixing, typically using a Silverson L4RT-A mixer fitted with a medium emulsor screen, operated for 3 minutes at 7,000 rpm.




(vii) Oil-in-water (O/W) emulsions were prepared as follows. The required amount of the selected oil and surfactant (sometimes referred to in the Examples as “emulsifier #2” as it corresponds to the second emulsifier in process (vi)) were mixed thoroughly. If the surfactant selected was not free-flowing at ambient temperature, heat was applied to bring the surfactant into a flowable condition before mixing with the oil. A measured amount of concentrated (62% w/w) aqueous solution of glyphosate IPA salt was added to the surfactant-oil mixture with agitation. The required amount of water was added to bring the concentration of glyphosate and other ingredients to the desired level. The composition was finally subjected to high-shear mixing, typically using a Silverson L4RT-A mixer fitted with a medium emulsor screen, operated for 3 minutes at 7,000 rpm.




(viii) Surfactant-containing aqueous solution concentrates having no oil component were prepared as follows. A concentrated (62% w/w) aqueous solution of glyphosate IPA salt was added in the desired amount to a weighed quantity of the selected surfactant(s). If the surfactant selected is not free-flowing at ambient temperature, heat was applied to bring the surfactant into a flowable condition before adding the glyphosate solution. The required amount of water was added to bring the concentration of glyphosate and other ingredients to the desired level. The composition was finally subjected to high-shear mixing, typically using a Silverson L4RT-A mixer fitted with a medium emulsor screen, operated for 3 minutes at 7,000 rpm.




(ix) For compositions containing a colloidal particulate, the required amount by weight of the selected colloidal particulate was suspended in a concentrated (62% w/w) aqueous solution of glyphosate IPA salt and agitated with cooling to ensure homogeneity. To the resulting suspension was added the required amount by weight of the selected surfactant(s). For a surfactant which is not free-flowing at ambient temperature, heat was applied to bring the surfactant into a flowable condition before adding it to the suspension. In those instances where an oil, such as butyl stearate, was also to be included in the composition, the oil was first thoroughly mixed with the surfactant and the surfactant-oil mixture added to the suspension. To complete the aqueous concentrate, the required amount of water was added to bring the concentration of glyphosate and other ingredients to the desired level. The concentrate was finally subjected to high-shear mixing, typically using a Silverson L4RT-A mixer fitted with a medium emulsor screen, operated for 3 minutes at 7,000 rpm.




(x) The procedure for preparing aqueous concentrate formulations containing lecithin and butyl stearate was different from that followed for other lecithin-containing concentrates. Exogenous chemical, for example glyphosate IPA salt, was first added, with mild agitation, to deionized water in a formulation jar. The selected surfactant (other than lecithin) was then added, while continuing the agitation, to form a preliminary exogenous chemical/surfactant mixture. Where the surfactant is not free-flowing at ambient temperature, the order of addition was not as above. Instead, the non-free-flowing surfactant was first added to water together with any other surfactant (other than lecithin) required in the composition, and was then heated to 55° C. in a shaker bath for 2 hours. The resulting mixture was allowed to cool, then exogenous chemical was added with mild agitation to form the preliminary exogenous chemical/surfactant mixture. A weighed amount of the selected lecithin was added to the preliminary exogenous chemical/surfactant mixture, with stirring to break up lumps. The mixture was left for about 1 hour to allow the lecithin to hydrate, then butyl stearate was added, with further stirring until no phase separation occurred. The mixture was then transferred to a microfluidizer (Microfluidics International Corporation, Model M-110F) and microfluidized for 3 to 5 cycles at 10,000 psi (69 MPa). In each cycle, the formulation jar was rinsed with microfluidized mixture. In the last cycle, the finished composition was collected in a clean dry beaker.




The following procedure was used for testing compositions of the Examples to determine herbicidal effectiveness, except where otherwise indicated.




Seeds of the plant species indicated were planted in 85 mm square pots in a soil mix which was previously steam sterilized and prefertilized with a 14-14-14 NPK slow release fertilizer at a rate of 3.6 kg/m3. The pots were placed in a greenhouse with sub-irrigation. About one week after emergence, seedlings were thinned as needed, including removal of any unhealthy or abnormal plants, to create a uniform series of test pots.




The plants were maintained for the duration of the test in the greenhouse where they received a minimum of 14 hours of light per day. If natural light was insufficient to achieve the daily requirement, artificial light with an intensity of approximately 475 microeinsteins was used to make up the difference. Exposure temperatures were not precisely controlled but averaged about 27° C. during the day and about 18° C. during the night. Plants were sub-irrigated throughout the test to ensure adequate soil moisture levels.




Pots were assigned to different treatments in a fully randomized experimental design with 3 replications. A set of pots was left untreated as a reference against which effects of the treatments could later be evaluated.




Application of glyphosate compositions was made by spraying with a track sprayer fitted with a 9501E nozzle calibrated to deliver a spray volume of 93 liters per hectare (1/ha) at a pressure of 166 kilopascals (kPa). After treatment, pots were returned to the greenhouse until ready for evaluation.




Treatments were made using dilute aqueous compositions. These could be prepared as spray compositions directly from their ingredients, or by dilution with water of preformulated concentrate compositions.




For evaluation of herbicidal effectiveness, all plants in the test were examined by a single practiced technician, who recorded percent inhibition, a visual measurement of the effectiveness of each treatment by comparison with untreated plants. Inhibition of 0% indicates no effect, and inhibition of 100% indicates that all of the plants are completely dead. Inhibition of 85% or more is in most cases considered acceptable for normal herbicidal use; however in greenhouse tests such as those of the Examples it is normal to apply compositions at rates which give less than 85% inhibition, as this makes it easier to discriminate among compositions having different levels of effectiveness.




Example 1




Glyphosate-containing spray compositions were prepared by tank-mixing Formulations B and C with excipients as shown in Table 1.




Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and 16 days after planting ECHCF, and evaluation of herbicidal inhibition was done 18 days after application. Results, averaged for all replicates of each treatment, are shown in Table 1.
















TABLE 1











Glyphosate




Glyphosate rate





Additive rate




% Inhibition
















composition




g a.e./ha




Additive




% v/v




ABUTH




ECHCF









Formulation C




175




none





40




75







350






69




89







500






97




100






Formulation B




175




none





45




37







350






73




66







500






83




97






Formulation B




175




L-77




0.25




64




30







175





0.50




77




27






Formulation B




175




FC-135




0.25




55




72







175





0.50




73




61






Formulation B




175




FC-135 + L-77 8:1




0.50




71




58







175




FC-135 + L-77 4:1




0.50




76




61







175




FC-135 + L-77 2:1




0.50




63




56







175




FC-135 + L-77 1:1




0.50




77




40







175




FC-135 + L-77 1:2




0.50




54




23







175




FC-135 + L-77 1:4




0.50




76




31







175




FC-135 + L-77 1:8




0.50




53




29






Formulation B




175




FC-135 + L-77 8:1




0.25




51




48







175




FC-135 + L-77 4:1




0.25




37




47







175




FC-135 + L-77 2:1




0.25




45




37







175




FC-135 + L-77 1:1




0.25




65




27







175




FC-135 + L-77 1:2




0.25




45




29







175




FC-135 + L-77 1:4




0.25




60




17







175




FC-135 + L-77 1:8




0.25




52




15














Tank mixtures of Fluorad FC-135 with Formulation B gave markedly superior herbicidal effectiveness on ABUTH by comparison with Formulation C, but did not match the herbicidal effectiveness of Formulation C on ECHCF. The antagonism of glyphosate activity on ECHCF seen with the nonionic organosilicone surfactant Silwet L-77 did not occur with the cationic fluoro-organic surfactant Fluorad FC-135.




Example 2




Aqueous spray compositions were prepared containing glyphosate sodium or IPA salts and excipient ingredients as shown in Table 2a. Process (ii) was followed for all compositions. using soybean lecithin (10-20% phospholipid, Sigma Type II-S). Without adjustment, the pH of the compositions was approximately 5. For those compositions having a pH of approximately 7 as shown in Table 2


a,


the pH was adjusted using the same base (sodium hydroxide or IPA) that formed the glyphosate salt.
















TABLE 2a













% w/w




Components


















Spray




Lecithin




Fluorad





sonicated




Glyphosate







composition




g/l




FC-135




L-77




with lecithin




salt




pH









2-01




5.0






none




IPA




5






2-02




5.0





0.50




none




IPA




5






2-03




5.0






none




Na




7






2-04




5.0





0.50




none




Na




7






2-05




5.0






none




IPA




7






2-06




5.0





0.50




none




IPA




7






2-07




5.0






none




Na




5






2-08




5.0





0.50




none




Na




5






2-09




2.5






none




IPA




5






2-10




2.5




0.50





none




IPA




5






2-11




5.0




0.50





none




IPA




5






2-12




5.0




0.33




0.17




none




IPA




5






2-13




5.0





0.50




L-77




IPA




5






2-14




5.0





0.50




L-77




Na




7






2-15




5.0





0.50




L-77




IPA




7






2-16




5.0





0.50




L-77




Na




5














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 17 days after application.




Formulation C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 2b.














TABLE 2b











Spray




Glyphosate rate




% Inhibition














composition




g a.e./ha




ABUTH




ECHCF

















Formulation C




100




8




54







200




54




75







300




77




90






Formulation C




100




62




10






+ Silwet L-77 0.5% v/v




200




91




25







300




95




27






2-01




100




59




64







200




74




83







300




82




99






2-02




100




66




44







200




73




45







300




92




76






2-03




100




17




29







200




37




72







300




70




89






2-04




100




48




24







200




67




50







300




81




61






2-05




100




40




44







200




77




89







300




79




95






2-06




100




76




43







200




87




74







300




90




85






2-07




100




40




50







200




66




54







300




84




83






2-08




100




69




34







200




57




70







300




78




66






2-09




100




44




62







200




83




82







300




90




91






2-10




100




84




83







200




97




85







300




95




93






2-11




100




79




65







200




89




84







300




98




98






2-12




100




74




63







200




93




84







300




94




92






2-13




100




86




85







200




91




92







300




97




97






2-14




100




56




17







200




69




48







300




87




81






2-15




100




61




39







200




87




73







300




83




78






2-16




100




42




32







200




35




78







300




59




85














Surprisingly strong herbicidal effectiveness was observed with compositions 2-10 and 2-11 containing lecithin and Fluorad FC-135 on both ABUTH and ECHCF, by comparison with otherwise similar compositions (2-09 and 2-01) lacking the Fluorad FC-135. Herbicidal effectiveness of composition 2-11 at the 100 g a.e./ha glyphosate rate was superior to that of Formulation C at a threefold higher rate on ABUTH and superior to that of Formulation C at a twofold higher rate on ECHCF.




Example 3




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 3a. Process (ii), indicated in Table 3a as involving “high” sonication power, was followed for all compositions, except that for composition 3-06 a different sonication procedure, referred to as “low” sonication power, was used. In this procedure the lecithin in water was sonicated in a Fisher Model FS 14H ultrasonic bath for 30 minutes. Soybean lecithin (10-20% phospholipid, Sigma Type II-S) was used for all compositions. Without adjustment, the pH of the compositions was approximately 5. For those compositions having a pH of approximately 7 as shown in Table 3a, the pH was adjusted using the same base (sodium hydroxide or IPA) that formed the glyphosate salt.















TABLE 3a











Spray





% w/w




Components

















compo-




Lecithin




Fluorad





sonicated





Sonication






sition




g/l




FC-135




L-77




with lecithin




pH




power




















3-01




5.0






none




5




high






3-02




5.0





0.50




none




5




high






3-03




5.0





0.50




L-77




5




high






3-04




5.0





0.50




glyphosate




5




high






3-05




5.0





0.50




L-77, glyphosate




5




high






3-06




5.0






none




7




low






3-07




5.0






none




7




high






3-08




5.0





0.50




none




7




high






3-09




5.0





0.50




L-77




7




high






3-10




5.0





0.50




glyphosate




7




high






3-11




5.0





0.50




L-77, glyphosate




7




high






3-12




5.0




0.50





none




5




high






3-13




5.0




0.50





FC-135




5




high






3-14




5.0




0.50





glyphosate




5




high






3-15




5.0




0.17




0.33




FC-135, glyphosate




5




high






3-16




5.0




0.17




0.33




none




5




high






3-17




5.0




0.17




0.33




FC-135, L-77




5




high






3-18




10.0






none




5




high






3-19




20.0






none




5




high






3-20




10.0





0.50




none




5




high






3-21




10.0





0.50




L-77




5




high






3-22




20.0





0.50




L-77




5




high






3-23




20.0





0.50




L-77, glyphosate




5




high














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B and C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 3b.
















TABLE 3b













Glyphosate rate




% Inhibition















Spray composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




11




12







200




55




43







300




65




38






Formulation B +




100




77




5






Silwet L-77 0.5% v/v




200




95




10







300




95




17






Formulation C




100




33




42







200




63




98







300




85




99






Formulation C +




100




78




7






Silwet L-77 0.5% v/v




200




95




19







300




98




54






3-01




100




63




22







200




77




69







300




92




82






3-02




100




79




30







200




96




67







300




98




70






3-03




100




81




29







200




96




70







300




97




86






3-04




100




85




32







200




94




60







300




98




61






3-05




100




82




34







200




98




60







300




96




69






3-06




100




55




40







200




91




69







300




97




90






3-07




100




77




29







200




93




82







300




97




100






3-08




100




83




48







200




95




67







300




94




74






3-09




100




83




37







200




95




75







300




99




83






3-10




100




77




36







200




99




75







300




98




69






3-11




100




81




38







200




94




81







300




97




76






3-12




100




56




47







200




91




90







300




97




95






3-13




100




81




41







200




94




58







300




97




84






3-14




100




77




37







200




94




70







300




96




94






3-15




100




76




61







200




95




79







300




96




85






3-16




100




95




84







200




94




56







300




75




32






3-17




100




78




44







200




93




86







300




94




87






3-18




100




59




27







200




94




84







300




96




100






3-19




100




74




44







200




94




74







300




95




95






3-20




100




79




62







200




89




78







300




92




93






3-21




100




66




69







200




80




79







300




86




88






3-22




100




44




69







200




83




97







300




74




94






3-23




100




50




71







200




68




91







300




85




76














Composition 3-12 containing lecithin and Fluorad FC-135 again showed surprisingly high herbicidal effectiveness by comparison with composition 3-01, lacking the Fluorad FC-135, and also by comparison with Formulation C. When efforts were made to encapsulate Fluorad FC-135 or glyphosate (compositions 3-13 or 3-14 respectively) in lecithin liposomes by sonication in the presence of the ingredients sought to be encapsulated, some further enhancement of herbicidal effectiveness was evident on ABUTH, but effectiveness was reduced on ECHCF. Overall, the best activity in this test was obtained without encapsulation.




Example 4




Compositions 3-01 to 3-12 of Example 3 were tested in this Example. Black nightshade (


Solanum nigrum


, SOLNI) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 26 days after planting SOLNI and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B and C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results. averaged for all replicates of each treatment, are shown in Table 4.
















TABLE 4












Glyphosate rate




% Inhibition







Spray composition




g a.e./ha




SOLNI




























Formulation B




100




28








200




35








300




70







Formulation B +




100




85







Silwet L-77 0.5% v/v




200




98








300




97







Formulation C




100




30








200




58








300




70







Formulation C +




100




78







Silwet L-77 0.5% v/v




200




82








300




94







3-01




100




47








200




77








300




93







3-02




100




33








200




50








300




78







3-03




100




36








200




79








300




90







3-04




100




33








200




72








300




84







3-05




100




38








200




68








300




82







3-06




100




84








200




92








300




96







3-07




100




58








200




75








300




85







3-08




100




50








200




83








300




91







3-09




100




50








200




72








300




83







3-10




100




53








200




75








300




78







3-11




100




75








200




96








300




100







3-12




100




62








200




93








300




99















Composition 3-12 containing lecithin and Fluorad FC-135, as in the test of Example 3, showed remarkably strong herbicidal effectiveness, this time on SOLNI.




Example 5




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 5


a.


Process (ii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was approximately 5.















TABLE 5a













% w/w

















Spray




Lecithin




Fluorad




Silwet





Components






composition




g/l




FC-135




L-77




KCl




sonicated with lecithin









5-01




5.0







glyphosate






5-02




5.0





0.50





L-77






5-03




5.0





0.50





L-77






5-04




5.0





1.00





L-77






5-05




5.0





0.20





none






5-06




5.0





1.00





none






5-07




5.0





0.20





L-77, glyphosate






5-08




5.0





0.50





L-77, glyphosate






5-09




5.0





1.00





L-77, glyphosate






5-10




2.5





0.10





L-77






5-11




2.5





0.25





L-77






5-12




2.5





0.50





L-77






5-13




2.5





0.10





none






5-14




2.5





0.25





none






5-15




2.5





0.10





L-77, glyphosate






5-16




2.5





0.25





L-77, glyphosate






5-17




2.5





0.50





L-77, glyphosate






5-18




5.0





0.50




0.02




L-77






5-19




5.0





0.50




0.02




L-77, glyphosate






5-20




5.0




0.50






none






5-21




5.0




0.50






glyphosate






5-22




5.0




0.33




0.17





none






5-23




5.0




0.33




0.17





glyphosate














Velvetleaf


Abutilon theophrasti,


ABUTH) and Japanese millet


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 16 days after planting ECHCF, and evaluation of herbicidal inhibition was done 17 days after application.




Formulations B and C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 5b.
















TABLE 5b













Glyphosate rate




% Inhibition















Spray composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




200




47




83







300




64




84







400




71




90






Formulation B +




200




83




58






Silwet L-77 0.5% v/v




300




94




76







400




100




85






Formulation C




200




46




96







300




68




90







400




75




93






Formulation C +




200




81




66






Silwet L-77 0.5% v/v




300




93




68







400




96




86






5-01




200




70




91







300




74




100







400




93




94






5-02




200




81




95







300




68




100







400




81




100






5-03




200




78




100







300




99




83







400




98




99






5-04




200




89




95







300




93




95







400




86




100






5-05




200




60




89







300




79




100







400




86




100






5-06




200




76




100







300




84




100







400




100




96






5-07




200




65




97







300




84




100







400




100




96






5-08




200




82




100







300




95




100







400




96




100






5-09




200




78




99







300




89




99







400




90




100






5-10




200




66




100







300




79




98







400




89




100






5-11




200




67




95







300




81




100







400




97




100






5-12




200




76




88







300




79




100







400




95




96






5-13




200




59




85







300




66




93







400




67




100






5-14




200




56




89







300




67




100







400




83




100






5-15




200




54




100







300




63




100






5-16




200




46




88







300




73




100







400




86




100






5-17




200




81




98







300




83




97







400




92




96






5-18




200




56




92







300




64




100







400




74




100






5-19




200




64




94







300




80




97







400




80




96






5-20




200




88




91







300




96




100







400




98




98






5-21




200




92




94







300




100




100







400




100




100






5-22




200




88




97







300




93




95







400




95




100






5-23




200




79




100







300




96




100







400




97




96














Glyphosate activity on ECHCF in this test was too high to make meaningful comparisons. However, on ABUTH, composition 5-20 containing lecithin and Fluorad FC-135 exhibited remarkably strong herbicidal effectiveness by comparison with composition 5-01 (no Fluorad FC-135) and Formulation C. As in previous testing, a slight further advantage on ABUTH was obtained by efforts to encapsulate the glyphosate in lecithin liposomes, as in composition 5-21. Compositions 5-22 and 5-23, containing both Fluorad FC-135 and Silwet L-77 in addition to lecithin, also showed remarkably good herbicidal effectiveness.




Example 6




Compositions 5-01 to 5-23 of Example 5 were tested in this Example. Momingglory (Ipomoea spp., IPOSS) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting IPOSS and evaluation of herbicidal inhibition was done 19 days after application.




Formulations B and C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 6.
















TABLE 6












Glyphosate rate




% Inhibition







Spray composition




g a.e./ha




IPOSS




























Formulation B




200




40








400




66







Formulation B +




200




68







Silwet L-77 0.5% v/v




400




79







Formulation C




200




62








400




71







Formulation C +




200




70







Silwet L-77 0.5% v/v




400




72







5-01




200




64








400




77







5-02




200




68








400




75







5-03




200




68








400




72







5-04




200




69








400




72







5-05




200




64








400




78







5-06




200




80








400




89







5-07




200




69








400




74







5-08




200




60








400




72







5-09




200




79








400




84







5-10




200




69








400




78







5-11




200




52








400




72







5-12




200




69








400




88







5-13




200




72








400




74







5-14




200




68








400




69







5-15




200




68








400




70







5-16




200




55








400




69







5-17




200




52








400




67







5-18




200




65








400




67







5-19




200




54








400




70







5-20




200




74








400




100







5-21




200




72








400




91







5-22




200




81








400




84







5-23




200




79








400




90















Once again, surprisingly strong herbicidal effectiveness, this time on IPOSS, was exhibited by compositions 5-20 to 5-23. all of which contain lecithin and Fluorad FC-135.




Example 7




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 7


a.


Process (ii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.















TABLE 7a













% w/w
















Spray




Lecithin




Fluorad




Silwet




Components






composition




g/l




FC-135




L-77




sonicated with lecithin









7-01




5.0





0.50




L-77






7-02




5.0





0.25




L-77






7-03




5.0





0.10




L-77






7-04




5.0






none






7-05




2.5





0.50




L-77






7-06




2.5





0.25




L-77






7-07




2.5





0.10




L-77






7-08




1.0





0.50




L-77






7-09




1.0





0.25




L-77






7-10




2.5





0.10




L-77






7-11




2.5




0.25




0.25




L-77






7-12




2.5




0.17




0.33




L-77






7-13




2.5




0.33




0.17




L-77






7-14




2.5




0.50





none






7-15




2.5




0.25





none






7-16




2.5




0.10





none






7-17




2.5





0.25




glyphosate






7-18




2.5





0.10




glyphosate






7-19




2.5





0.50




glyphosate






7-20




5.0





0.50




L-77, glyphosate






7-21




2.5





0.25




L-77, glyphosate






7-22




1.0





0.25




L-77, glyphosate






7-23




1.0





0.10




L-77, glyphosate














Velvetleaf (


Abutilon theophrasti,


ABUTH), Japanese millet (


Echinochloa crus


-


galli,


ECHCF), and prickly sida (


Sida spinosa,


SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 20 days after planting ABUTH and ECHCF. Planting date for SIDSP was not recorded. Evaluation of herbicidal inhibition was done 19 days after application.




Formulations B and C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 7b.















TABLE 7b













Glyphosate rate




% Inhibition















Spray composition




g a.e./ha




ABUTH




ECHCF




SIDSP









Formulation B




150




33




39




29







250




44




43




66







350




83




45




60






Formulation B +




150




81




7




46






Silwet L-77 0.5% v/v




250




88




21




64







350




96




32




66






Formulation C




150




61




59




58







250




77




92




85







350




91




92




83






Formulation C +




150




76




10




65






Silwet L-77 0.5% v/v




250




87




17




60







350




92




39




64






7-01




150




87




43




47







250




88




41




60







350




96




53




66






7-02




150




66




51




61







250




85




81




63







350




84




89




75






7-03




150




66




54




65







250




70




63




60







350




94




96




87






7-04




150




73




58




61







250




85




83




90







350




91




100




83






7-05




150




76




44




49







250




85




55




56







350




93




79




64






7-06




150




64




73




56







250




71




78




61







350




81




79




77






7-07




150




53




41




59







250




74




78




68







350




78




90




75






7-08




150




83




33




59







250




82




39




75







350




95




59




69






7-09




150




78




32




46







250




85




42




75







350




91




62




67






7-10




150




26




36




43







250




69




73




75







350




76




81




73






7-11




150




83




79




72







250




96




93




78







350




99




97




84






7-12




150




78




57




58







250




89




78




66







350




94




93




75






7-13




150




83




84




54







250




94




93




67







350




99




97




93






7-14




150




80




68




69







250




85




88




79







350




97




94




99






7-15




150




75




80




62







250




93




93




76







350




95




91




94






7-16




150




75




69




60







250




88




91




77







350




89




92




75






7-17




150




77




69




67







250




88




91




86







350




93




97




96






7-18




150




71




63




66







250




74




85




82







350




89




85




83






7-19




150




74




62




77







250




86




80




93







350




92




96




96






7-20




150




39




46




38







250




80




49




69







350




91




64




69






7-21




150




65




50




34







250




64




52




52







350




78




67




62






7-22




150




68




18




35







250




79




42




43







350




87




49




58






7-23




150




24




46




38







250




62




49




42







350




91




53




67














Compositions 7-14 to 7-16, containing 0.25% lecithin together with Fluorad FC-135, provided excellent herbicidal effectiveness on all three species tested. Even at the lowest concentration of Fluorad FC-135 (0.1% in composition 7-16), effectiveness was substantially maintained on ABUTH and ECHCF, although some loss of effectiveness was evident on SIDSP. Compositions 7-11 to 7-13, containing lecithin, Fluorad FC-135 and Silwet L-77, also performed well in this test, not showing the antagonism on ECHCF characteristic of compositions containing Silwet L-77 but no Fluorad FC-135.




Example 8




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 8a. Process (ii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti).




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 8a. The pH of all compositions was adjusted to approximately 7.















TABLE 8a













% w/w
















Spray




Lecithin




Fluorad




Silwet




Components






composition




g/l




FC-135




L-77




sonicated with lecithin









8-01




5.0





0.50




L-77






8-02




5.0





0.25




L-77






8-03




5.0





0.10




L-77






8-04




5.0






none






8-05




2.5





0.50




L-77






8-06




2.5





0.25




L-77






8-07




2.5





0.10




L-77






8-08




1.0





0.50




L-77






8-09




1.0





0.25




L-77






8-10




2.5





0.10




L-77






8-11




2.5




0.25




0.25




L-77






8-12




2.5




0.17




0.33




L-77






8-13




2.5




0.33




0.17




L-77






8-14




2.5




0.50





none






8-15




2.5




0.25





none






8-16




2.5




0.10





none






8-17




2.5





0.25




glyphosate






8-18




2.5





0.10




glyphosate






8-19




2.5





0.50




glyphosate














Yellow nutsedge (


Cyperus esculentus,


CYPES) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 21 days after planting CYPES, and evaluation of herbicidal inhibition was done 27 days after application.




Formulations B and C, alone and tank; mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 8b.














TABLE 8b










Glyphosate rate




% Inhibition






Spray composition




g a.e./ha




CYPES

























Formulation B




500




92







1000




95







5000




100






Formulation B +




500




100






Silwet L-77 0.5% v/v




1000




87







5000




100






Formulation C




500




87







1000




96







5000




100






Formulation C +




500




98






Silwet L-77 0.5% v/v




1000




94







5000




100






8-01




500




91







1000




100







1500




97






8-02




500




83







1000




100







1500




100






8-03




500




90







1000




88







1500




71






8-04




500




88







1000




100







1500




100






8-05




500




84







1000




99







1500




95






8-06




500




90







1000




88







1500




99






8-07




500




78







1000




94







1500




97






8-08




500




93







1000




96







1500




100






8-09




500




87







1000




88







1500




100






8-10




500




86







1000




100







1500




100






8-11




500




95







1000




94







1500




100






8-12




500




92







1000




92







1500




100






8-13




500




87







1000




97







1500




100






8-14




500




82







1000




100







1500




100






8-15




500




85







1000




90







1500




95






8-16




500




87







1000




91







1500




100






8-17




500




83







1000




90







1500




95






8-18




500




93







1000




100







1500




95






8-19




500




86







1000




95







1500




100














The commercial standard Formulation C exhibited very high herbicidal effectiveness in this test and for this reason it is not possible to discern enhancements. There is a suggestion at the lowest glyphosate rate (500 g a.e./ha), effectiveness of compositions containing lecithin and Fluorad FC-135 (8-14 to 8-16) on CYPES surprisingly improved with decreasing Fluorad FC-135 concentration.




Example 9




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 9a. Process (ii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.















TABLE 9a













% w/w
















Spray




Lecithin




Fluorad




Silwet




Components






composition




g/l




FC-135




L-77




sonicated with lecithin









9-01




5.0






none






9-02




5.0





0.50




none






9-03




5.0





0.50




L-77






9-04




2.5






none






9-05




2.5





0.50




none






9-06




2.5





0.50




L-77






9-07




1.0






none






9-08




1.0





0.50




none






9-09




1.0





0.50




L-77






9-10




0.5






none






9-11




0.5





0.50




none






9-12




0.5





0.50




L-77






9-13




1.0





0.25




none






9-14




1.0





0.25




L-77






9-15




1.0





0.10




none






9-16




1.0





0.10




L-77






9-17




1.0




0.50





none






9-18




1.0




0.20





none






9-19




1.0




0.10





none






9-20




0.5




0.50





none






9-21




0.5




0.20





none














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. There was no record of the dates of planting. Evaluation of herbicidal inhibition was done 16 days after application.




In addition to compositions 9-01 to 9-21, spray compositions were prepared by tank mixing Formulations B and C with 0.5% Fluorad FC-135. Formulations B and C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 9b.















TABLE 9b













Glyphosate rate




% Inhibition














Spray composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




64




77







250




81




80







350




88




97






Formulation B +




150




42




38






Silwet L-77 0.5% v/v




250




56




49







350




67




64






Formulation C




150




61




89







250




75




91







350




92




99






Formulation C +




150




92




40






Silwet L-77 0.5% v/v




250




95




40







350




94




74






Formulation B +




150




87




34






Fluorad FC-135 0.5% w/v




250




90




44







350




97




47






Formulation C +




150




79




85






Fluorad FC-135 0.5% w/v




250




77




86







350




92




91






9-01




150




75




69







250




84




89







350




98




98






9-02




150




86




54







250




96




74







350




99




86






9-03




150




86




66







250




91




77







350




96




86






9-04




150




68




73







250




97




85







350




94




92






9-05




150




90




55







250




96




69







350




91




82






9-06




150




87




43







250




91




68







350




97




83






9-07




150




56




76







250




81




88







350




89




96






9-08




150




85




35







250




93




51







350




98




66






9-09




150




94




45







250




97




47







350




98




52






9-10




150




62




60







250




85




78







350




93




88






9-11




150




90




32







250




92




42







350




98




59






9-12




150




93




38







250




93




56







350




95




72






9-13




150




85




39







250




89




66







350




94




79






9-14




150




83




70







250




93




45







350




93




70






9-15




150




65




54







250




85




79







350




91




89






9-16




150




75




65







250




83




79







350




90




84






9-17




150




81




94







250




88




97







350




100




99






9-18




150




79




89







250




95




91







350




98




98






9-19




150




77




85







250




91




96







350




95




97






9-20




150




77




71







250




86




92







350




100




93






9-21




150




75




91







250




84




97







350




96




95














Compositions of this Example (9-17 to 9-21) containing very low concentrations of lecithin and Fluorad FC-135 exhibited remarkably high herbicidal effectiveness. Even a composition (9-19) with just 0.1% lecithin and 0.1% Fluorad FC-135 was much more effective on ABUTH than commercial standard Formulation C, and equally as effective on ECHCF as Formulation C. The apparently strong antagonism on ECHCF seen when Formulation B was tank mixed with 0.5% Fluorad FC-135 in this test is uncharacteristic and has not been seen in other tests (see. for example, Example 12 herein); indeed the data for this set of treatments is so out of line that it is believed they may be due to an error in application.




Example 10




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 10


a.


Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.















TABLE 10a











Spray





% w/w




Components

















compo-




Lecithin




Fluorad




Silwet




Methyl




Sodium




sonicated with






sition




g/I




FC-135




L-77




caprate




cholate




lecithin









10-01




5.0








none






10-02




5.0





0.50






none






10-03




5.0





0.50






L-77






10-04




2.5








none






10-05




0.5








none






10-06




2.5





0.50






none






10-07




2.5





0.50






L-77






10-08




0.5





0.50






none






10-09




0.5





0.50






L-77






10-10




2.5




0.25







none






10-11




2.5




0.10







none






10-12




2.5




0.05







none






10-13




0.5




0.25







none






10-14




0.5




0.10







none






10-15




0.5




0.05







none






10-16




2.5






0.10





Me caprate






10-17




2.5







0.10




Na cholate














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




In addition to compositions 10-01 to 10-17. spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 10b.















TABLE 10b













Glyphosate rate




% Inhibition














Spray composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




200




53




69







300




76




85







400




77




81






Formulation B +




200




100




28






Silwet L-77 0.5% v/v




300




100




35







400




100




47






Formulation C




200




57




81







300




73




90







400




98




94






Formulation C +




200




99




28






Silwet L-77 0.5% v/v




300




98




53







400




99




56






Formulation B +




200




76




85






Fluorad FC-135 0.25% w/v




300




95




81







400




100




100






Formulation B +




200




77




70






Fluorad FC-135 0.1% w/v




300




94




81







400




98




87






Formulation B +




200




65




73






Fluorad FC-135 0.05% w/v




300




84




94







400




88




96






Formulation C +




200




83




78






Fluorad FC-135 0.25% w/v




300




98




94







400




97




95






Formulation C +




200




65




66






Fluorad FC-135 0.1% w/v




300




89




86







400




97




89






Formulation C +




200




70




78






Fluorad FC-135 0.05% w/v




300




79




84







400




96




98






10-01




200




93




71







300




91




89







400




97




97






10-02




200




95




59







300




97




68







400




99




79






10-03




200




97




55







300




98




62







400




100




76






10-04




200




83




72







300




87




84







400




95




100






10-05




200




69




78







300




92




93







400




98




97






10-06




200




94




61







300




99




67







400




100




76






10-07




200




99




52







300




99




63







400




100




80






10-08




200




96




47







300




99




57







400




99




55






10-09




200




99




23







300




98




58







400




100




53






10-10




200




89




91







300




91




99







400




98




100






10-11




200




81




91







300




91




99







400




92




100






10-12




200




66




96







300




86




100







400




94




99






10-13




200




80




97







300




98




98







400




99




100






10-14




200




68




92







300




89




100







400




99




98






10-15




200




84




95







300




94




100







400




97




100






10-16




200




73




94







300




89




100







400




99




100






10-17




200




58




94







300




77




96







400




90




90














Tank mixture of Fluorad FC-135 at concentrations as low as 0.05% with Formulation B resulted in remarkably strong herbicidal efficacy in this test. The antagonism on ECHCF seen with the nonionic organosilicone surfactant Silwet L-77 did not occur with the cationic fluoro-organic surfactant Fluorad FC-135. Noteworthy was the outstanding herbicidal effectiveness provided by a composition (10-15) containing just 0.05% lecithin and 0.05% Fluorad FC-135. In this test addition of 0.1% methyl caprate to 0.25% lecithin, the methyl caprate being sonicated together with the lecithin, enhanced performance on ECHCF but not on ABUTH (compare compositions 10-16 and 10-04).




Example 11




Compositions 10-01 to 10-17 of Example 10. and tank mixtures of Formulations B and C with Fluorad FC-135, were tested in this Example. Prickly sida (


Sida spinosa,


SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 22 days after planting SIDSP, and evaluation of herbicidal inhibition was done 19 days after application.




Formulations B and C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 11.














TABLE 11










Glyphosate rate




% Inhibition






Spray composition




g a.e./ha




SIDSP

























Formulation B




200




46







300




75







400




80






Formulation B +




200




96






Silwet L-77 0.5% v/v




300




89







400




87






Formulation C




200




80







300




98







400




98






Formulation C +




200




75






Silwet L-77 0.5% v/v




300




91







400




94






Formulation B +




200




82






Fluorad FC-135 0.25% w/v




300




94







400




98






Formulation B +




200




70






Fluorad FC-135 0.1% w/v




300




93







400




88






Formulation B +




200




79






Fluorad FC-135 0.05% w/v




300




92







400




99






Formulation C +




200




79






Fluorad FC-135 0.25% w/v




300




97







400




97






Formulation C +




200




90






Fluorad FC-135 0.1% w/v




300




96







400




97






Formulation C +




200




80






Fluorad FC-135 0.05% w/v




300




96







400




99






10-01




200




93







300




97







400




98






10-02




200




71







300




89







400




89






10-03




200




71







300




87







400




98






10-04




200




76







300




100







400




100






10-05




200




91







300




99







400




97






10-06




200




57







300




95







400




88






10-07




200




64







300




68







400




94






10-08




200




89







300




96







400




99






10-09




200




80







300




77







400




94






10-10




200




90







300




94







400




98






10-11




200




81







300




100







400




96






10-12




200




86







300




92







400




95






10-13




200




86







300




99







400




100






10-14




200




97







300




100







400




100







200




99







300




100







400




100






10-16




200




92







300




100







400




100






10-17




200




92







300




99







400




100














Herbicidal effectiveness of Formulation C was very high on SIDSP in this test and accordingly enhancements are difficult to discern. However, remarkably strong performance was again seen with composition 10-15. containing just 0.05% lecithin and 0.05% Fluorad FC-135.




Example 12




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 12


a.


Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.

















TABLE 12a
















Components







Leci-




% w/w





sonicated

















Spray




thin




Fluorad




Silwet




Other




(*) Other




with






comp.




g/l




FC-135




L-77




(*)




ingredient




lecithin




















12-01




5.0








none






12-02




5.0





0.50






L-77






12-03




2.5








none






12-04




2.5




0.50







none






12-05




2.5




0.20







none






12-06




2.5




0.10







none






12-07




5.0






0.50




Diacid 1550




Diacid






12-08




5.0






0.10




Diacid 1550




Diacid






12-09




2.5






0.25




Diacid 1550




Diacid






12-10




2.5




0.25





0.05




Diacid 1550




Diacid






12-11




5.0




0.10





0.50




Genapol




Genapol











UD-030






12-12




5.0




0.05





0.20




Genapol




Genapol











UD-030






12-13




5.0




0.25





0.50




Neodol 25-3




Neodol






12-14




5.0




0.10





0.20




Neodol 25-3




Neodol














Velvetleaf (


Abutilon theophrasti,


ABUTH). Japanese millet (


Echinochloa crus


-


galli,


ECHCF) and momingglory (Ipomoea spp., IPOSS) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH, 18 days after planting ECHCF and 9 days after planting IPOSS. Evaluation of herbicidal inhibition was done 15 days after application.




In addition to compositions 12-01 to 12-14, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 12b.















TABLE 12b













Glyphosate








rate




% Inhibition















Spray composition




g a.e./ha




ABUTH




ECHCF




IPOSS


















Formulation B




200




24




53




33







300




47




37




37







400




64




46




64






Formulation B +




200




85




3




66






Silwet L-77 0.5% v/v




300




97




19




77







400




98




18




82






Formulation C




200




39




69




38







300




71




90




67







400




87




100




76






Formulation C +




200




90




8




72






Silwet L-77 0.5% v/v




300




95




50




79







400




100




90




73






Formulation B +




200




75




71




65






Fluorad FC-135 0.5% w/v




300




94




92




79







400




98




100




77






Formulation B +




200




75




67




67






Fluorad FC-135 0.25% w/v




300




85




73




71







400




96




97




75






Formulation B +




200




61




53




48






Fluorad FC-135 0.1% w/v




300




82




98




72







400




95




86




70






Formulation C +




200




81




61




69






Fluorad FC-135 0.5% w/v




300




75




75




71







400




84




84




77






Formulation C +




200




35




58




67






Fluorad FC-135 0.25% w/v




300




68




97




64







400




92




96




73






Formulation C +




200




40




84




51






Fluorad FC-135 0.1% w/v




300




79




94




58







400




99




86




74






12-01




200




69




69




62







300




82




82




73







400




88




84




77






12-02




200




81




75




67







300




83




74




72







400




95




93




75






12-03




200




48




69




70







300




82




93




71







400




94




100




72






12-04




200




68




78




64







300




90




94




76







400




96




99




79






12-05




200




75




86




68







300




86




95




72







400




96




89




80






12-06




200




80




95




57







300




85




82




60







400




96




91




73






12-07




200




41




72




64







300




76




82




68







400




80




98




77






12-08




200




40




71




70







300




51




91




76







400




77




98




72






12-09




200




43




74




64







300




58




95




76







400




73




100




77






12-10




200




43




85




65







300




74




75




65







400




83




99




76






12-11




200




39




71




66







300




61




88




71







400




89




99




73






12-12




200




54




57




59







300




79




77




75







400




89




84




71






12-13




200




69




72




69







300




59




66




69







400




86




81




76






12-14




200




54




62




65







300




65




77




69







400




84




81




74














Tank mixtures of Formulation B with Fluorad FC-135 gave greater herbicidal effectiveness than Formulation C alone, without the attendant antagonism on ECHCF so characteristic of Silwet L-77. Addition of Fluorad FC-135 to glyphosate compositions containing 0.25% lecithin enhanced herbicidal effectiveness on ABUTH and ECHCF, but not, in this test, on IPOSS (compare compositions 12-04 to 12-06 with composition 12-03).




Example 13




Compositions 12-01 to 12-14 of Example 12, and tank mixtures of Formulations B and C with Fluorad FC-135, were tested in this Example. Prickly sida (


Sida spinosa,


SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 23 days after planting SIDSP, and after application.




Formulations B and C, alone and tank mixed with 0.5% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 13.
















TABLE 13












Glyphosate rate




% Inhibition







Spray composition




g a.e./ha




SIDSP













Formulation B




200




37








300




47








400




50







Formulation B +




200




93







Silwet L-77 0.5% v/v




300




100








400




99







Formulation C




200




47








300




63








400




86







Formulation C +




200




88







Silwet L-77 0.5% v/v




300




92








400




99







Formulation B +




200




51







Fluorad FC-135 0.5% w/v




300




79








400




84







Formulation B +




200




49







Fluorad FC-135 0.25% w/v




300




53








400




85







Formulation B +




200




44







Fluorad FC-135 0.1% w/v




300




58








400




70







Formulation C +




200




74







Fluorad FC-135 0.5% w/v




300




89








400




97







Formulation C +




200




52







Fluorad FC-135 0.25% w/v




300




70








400




75







Formulation C +




200




45







Fluorad FC-135 0.1% w/v




300




74








400




87







12-01




200




62








300




76








400




89







12-02




200




59








300




54








400




73







12-03




200




56








300




89








400




80







12-04




200




72








300




89








400




96







12-05




200




66








300




87








400




84







12-06




200




60








300




74








400




86







12-07




200




57








300




78








400




89







12-08




200




59








300




67








400




70







12-09




200




57








300




65








400




74







12-10




200




53








300




77








400




77







12-11




200




58








300




71








400




87







12-12




200




54








300




70








400




82







12-13




200




65








300




75








400




82







12-14




200




61








300




77








400




81















On SIDSP in this test, tank mix addition of Fluorad FC-135 to Formulation B enhanced herbicidal effectiveness over that obtained with Formulation C alone, only at the 0.5% concentration of Fluorad FC-135. Likewise, when added to a glyphosate composition containing 0.25% lecithin, Fluorad FC-135 enhanced herbicidal effectiveness most significantly at the 0.5% concentration (composition 12-04).




Example 14




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 14


a.


Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The following compositions had a pH of approximately 5: 14-01, 14-03, 14-07, 14-08, 14-10 and 14-12 to 14-17. All others were adjusted to a pH of approximately 7.















TABLE 14a













% w/w




Components
















Spray




Lecithin




Fluorad




Silwet




Diacid




sonicated with






composition




g/l




FC-135




L-77




1550




lecithin









14-01




5.0







none






14-02




5.0







none






14-03




2.5







none






14-04




2.5







none






14-05




5.0







glyphosate






14-06




5.0





0.50





L-77






14-07




5.0





0.50





L-77






14-08




2.5





0.50





L-77






14-09




2.5





0.50





L-77






14-10




2.5





0.25





glyphosate






14-11




2.5





0.25





glyphosate






14-12




2.5




0.25






none






14-13




2.5




0.25






glyphosate






14-14




2.5




0.10






none






14-15




2.5




0.10






glyphosate






14-16




2.5





0.25




0.25




L-77, Diacid






14-17




2.5





0.10




0.05




L-77, Diacid














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and 20 days after planting ECHCF, and evaluation of herbicidal inhibition was done 20 days after application.




In addition to compositions 14-01 to 14-17, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at two concentrations. Formulations B and C, alone and tank mixed with 0.5% and 0.25% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 14b.















TABLE 14b













Glyphosate rate




% Inhibition














Spray composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




200




53




43







300




73




50







400




91




74






Formulation B +




200




86




24






Silwet L-77 0.5% v/v




300




88




15







400




94




58






Formulation B +




200




80




22






Silwet L-77 0.25% w/v




300




93




38







400




87




38






Formulation C




200




56




88







300




86




98







400




94




98






Formulation C +




200




87




23






Silwet L-77 0.5% v/v




300




93




52







400




91




60






Formulation C +




200




79




42






Silwet L-77 0.25% v/v




300




83




73







400




87




95






Formulation B +




200




79




49






Fluorad FC-135 0.25% w/v




300




89




77







400




94




85






Formulation B +




200




73




64






Fluorad FC-135 0.1% w/v




300




89




68







400




92




75






Formulation C +




200




73




86






Fluorad FC-135 0.25% w/v




300




75




90







400




90




95






Formulation C +




200




53




97






Fluorad FC-135 0.1% w/v




300




89




96







400




91




99






14-01




200




71




66







300




89




62







400




97




85






14-02




200




83




52







300




89




72







400




82




93






14-03




200




54




53







300




89




84







400




93




77






14-04




200




81




38







300




94




76







400




98




88






14-05




200




85




53







300




95




80







400




94




91






14-06




200




80




0







300




95




100







400




98




94






14-07




200




72




50







300




95




84







400




98




92






14-08




200




81




69







300




99




83







400




100




80






14-09




200




86




38







300




94




80







400




96




90






14-10




200




58




67







300




82




85







400




92




90






14-11




200




83




64







300




88




74







400




90




88






14-12




200




89




90







300




100




88







400




100




98






14-13




200




95




91







300




93




97







400




100




98






14-14




200




88




93







300




93




85







400




98




90






14-15




200




85




87







300




98




98







400




96




100






14-16




200




76




72







300




83




87







400




89




97






14-17




200




53




67







300




48




62







400




82




85














Compositions 14-12 to 14-15, containing 0.25% lecithin together with Fluorad FC-1 35, exhibited much greater herbicidal effectiveness on both ABUTH and ECHCF than composition 14-03, containing 0.25% lecithin but no Fluorad FC-135, or even composition 14-01, containing 0.5% lecithin but no Fluorad FC-135. No great or consistent difference was seen between compositions where glyphosate had been sonicated together with the lecithin (14-13 and 14-15) than where the lecithin had been sonicated alone (14-12 and 14-14).




Example 15




Compositions 14-01 to 14-17 of Example 14, and tank mixtures of Formulations B and C with Fluorad FC-135, were tested in this Example. Prickly sida (


Sida spinosa,


SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 22 days after planting SIDSP, and evaluation of herbicidal inhibition was done 19 days after application.




Formulations B and C, alone and tank mixed with 0.5% and 0.25% Silwet L-77, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 15.














TABLE 15










Glyphosate rate




% Inhibition






Spray composition




g a.e./ha




SIDSP











Formulation B




200




23







300




37







400




32






Formulation B +




200




30






Silwet L-77 0.5% v/v




300




39







400




45






Formulation B




200




28






Silwet L-77 0.25% w/v




300




49







400




28






Formulation C




200




41







300




54







400




84






Formulation C +




200




43






Silwet L-77 0.5% v/v




300




66







400




86






Formulation C +




200




17






Silwet L-77 0.25% v/v




300




35







400




58






Formulation B +




200




48






Fluorad FC-135 0.25% w/v




300




60







400




62






Formulation B +




200




31






Fluorad FC-135 0.1% w/v




300




47







400




75






Formulation C +




200




43






Fluorad FC-135 0.25% w/v




300




57







400




71






Formulation C +




200




32






Fluorad FC-135 0.1% w/v




300




71







400




63






14-01




200




51







300




55







400




76






14-02




200




51







300




68







400




84






14-03




200




55







300




51







400




72






14-04




200




50







300




64







400




75






14-05




200




46







300




53







400




61






14-06




200




40







300




44







400




73






14-07




200




23







300




32







400




39






14-08




200




18







300




44







400




57






14-09




200




25







300




30







400




43






14-10




200




19







300




36







400




38






14-11




200




35







300




48







400




57






14-12




200




65







300




80







400




88






14-13




200




68







300




75







400




87






14-14




200




76







300




76







400




72






14-15




200




54







300




73







400




84






14-16




200




44







300




51







400




63






14-17




200




23







300




45







400




57














Compositions 14-12 to 14-15, containing 0.25% lecithin together with Fluorad FC-135, exhibited greater herbicidal effectiveness on SIDSP than composition 14-03, containing 0.25% lecithin but no Fluorad FC-135, or even composition 14-01, containing 0.5% lecithin but no Fluorad FC-135. No great or consistent difference was seen between compositions where glyphosate had been sonicated together with the lecithin (14-13 and 14-15) than where the lecithin had been sonicated alone (14-12 and 14-14).




Example 16




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 16


a.


Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.

















TABLE 16a













Leci-




% w/w





Components
















Spray




thin




Fluorad





(*) Other




sonicated with






comp.




g/l




FC-135




Other (*)




ingredient




lecithin









16-01




2.5







none






16-02




2.5







glyphosate






16-03




2.5




0.25






none






16-04




2.5




0.25






glyphosate






16-05




2.5





0.25




Silwet 800




none






16-06




2.5





0.25




Silwet 800




Silwet 800






16-07




2.5





0.25




Silwet 800




Silwet,











glyphosate






16-08




0.5







none






16-09




0.5







glyphosate






16-10




0.5




0.05






none






16-11




0.5




0.05






glyphosate






16-12




0.5




0.03




0.02




Silwet L-77




Silwet L-77






16-13




0.5





0.05




methyl caprate




Me caprate






16-14




0.5




0.05




0.05




methyl caprate




Me caprate






16-15




0.5




0.05




0.05




methyl caprate




Me caprate,











glyphosate






16-16




0.5





0.01




PVA




none






16-17




0.5





0.01




PVA




glyphosate






16-18




0.5




0.05




0.01




PVA




glyphosate






16-19




0.5





0.05 + 0.01




L-77 + PVA




Silwet L-77














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicidal inhibition was done 17 days after application.




In addition to compositions 16-01 to 16-19, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at two concentrations. Formulations B and C, alone and tank mixed with 0.5% Silwet 800, were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 16b.















TABLE 16b













Glyphosate rate




% Inhibition














Spray composition




g a.e./ha




ABUTH




ECHCF









Formulation B




150




13




28







250




37




51







350




56




38






Formulation B +




150




81




15






Silwet 800 0.25% v/v




250




89




17







350




91




20






Formulation C




150




32




65







250




59




91







350




85




89






Formulation C +




150




91




17






Silwet 800 0.25% v/v




250




91




23







350




95




48






Formulation B +




150




31




58






Fluorad FC-135 0.25% w/v




250




53




68







350




71




84






Formulation B +




150




31




29






Fluorad FC-135 0.05% w/v




250




44




69







350




95




79






Formulation C +




150




46




45






Fluorad FC-135 0.25% w/v




250




69




79







350




86




77






Formulation C +




150




44




57






Fluorad FC-135 0.05% w/v




250




60




87







350




86




88






16-01




150




55




50







250




87




81







350




89




88






16-02




150




56




54







250




89




69







350




87




98






16-03




150




89




68







250




89




84







350




91




90






16-04




150




63




68







250




89




86







350




99




89






16-05




150




81




51







250




87




84







350




94




26






16-06




150




67




0







250




93




62







350




94




81






16-07




150




81




35







250




84




51







350




95




62






16-08




150




59




51







250




84




69







350




98




90






16-09




150




64




59







250




85




61







350




94




96






16-10




150




73




74







250




87




83







350




98




96






16-11




150




76




64







250




88




79







350




94




81






16-12




150




59




46







250




82




88







350




92




82






16-13




150




61




45







250




90




69







350




93




90






16-14




150




76




50







250




95




73







350




99




91






16-15




150




78




67







250




95




80







350




99




85






16-16




150




48




42







250




77




87







350




87




75






16-17




150




47




63







250




85




67







350




90




78






16-18




150




55




46







250




82




77







350




90




87






16-19




150




32




23







250




43




31







350




76




65














As in Example 10, glyphosate compositions (16-10 and 16-11) containing just 0.05% lecithin and 0.05% Fluorad FC-135 exhibited surprisingly great herbicidal efficacy in this test. Sonicating the lecithin in the presence of glyphosate in an effort to encapsulate some of the glyphosate (composition 16-11) did not give an advantage in performance over sonicating the lecithin alone (composition 16-10); indeed on ECHCF herbicidal efficacy was slightly better without such efforts to encapsulate the glyphosate. Addition of methyl caprate to compositions containing lecithin with or without Fluorad FC-135 (16-13 to 16-15) improved herbicidal effectiveness on ABUTH but had little effect on ECHCF.




Example 17




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 17


a.


Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was, adjusted to approximately 7.
















TABLE 17a











Spray





% w/w





Components
















compo-




Lecithin




Fluorad





(*) Other




sonicated with






sition




g/l




FC-135




Other (*)




ingredient




lecithin









17-01




2.5







none






17-02




2.5




0.25






none






17-03




2.5




0.25






glyphosate






17-04




2.5




0.25




0.025




PVA




none






17-05




1.0







none






17-06




1.0







glyphosate






17-07




1.0




0.10






none






17-08




1.0




0.10






glyphosate






17-09




1.0




0.05






none






17-10




1.0




0.05






glyphosate






17-11




1.0





0.100




PVA




none






17-12




1.0





0.025




PVA




none






17-13




1.0




0.05




0.025




PVA




none






17-14




1.0





0.100




sodium cholate




Na cholate






17-15




1.0





0.020




sodium cholate




Na cholate






17-16




1.0




0.05




0.020




sodium cholate




Na cholate






17-17




0.5







none






17-18




0.5




0.05






glyphosate






17-19




0.5




0.05




0.020




sodium cholate




Na cholate














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




In addition to compositions 17-01 to 17-19, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 17b.














TABLE 17b












Glyphosate rate




% Inhibition














Spray composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




200




32




25







300




50




34







400




54




35






Formulation C




200




59




92







300




76




100







400




93




97






Formulation B




200




43




48






+Fluorad FC-135 0.25% w/v




300




64




52







400




84




71






Formulation B




200




61




78






+Fluorad FC-135 0.1% w/v




300




65




59







400




100




86






Formulation B




200




58




30






+Fluorad FC-135 0.05% w/v




300




82




55







400




88




77






Formulation C




200




53




55






+Fluorad FC-135 0.25% w/v




300




76




68







400




88




93






Formulation C




200




59




70






+Fluorad FC-135 0.1% w/v




300




89




85







400




93




83






Formulation C




200




60




72






+Fluorad FC-135 0.05 % w/v




300




82




100







400




94




94






17-01




200




73




52







300




88




80







400




94




90






17-02




200




83




80







300




96




83







400




97




95






17-03




200




86




73







300




95




79







400




98




94






17-04




200




73




72







300




94




86







400




96




93






17-05




200




67




68







300




94




74







400




96




91






17-06




200




65




61







300




79




82







400




91




81






17-07




200




75




65







300




92




84







400




98




91






17-08




200




66




70







300




87




96







400




97




97






17-09




200




83




73







300




9




83







400




97




89






17-10




200




89




70







300




92




79







400




91




74






17-11




200




65




58







300




86




86







400




97




100






17-12




200




75




64







300




79




85







400




91




87






17-13




200




79




53







300




81




83







400




96




88






17-14




200




56




69







300




80




95







400




92




93






17-15




200




57




77







300




67




91







400




88




90






17-16




200




88




82







300




85




87







400




76




72






17-17




200




53




66







300




71




72







400




87




83






17-18




200




89




85







300




79




72







400




65




60






17-19




200




77




65







300




87




85







400




92




94














In glyphosate compositions containing lecithin and Fluorad FC-135, no consistent difference in herbicidal effectiveness was observed between those where lecithin was sonicated alone (17-02, 17-07, 17-09) and those where glyphosate and lecithin were sonicated together (17-03, 17-08, 17-10). The anomalous inversion of the apparent rate response to glyphosate seen with composition 17-18 is believed to be the result of an error in application or recording and the data for this composition should be ignored in this Example.




Example 18




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 18


a.


Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.















TABLE 18a













% w/w
















Spray




Lecithin




Fluorad





Components






composition




g/l




FC-135




PVA




sonicated with lecithin









18-01




2.5






none






18-02




1.0






none






18-03




0.5






none






18-04




0.2






none






18-05




1.0




0.25





glyphosate






18-06




1.0




0.25





glyphosate






18-07




1.0




0.10





none






18-08




1.0




0.10





glyphosate






18-09




0.5




0.05





none






18-10




0.5




0.05





glyphosate






18-11




2.5





0.10




none














Hemp sesbania (


Sesbania exaltata,


SEBEX) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 22 days after planting SEBEX, and evaluation of herbicidal inhibition was done 21 days after application.




In addition to compositions 18-01 to 18-1 1. spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone, and Formulation B tank mixed with 0.1% PVA (polyvinyl alcohol), were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 18b.
















TABLE 18b












Glyphosate rate




% Inhibition







Spray composition




g a.e./ha




SEBEX




























Formulation B




500




43








1000




54








1500




44







Formulation B




500




53







+PVA 0.1% w/v




1000




45








1500




44







Formulation C




500




56








1000




62








1500




63







Formulation B




500




40







+Fluorad FC-135 0.25% w/v




1000




45








1500




60







Formulation B




500




33







+Fluorad FC-135 0.1% w/v




1000




51








1500




53







Formulation B




500




21







+Fluorad FC-135 0.05% w/v




1000




18








1500




29







Formulation C




500




34







+Fluorad FC-135 0.25% w/v




1000




41








1500




58







Formulation C




500




50







+Fluorad FC-135 0.1% w/v




1000




43








1500




52







Formulation C




500




48







+Fluorad FC-135 0.05% w/v




1000




49








1500




46







18-01




500




22








1000




33








1500




37







18-02




500




16








1000




24








1500




28







18-03




500




15








1000




24








1500




27







18-04




500




17








1000




13








1500




31







18-05




500




28








1000




64








1500




68







18-06




500




64








1000




51








1500




61







18-07




500




65








1000




51








1500




63







18-08




500




50








1000




56








1500




30







18-09




500




40








1000




59








1500




66







18-10




500




31








1000




23








500




49







18-11




500




43








1000




39








500




74















Glyphosate activity on SEBEX was extremely weak in this test and no firm conclusions can be drawn.




Example 19




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 19a. Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.















TABLE 19a









Spray




Lecithin




% w/w




Components






composition




g/l




Fluorad FC-135




sonicated with lecithin











19-01




2.5





none






19-02




1.0





none






19-03




0.5





none






19-04




0.2





none






19-05




1.0




0.25




none






19-06




1.0




0.25




glyphosate














Sicklepod (


Cassia obtusifolia,


CASOB) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 22 days after planting CASOB, and evaluation of herbicidal inhibition was done 21 days after application.




In addition to compositions 19-01 to 19-06, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-35 at two concentrations. Formulations B and C alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 19b.
















TABLE 19b












Glyphosate rate




% Inhibition







Spray composition




g a.e./ha




CASOB




























Formulation B




500




35








800




37








1200




34







Formulation C




500




49








800




49








1200




66







Formulation B




500




45







+Fluorad FC-135




800




50







0.25% w/v




1200




71







Formulation B




500




49







+Fluorad FC-135




800




49







0.1% w/v




1200




78







Formulation C




500




60







+Fluorad FC-135




800




75







0.25% w/v




1200




68







Formulation C




500




47







+Fluorad FC-135




800




85







0.1% w/v




1200




74







19-01




500




54








800




51








1200




43







19-02




500




37








800




69








1200




52







19-03




500




35








1200




43







19-04




500




71








800




69








1200




57







19-05




500




47








800




73








1200




89







19-06




500




49








800




5I








1200




73















On CASOB, the addition of Fluorad FC-135 to a glyphosate composition containing lecithin significantly enhanced herbicidal effectiveness (compare compositions 19-05 and 19-02). However, where glyphosate was sonicated together with the lecithin (composition 19-06), herbicidal effectiveness was reduced.




Example 20




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 20a. Process (iii) was followed for all compositions. using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.















TABLE 20a













% w/w
















Spray




Lecithin




Fluorad




Diacid




Components






composition




g/l




FC-135




1550




sonicated with lecithin









20-01




2.5






none






20-02




0.5






none






20-03




0.2






none






20-04




2.5




0.05





none






20-05




0.5




0.05





none






20-06




0.2




0.05





none






20-07




0.5





0.05




Diacid














Common lambsquarter (


Chenopodium album,


CHEAL) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 31 days after planting CHEAL, and evaluation of herbicidal inhibition was done 18 days after application.




In addition to compositions 20-01 to 20-07, spray compositions were prepared by tank mixing Formulations B and C with 0.5% Fluorad FC-135. Formulations B and C alone were applied as comparative treatment. Results, averaged for all replicates of each treatment, are shown in Table 20b.
















TABLE 20b












Glyphosate rate




% Inhibition







Spray composition




g a.e./ha




CHEAL




























Formulation B




150




0








250




0








350




3







Formulation C




150




18








250




68








350




98







Formulation B




150




0







+Fluorad FC-135 0.05% w/v




250




50








350




5







Formulation C




150




3







+Fluorad FC-135 0.05% w/v




250




50








350




60







20-01




150




0








250




27








350




60







20-02




150




0








250




5








350




8







20-03




150




5








250




0








350




8







20-04




150




18








250




29








350




63







20-05




150




17








250




14








350




87







20-06




150




44








250




40








350




38







20-07




150




10








250




35








350




73















Glyphosate activity on CHEAL was very weak in this test and no definitive conclusions can be drawn. However. none of the compositions of the invention performed as well as the commercial standard Formulation C in this test. Fluorad FC-135 at the extremely low concentration of 0.05% was ineffective as a tank-mix additive, but addition of 0.05% Fluorad FC-135 did enhance the performance of compositions containing lecithin (compare compositions 20-04 to 20-06 with 20-01 to 20-03).




Example 21




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 21a. Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.















TABLE 21a













% w/w




Components
















Spray




Lecithin




Fluorad




Aerosol




Methyl




sonicated






composition




g/l




FC-135




OT




caprate




with lecithin



















21-01




2.5







none






21-02




2.5







glyphosate






21-03




1.0







none






21-04




1.0







glyphosate






21-05




0.5







none






21-06




0.5







glyphosate






21-07




0.2







none






21-08




0.2







glyphosate






21-09




0.5





0.05





none






21-10




0.5





0.05





AOT, glyphosate






21-11




0.5





0.05





AOT






21-12




2.5




0.25






none






21-13




0.5




0.05






none






21-14




0.5




0.05






glyphosate






21-15




0.5






0.05




Me caprate






21-16




0.5




0.05





0.05




Me caprate






21-17




0.2




0.02






none






21-18




0.2




0.02






glyphosate






21-19




0.2






0.02




Me caprate














Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF), and prickly sida (


Sida spinosa


, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 22 days after planting ECHCF. No record was found for the planting date for SIDSP. Evaluation of herbicidal inhibition was done 20 days after application.




In addition to compositions 21-01 to 21-19, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 21b.














TABLE 21b












Glyphosate








rate




% Inhibition















Spray composition




g a.e./ha




ABUTH




ECHCF




SIDSP


















Formulation B




150




16




23




30







250




17




33




57







350




24




43




65






Formulation C




50




18




58




53







250




30




71




79







350




49




83




94






Formulation B




150




27




59




56






+Fluorad FC-135




250




45




84




81






0.25% w/v




350




55




82




91






Formulation B




150




17




43




56






+Fluorad FC-135




250




21




56




75






0.1% w/v




350




64




80




90






Formulation B




150




22




27




38






+Fluorad FC-135




250




37




49




69






0.02% w/v




350




48




68




94






Formulation C




150




41




41




59






+Fluorad FC-135




250




57




53




85






0.25% w/v




350




67




67




94






Formulation C




150




26




39




67






+Fluorad FC-135




250




46




66




88






0.05% w/v




350




75




73




93






Formulation C




150




30




52




66






+Fluorad FC-135




250




67




50




89






0.02% w/v




350




61




88




92






21-01




150




35




62




64







250




63




77




90







350




71




83




85






21-02




150




35




44




67







250




53




79




86







350




58




92




90






21-03




150




37




50




71







250




53




76




90







350




73




63




97






21-04




150




29




46




61







250




43




77




85







350




70




85




96






21-05




150




12




36




59







250




43




55




83







350




53




77




87






21-06




150




19




69




67







250




62




47




84







350




58




60




95






21-07




150




14




59




59







250




39




63




75







350




46




77




91






21-08




150




36




37




64







250




38




68




82







350




47




80




79






21-09




150




8




35




27







250




9




51




56







350




36




58




67






21-10




150




5




33




24







250




15




73




47







350




30




66




67






21-11




150




38




49




73







250




62




75




89







350




71




75




98






21-12




150




7




41




21







250




18




67




38







350




30




64




61






21-13




150




39




72




65







250




65




55




76







350




70




68




90






21-14




150




51




53




66







250




60




82




85







350




65




83




95






21-15




150




15




59




61







250




31




54




83







350




57




67




84






21-16




50




36




79




66







250




50




60




95







350




71




95




95






21-17




150




30




52




75







250




54




60




84







350




48




84




93






21-18




50




43




75




69







250




47




78




88







350




missing




missing




90






21-19




50




13




42




61







250




29




51




79







350




42




69




90














In this test the concentration of Fluorad FC-135 which had to be added in tank-mix to Formulation B to bring its herbicidal performance up to that of Formulation C was approximately 0.25% for ECHCF, 0.1% for SIDSP and 0.02% for ABUTH. The herbicidal effectiveness of composition 21-12 (0.25% lecithin, 0.25% Fluorad FC-135) was uncharacteristically weak in this test. However, composition 21-13 (0.05% lecithin, 0.05% Fluorad FC-135) performed well as in previous tests, exceeding the herbicidal effectiveness of Formulation C on ABUTH, at least equalling it on SIDSP and not quite equalling it on ECHCF. Contrary to results obtained in other tests, improved effectiveness on ECHCF and SIDSP was obtained by sonicating the glyphosate with the lecithin (composition 21-14 versus 21-13). The inclusion of methyl caprate (compositions 21-15 and 21-16) also improved efficacy on these species. Surprisingly high herbicidal effectiveness was seen in this test with compositions containing ultra-low concentrations of lecithin and Fluorad FC-135 (0.02% of each, 21-17 and 21-18).




Example 22




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 22a. Process (iv) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of these compositions was not recorded.













TABLE 22a












% w/w















Concentrate




Glyphosate






Fluorad






composition




a.e.




Lecithin




MON 0818




FC-135


















22-01




10






5.0






22-02




10






10.0






22-03




10






12.5






22-04




10






15.0






22-05




10






20.0






22-06




10






30.0






22-07




15




4.0




1.0






22-08




20




5.0




0.5






22-09




20




5.0




1.0






22-10




20




5.0




2.0






22-11




20




4.0




1.0






22-12




25




5.0




0.5






22-13




25




5.0




1.0






22-14




25




5.0




2.0






22-15




25




4.0




1.0






22-16




25




5.0




5.0














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and 16 days after planting ECHCF, and evaluation of herbicidal inhibition was done 14 days after application.




Formulation C was applied as a comparative treatment. Results, averaged for all replicates of each treatment, are shown in Table 22b.















TABLE 22b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation C




56




13




45







112




43




75







224




64




94







448




88




97






22-01




112




38




61







224




56




80







448




76




97






22-02




112




50




51







224




69




91







448




81




97






22-03




112




51




63







224




64




83







448




81




96






22-04




112




53




61







224




71




91







448




78




95






22-05




112




41




56







224




70




85







448




75




97






22-06




112




38




53







224




63




89







448




75




94






22-07




112




48




53







224




49




84







448




75




90






22-08




112




31




60







224




53




84







448




66




90






22-09




112




26




56







224




53




85







448




78




96






22-10




112




36




60







224




53




85







448




79




98






22-11




112




41




59







224




49




73







448




76




95






22-12




112




30




56







224




50




74







448




65




89






22-13




112




34




55







224




44




80







448




73




95






22-14




112




39




61







224




56




85







448




69




91






22-15




112




31




55







224




56




69







448




79




95






22-16




112




29




64







224




58




86







448




78




91














None of the concentrate compositions of this Example containing 10% glyphosate a.e. and varying amounts of Fluorad FC-135 (22-01 to 22-06) exhibited greater herbicidal effectiveness than the commercial standard Formulation C. It should be noted that the amounts of Fluorad FC-135 used in this Example were extremely high, the weight/weight ratio of Fluorad FC-135 to glyphosate a.e. ranging from 1:2 to 3:1.




Example 23




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 23a. Process (iv) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was approximately 5.















TABLE 23a













% w/w




Components
















Concentrate




Glyphosate





MON




Fluorad




sonicated






composition




a.e.




Lecithin




0818




FC-135




with lecithin









23-01




20




5.0




2.0





none






23-02




20




4.0




1.0





none






23-03




20




5.0




2.0





glyphosate






23-04




20




4.0




1.0





glyphosate






23-05




20




5.0




2.0




5.0




none














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and 18 days after planting ECHCF, and evaluation of herbicidal inhibition was done 14 days after application.




Formulations B and C were applied as comparative treatments. Results, averaged for all replicates of each treatment., are shown in Table 23b.















TABLE 23b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




112




33




53







224




58




78







336




80




89







448




79




88






Formulation C




112




49




79







224




59




94







336




84




100







448




95




100






23-01




112




39




66






224




63




93






336




81




98






448




86




100






23-02




112




29




46






224




55




83






336




79




91






448




85




95






23-03




112




30




59






224




60




98






336




80




100






448




81




100






23-04




112




26




51






224




53




83






336




76




86






448




86




99






23-05




112




46




51






224




59




89






336




79




96






448




89




98














Concentrate composition 23-05 (5% lecithin, 2% MON 0818, 5% Fluorad FC-135) did not exhibit greater herbicidal effectiveness in this test than composition 23-01 lacking the Fluorad FC-135.




Example 24




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 24a. Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of these compositions was not recorded.















TABLE 24a









Spray




Lecithin




% w/w




Components






composition




g/l




Fluorad FC-135




sonicated with lecithin











24-01




2.5





none






24-02




1.0





none






24-03




0.5





none






24-04




0.2





none






24-05




0.1





none






24-06




2.5




0.25




none






24-07




0.5




0.05




none






24-08




0.2




0.02




none






24-09




0.2




0.02




glyphosate






24-10




0.2




0.02




FC-135






24-11




0.1




0.01




none






24-12




0.1




0.01




glyphosate






24-13




0.1




0.02




FC-135






24-14




0.5




0.02




none






24-15




0.5




0.02




glyphosate






24-16




0.5




0.02




FC-135














Yellow nutsedge (


Cyperus esculentus


, CYPES) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 29 days after planting, and evaluation of herbicidal inhibition was done 33 days after application.




In addition to compositions 24-01 to 24-16, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone were applied as comparative treatments. Results. averaged for all replicates of each treatment, are shown in Table 24b.
















TABLE 24b












Glyphosate rate




% Inhibition







Spray composition




g a.e./ha




CYPES




























Formulation B




400




32








750




68








1000




70







Formulation C




400




25








750




66








1000




89







Formulation B




400




49







+ Fluorad FC-135 0.25% w/v




750




75








1000




82







Formulation B




400




53







+ Fluorad FC-135 0.05% w/v




750




74








1000




64







Formulation B




400




56







+ Fluorad FC-135 0.02% w/v




750




83








1000




83







Formulation B




400




61







+ Fluorad FC-135 0.01% w/v




750




67







1000




88







Formulation C




400




73







+ Fluorad FC-135 0.25% w/v




750




47







1000




79







Formulation C




400




50







+ Fluorad FC-1350.05% w/v




750




73








1000




81







Formulation C




400




41







+ Fluorad FC-135 0.02% w/v




750




79








1000




81







Formulation C




400




67







+ Fluorad FC-135 0.01% w/v




750




77








1000




72







24-01




400




62








750




73








1000




100







24-02




400




61








750




85








1000




92







24-03




400




81








750




83








1000




87







24-04




400




59








750




79








1000




79







24-05




400




69








750




69








1000




91







24-06




400




75








750




80








1000




96







24-07




400




65








750




69








1000




89







24-08




400




67








750




69








1000




87







24-09




400




76








750




77








1000




80







24-10




400




71








750




75








1000




86







24-11




400




69








750




77








1000




85







24-12




400




59








750




85








1000




95







24-13




400




61








750




75








1000




81







24-14




400




64








750




83








1000




90







24-15




400




53








750




81








1000




86







24-16




400




85








750




86








1000




81















The tank-mix treatments of this Example show surprisingly little effect on herbicidal effectiveness on CYPES of reducing Fluorad FC-135 concentration from 0.25% all the way down to 0.01%. At this extraordinarily low concentration, the tank mix of Formulation B with Fluorad FC-135 still performed equal or better than Formulation C alone. Lecithin alone was an unexpectedly effective excipient for glyphosate in this test (see compositions 24-01 to 24-05) and the addition of Fluorad FC-135 to lecithin did not in every case give further enhancement of herbicidal efficacy.




Example 25




Glyphosate-containing spray compositions were prepared by tank-mixing Formulation B with excipients as shown in Table 25. Soybean lecithin (20% phospholipid, Avanti) was used in the form of a 10% dispersion prepared by sonication as in process (iii).




Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 21 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicidal inhibition was done 21 days after application. Results, averaged for all replicates of each treatment, are shown in Table 25.















TABLE 25













Add.




% Inhibition
















Glyphosate




Glyphosate rate





rate




AB-







composition




g a.e./ha




Additive




% w/v




UTH




ECHCF



















Formulation B




56






3




17







112






7




38







224






30




58







336






60




67






None




0




MON 0818




5.0




7




30








Fluorad




5.0




5




3








FC-135








lecithin




5.0




0




0






Formulation B




56




MON 0818




0.005




0




48







112






3




60







224






53




85







336






58




87






Formulation B




56




MON 0818




0.01




3




50







112






10




67







224






52




87







336






67




92






Formulation B




56




MON 0818




0.05




7




52







112






10




67







224






60




93







336






68




96






Formulation B




56




MON 0818




0.1




10




55







112






12




70







224






57




97







336






80




97






Formulation B




56




MON 0818




0.2




10




65







112






22




70







224






58




97







336






85




97






Formulation B




56




MON 0818




0.5




13




65







112






33




77







224






72




99







336






88




100






Formulation B




56




MON 0818




1.0




15




68







112






55




80







224






78




98







336






95




100






Formulation B




56




MON 0818




2.0




27




75







112






62




78







224






83




100







336






100




99






Formulation B




56




MON 0818




5.0




23




55







112






53




77







224






72




90







336






97




88






Formulation B




56




Fluorad




0.005




2




47







112




FC-135





10




50







224






25




70







336






55




78






Formulation B




56




Fluorad




0.01




7




40







112




FC-135





15




57







224






70




67







336






80




80






Formulation B




56




Fluorad




0.05




2




48







112




FC-135





15




57







224






70




78







336






78




88






Formulation B




56




Fluorad




0.1




5




45







112




FC-135





18




58







224






75




87







336






80




90






Formulation B




56




Fluorad




0.2




12




48







112




FC-135





27




60







224






75




90







336






97




93






Formulation B




56




Fluorad




0.5




3




47







112




FC-135





12




57







224






75




80







336






78




83






Formulation B




56




Fluorad




1.0




5




43







112




FC-135





10




52







224






77




75







336






78




77






Formulation B




56




Fluorad




2.0




7




42







112




FC-135





10




47







224






65




65







336






72




77






Formulation B




56




Fluorad




5.0




2




38







112




FC-135





5




47







224






63




60







336






67




63






Formulation B




56




lecithin




0.005




0




10







112






10




45







224






67




70







336






67




77






Formulation B




56




lecithin




0.01




2




20







112






12




47







224






63




70







336






68




85






Formulation B




56




lecithin




0.05




3




32







112






12




52







224






63




73







336






72




82






Formulation B




56




lecithin




0.1




8




37







112






10




50







224






65




73







336






78




83






Formulation B




56




lecithin




0.2




5




45







112






43




63







224






68




82







336






80




92






Formulation B




56




lecithin




0.5




13




50







112






42




65







224






67




88







336






68




87






Formulation B




56




lecithin




1.0




13




52







112






50




72







224






67




80







336






68




88






Formulation B




56




lecithin




2.0




10




53







112






37




72







224






72




88







336






87




97






Formulation B




56




lecithin




5.0




10




50







112






55




73







224






72




80







336






78




95














This test was an expanded rate titration study of MON 0818, Fluorad FC-135 and lecithin as tank-mix adjuvants for glyphosate as Formulation B. On ABUTH, the optimum adjuvant concentration was 2.0% for MON 0818, 0.2% for Fluorad FC-135 and 0.2% or higher for lecithin. On ECHCF, the optimum adjuvant concentration was 0.5% to 2.0% for MON 0818, 0.2% for Fluorad FC-135 and 2.0% for lecithin.




Example 26




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 26a. Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.

















TABLE 26a













Spray




Lecithin




% w/w

















composition




g/l




Fluorad FC-135




Aerosol OT




















26-01






0.1







26-02






0.05







26-03






0.02







26-04





0.1




0.1







26-05





0.05




0.05







26-06





0.02




0.02







26-07




1.0





0.10







26-08




1.0




0.10




0.10







26-09




1.0







26-10




1.0




0.10







26-11




0.5







26-12




0.5





0.05







26-13




0.5




0.05







26-14




0.5




0.05




0.05







26-15




0.2








26-16




0.2





0.02







26-17




0.2




0.02







26-18




0.2




0.02




0.02















Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and prickly sida (Sida spinosa, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH, 19 days after planting ECHCF, and 26 days after planting SIDSP. Evaluation of herbicidal inhibition was done for ABUTH and ECHCF 15 days after application and for SIDSP 21 days after application.




In addition to compositions 26-01 to 26-18, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 26b.















TABLE 26b













Glyphosate rate




% Inhibition















Spray composition




g a.e./ha




ABUTH




ECHCF




SIDSP


















Formulation B




150




37




71




57







250




57




79




69







400




74




86




80







500




79




89




74






Formulation C




150




48




42




58







250




71




80




81







400




88




100




88







500




92




100




86






Formulation B




150




87




62




66






+ Fluorad FC-135 0.1%




250




87




96




70






w/v




400




91




94




75






Formulation B




150




61




48




65






+ Fluorad FC-135 0.05%




250




81




69




71






w/v




400




90




91




67






Formulation B




150




58




32




62






+ Fluorad FC-135 0.02%




250




75




49




51






w/v




400




81




83




73






Formulation C




150




78




61




76






+ Fluorad FC-135 0.1%




250




79




77




81






w/v




400




93




100




78






Formulation C




150




43




86




69






+ Fluorad FC-135 0.05%




250




79




100




80






w/v




400




95




98




84






Formulation C




150




39




56




77






+ Fluorad FC-135 0.02%




250




77




100




86






w/v




400




88




100




80






26-01




150




63




48




49







250




70




69




66







400




85




84




63






26-02




150




32




36




55







250




64




74




65







400




77




92




69






26-03




150




30




78




51







250




59




79




66







400




83




93




74






26-04




150




86




50




65







250




74




98




71







400




81




89




75






26-05




150




85




55




60







250




81




75




73







400




82




81




64






26-06




150




61




67




45







250




66




78




61







400




83




77




67






26-07




150




46




38




44







250




56




85




64







400




75




96




78






26-08




150




88




63




70







250




87




73




79







400




91




82




75






26-09




150




63




72




61







250




87




73




71







400




89




87




80






26-10




150




81




72




61







250




85




62




82







400




87




89




76






26-11




150




54




57




68







250




80




90




74







400




84




95




66






26-12




150




27




53




47







250




57




71




67







400




72




91




70






26-13




150




78




59




64







250




80




84




80







400




89




76




77






26-14




150




84




52




68







250




88




69




75







400




90




84




66






26-15




150




51




57




55







250




81




55




71







400




88




83




69






26-16




150




40




68




46







250




74




89




60







400




77




98




63






26-17




150




64




44




58







250




80




93




81







400




87




99




69






26-18




150




64




87




50







250




77




75




70







400




90




89




50














This test was designed in part to explore the relative contribution of Fluorad FC-135 and lecithin to the herbicidal effectiveness of glyphosate compositions comprising both of these excipient substances. Fluorad FC-135 was applied as sole excipient at concentrations of 1.0%, 0.5% and 0.2% (see tank-mix treatments with Formulation B). Lecithin was applied as sole excipient at the same three concentrations in compositions 26-09, 26-11 and 26-15. Combinations of the two excipients at equal concentrations were applied in corresponding compositions 26-10, 26-13 and 26-17. The data are highly variable but an overall trend can be discerned. When only one of the two excipients was present, herbicidal effectiveness tended to drop off as the concentration of that excipient was reduced. When both excipients were present, there was scarcely any decline in herbicidal effectiveness as excipient concentration was reduced. Although averages of data from three glyphosate rates across three species can be misleading, it is helpful in this case to reduce the mass of individual data to the following such averages of percent inhibition:





















Glyphosate (Formulation B)




68%







Glyphosate + 0.1% Fluorad FC-135




81%







Glyphosate + 0.05% Fluorad FC-135




71%







Glyphosate + 0.02% Fluorad FC-135




63%







Glyphosate + 0.1% lecithin




76%







Glyphosate + 0.05% lecithin




74%







Glyphosate + 0.02% lecithin




68%







Glyphosate + 0.1% Fluorad FC-135 + 0.1% lecithin




77%







Glyphosate + 0.05% Fluorad FC-135 + 0.05% lecithin




76%







Glyphosate + 0.02% Fluorad FC-135 + 0.02% lecithin




75%







Glyphosate commercial standard (Formulation C)




73%















Thus, when both excipients are used together, a fivefold decrease in excipient concentration results in a decline in overall herbicidal effectiveness of only 2 percentage points, still retaining overall effectiveness at least equal to that of the commercial standard.




Example 27




Glyphosate-containing spray compositions were prepared by tank-mixing Formulations B with excipients as shown in Table 27. Soybean lecithin (20% phospholipid, Avanti) was used in the form of a 10% dispersion prepared by sonication as in process (iii).




Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 15 days after planting ECHCF, and evaluation of herbicidal inhibition was done 19 days after application. Results, averaged for all replicates of each treatment, are shown in Table 27.

















TABLE 27















Addi-








Glyphosate





tive
















Glyphosate




rate





rate




% Inhibition
















composition




g a.e./ha




Additive




% v/v




ABUTH




ECHCF



















Formulation B




56




none





0




3







112






5




13







224






40




40







336






83




77






Formulation B




56




Fluorad




0.005




0




7







112




FC-135





3




10







224






45




53







336






58




78






Formulation B




56




Fluorad




0.01




0




8







112




FC-135





2




12







224






45




60







336






67




87






Formulation B




56




Fluorad




0.05




2




8







112




FC-135





20




23







224






72




88







336






90




93






Formulation B




56




Fluorad




0.1




3




10







112




FC-135





33




38







224






73




88







336






93




92






Formulation B




56




Fluorad




0.2




10




17







112




FC-135





33




47







224






77




85







336






93




92






Formulation B




56




Fluorad




0.5




7




13







112




FC-135





37




37







224






80




85







336






96




95






Formulation B




56




Fluorad




1.0




3




7







112




FC-135





27




35







224






72




87







336






88




92






Formulation B




56




Fluorad




2.0




0




0







112




FC-135





27




18







224






72




75







336






87




87






Formulation B




56




Fluorad




5.0




0




0







112




FC-135





12




13







224






43




50







336






58




53






Formulation B




56




lecithin/




0.005




0




2







112




FC-135 (1:1)





7




13







224






65




63







336






83




82






Formulation B




56




lecithin/




0.01




0




0







112




FC-135 (1:1)





3




10







224






42




63







336






73




82






Formulation B




56




lecithin/




0.05




0




0







112




FC-135 (1:1)





42




13







224






68




73







336






98




73






Formulation B




56




lecithin/




0.1




0




0







112




FC-135 (1:1)





37




20







224






62




68







336






94




77






Formulation B




56




lecithin/




0.2




0




2







112




FC-135 (1:1)





33




28







224






67




68







336






100




78






Formulation B




56




lecithin/




0.5




7




0







112




FC-135 (1:1)





40




18







224






68




68







336






90




73






Formulation B




56




lecithin/




1.0




17




3







112




FC-135 (1:1)





43




45







224






83




88







336






95




94






Formulation B




56




lecithin/




2.0




10




23







112




FC-135 (1:1)





32




42







224






63




73







336






88




87






Formulation B




56




lecithin/




5.0




2




3







112




FC-135 (1:1)





18




28







224






50




72







336






85




87






Formulation B




56




lecithin




0.005




2




2







112






3




10







224






45




50







336






58




72






Formulation B




56




lecithin




0.01




0




2







112






2




12







224






40




52







336






65




75






Formulation B




56




lecithin




0.05




2




2







112






0




10







224






40




45







336






57




70






Formulation B




56




lecithin




0.1




2




7







112






2




13







224






33




37







336






48




67






Formulation B




56




lecithin




0.2




3




3







112






3




13







224






32




35







336






47




68






Formulation B




56




lecithin




0.5




2




3







112






8




15







224






47




53







336






67




65






Formulation B




56




lecithin




1.0




2




5







112






10




15







224






33




55







336






70




77






Formulation B




56




lecithin




2.0




5




8







112






12




17







224






48




52







336






68




77






Formulation B




56




lecithin




5.0




5




17







112






23




17







224






52




55







336






73




78














This tank-mix study more clearly demonstrates the surprising interaction seen in Example 26 between lecithin and Fluorad FC-135 as excipients for glyphosate. For example, glyphosate alone over four rates gave average inhibition of ABUTH of 32%. Adding Fluorad FC-135 at a concentration of 0.5% boosted the average inhibition to 55%, but adding lecithin at the same concentration did not raise average inhibition above 32%. A 1:1 combination of both excipients at the same total concentration gave an average inhibition of51%. At a concentration of 0.1%, Fluorad FC-135 gave average inhibition of 50%, lecithin 21% (i.e. a reduction in effectiveness of glyphosate) and the 1:1 combination 48%. Thus, as in Example 26, the decline in herbicidal effectiveness with reducing excipient rate was much less pronounced with the combination than with either excipient on its own.




Example 28




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 28a. Process (i) was followed for compositions 28-01 to 28-06. Process (iv) was followed for compositions 28-07 to 28-11, using soybean lecithin (20% phospholipid. Avanti). For compositions 28-12 and 28-13, process (iv) was also used, but Aerosol OT was the aggregate-forming material employed in place of lecithin. The pH of all compositions was approximately 5.













TABLE 28a











Concen-














trate




% w/w


















compo-




Glyphosate




Leci-




Fluorad




MON





(*) Other






sition




a.e.




thin




FC-135




0818




Other (*)




components




















28-01




20







1.0




PVA






28-02




20





5.0





1.0




PVA






28-03




20





2.0





1.0




PVA






28-04




20





1.0





1.0




PVA






28-05




20







0.5




Kelzan






28-06




20





2.0





0.5




Kelzan






28-07




20




2.0





0.04








28-08




20




2.0




2.0




0.04








28-09




20




2.0




2.0




0.02








28-10




20




2.0





0.04




25.0




Silwet 800






28-11




20




2.0




2.0




0.04




25.0




Silwet 800






28-12




20







5.0




Aerosol OT






28-13




20







5.0 + 25.0




Aerosol OT












+












Silwet 800














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and 17 days after planting ECHCF, and evaluation of herbicidal inhibition was done 38 days after application.




Formulations B and C were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 28b.

















TABLE 28b













Concentrate




Glyphosate rate




% Inhibition

















composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




56




0




8








112




4




33








224




45




40








336




69




65







Formulation C




56




0




10








112




5




43








224




68




73








336




87




94







28-01




112




0




40








224




50




76








336




76




85







28-02




112




1




35








224




30




70








336




69




96







28-03




112




6




35








224




35




58








336




65




84







28-04




112




1




35








224




70




60








336




69




85







28-05




112




1




35








224




63




68








336




80




88







28-06




112




0




25








224




40




55








336




66




73







28-07




112




11




35








224




45




68








336




65




86







28-08




112




9




38








224




65




60








336




66




75







28-09




112




10




33








224




56




60








336




78




75







28-10




112




30




5








224




79




30








336




90




35







28-11




112




60




5








224




79




33








336




96




30







28-12




112




8




11








224




53




40








336




66




64







28-13




112




40




6








224




91




33








336




98




38















Concentrate compositions 28-08 and 28-09 did not in this test exhibit herbicidal effectiveness equal to Formulation C.




Example 29




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 29a. Process (iii) was followed for all compositions, using soybean lecithin (20% or 45% phospholipid as indicated below, both sourced from Avanti). The pH of all compositions was adjusted to approximately 7.

















TABLE 29a













Spray





Lecithin




% w/w
















composition




g/l




phospholipid %




Fluorad FC-135











29-01




0.25




20








29-02




0.05




20







29-03




0.02




20







29-04




0.01




20







29-05




0.25




20




0.25







29-06




0.05




20




0.05







29-07




0.02




20




0.02







29-08




0.01




20




0.01







29-09




0.25




45







29-10




0.05




45







29-11




0.02




45







29-12




0.01




45







29-13




0.25




45




0.25







29-14




0.05




45




0.05







29-15




0.02




45




0.02







29-16




0.01




45




0.01















Yellow nutsedge (


Cyperus esculentus


, CYPES) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 27 days after planting CYPES. Evaluation was done 27 days after application.




In addition to compositions 29-01 to 29-16 spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 29b.
















TABLE 29b












Glyphosate rate




% Inhibition







Spray composition




g a.e./ha




CYPES




























Formulation B




500




25








800




41








1200




59







Formulation C




500




29








800




43








1200




62







Formulation B +




500




60







Fluorad FC-135 0.25% w/v




800




57








1200




79







Formulation B +




500




63







Fluorad FC-135 0.05% w/v




800




54








1200




65







Formulation B +




500




50







Fluorad FC-135 0.02% w/v




800




71








1200




60







Formulation B +




500




27







Fluorad FC-135 0.01% w/v




800




35








1200




81







Formulation C +




500




41







Fluorad FC-135 0.25% w/v




800




72








1200




75







Formulation C +




500




52







Fluorad FC-135 0.05% w/v




800




43








1200




63







Formulation C +




500




76







Fluorad FC-135 0.02% w/v




800




72








1200




82







Formulation C +




500




38







Fluorad FC-135 0.01% w/v




800




59








1200




72







29-01




500




51








800




70








1200




64







29-02




500




58








800




69








1200




77







29-03




500




49








800




67








1200




85







29-04




500




51








800




76








1200




77







29-05




500




37








800




73








1200




100 







29-06




400




72








750




62








1000




67







29-07




400




68








750




75








1000




86







29-08




400




59








750




78








1000




88







29-09




400




72








750




80








1000




88







29-10




400




67








750




77








1000




89







29-11




400




67








750




75








1000




66







29-12




400




55








750




75








1000




83







29-13




400




33








750




59








1000




73







29-14




400




63








750




77








1000




76







29-15




400




35








750




75








1000




88







29-16




400




77








750




66








1000




86















This test was conducted to investigate the effect of phospholipid content of lecithin on herbicidal efficacy of lecithin-containing glyphosate compositions. No clear pattern emerged from this study, but overall it appeared that the crude lecithin (20% phospholipid) provided greater herbicidal effectiveness on CYPES than the de-oiled lecithin (45% phospholipid), suggesting that the oil present in crude lecithin might be having an adjuvant effect on this species.




Example 30




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 30a. Process (iii) was followed for all compositions, using soybean lecithin (20%, 45% or 95% phospholipid as indicated below, all sourced from Avanti). The pH of all compositions was adjusted to approximately 7.

















TABLE 30a













Spray





Lecithin




% w/w
















composition




g/l




phospholipid %




Fluorad FC-135











30-01




0.5




20








30-02




0.2




20







30-03




0.1




20







30-04




0.5




45







30-05




0.2




45







30-06




0.1




45







30-07




0.5




95







30-08




0.2




95







30-09




0.1




95







30-10




0.5




20




0.05







30-11




0.5




45




0.05







30-12




0.5




95




0.05







30-13




0.2




20




0.02







30-14




0.2




45




0.02







30-15




0.2




95




0.02







30-16




0.1




20




0.01







30-17




0.1




45




0.01







30-18




0.1




95




0.01















Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and prickly sida (Sida spinosa, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH, 19 days after planting ECHCF, and 23 days after planting SIDSP. Evaluation of herbicidal inhibition was done 15 days after application.




In addition to compositions 30-01 to 30-18, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-1 35 at various concentrations. Formulations B and C alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 30b.















TABLE 30b













Glyphosate








rate




% Inhibition















Spray composition




g a.e./ha




ABUTH




ECHCF




SIDSP


















Formulation B




100




10




25




33







200




22




29




49







300




50




62




61







400




62




62




64






Formulation C




100




14




40




34







200




53




98




66







300




74




100




84







400




86




100




93






Formulation B +




100




18




25




34






Fluorad FC-135 0.05% w/v




200




50




58




52







300




68




83




70






Formulation B +




100




10




21




29






Fluorad FC-135 0.02% w/v




200




64




40




46







300




79




62




64






Formulation B +




100




10




21




34






Fluorad FC-135 0.01% w/v




200




34




27




44







300




73




74




69






Formulation C +




100




65




53




58






Fluorad FC-135 0.05% w/v




200




73




77




65







300




94




99




73






Formulation C +




100




68




94




61






Fluorad FC-135 0.02% w/v




200




63




93




66







300




85




90




79






Formulation C +




100




72




67




53






Fluorad FC-135 0.01% w/v




200




69




99




61







300




81




99




83






30-01




100




32




26




39







200




72




60




56







300




84




72




69






30-02




100




14




23




43







200




70




42




63







300




83




74




68






30-03




100




6




25




42







200




55




47




57







300




65




64




72






30-04




100




29




31




42







200




55




65




60







300




82




54




73






30-05




100




14




22




41







200




32




35




66







300




81




98




70






30-06




100




9




26




29







200




47




48




57







300




69




71




71






30-07




100




30




22




50







200




73




50




69







300




82




86




67






30-08




100




41




23




53







200




57




38




69







300




76




46




84






30-09




100




32




17




45







200




60




37




67







300




78




77




73






30-10




100




58




27




62







200




91




42




79







300




93




95




77






30-11




100




66




58




63







200




91




79




69







300




91




84




84






30-12




100




61




27




67







200




90




72




77







300




93




83




84






30-13




100




61




24




51







200




88




48




69







300




94




54




75






30-14




100




66




25




56







200




90




49




72







300




93




73




85






30-15




100




63




23




61







200




88




33




72







300




95




75




81






30-16




100




75




25




56







200




87




37




74







300




93




71




77






30-17




100




63




17




59







200




92




27




73







300




92




83




78






30-18




100




67




22




53







200




91




38




68







300




91




46




77














In general, across the three species included in this test, compositions containing the 45% phospholipid grade of soybean lecithin provided slightly greater herbicidal effectiveness than those containing the 20% grade. Any further improvement obtained by using the 95% grade was minimal and would likely not justify the considerably increased cost of this grade. The data of this test clearly show a non-additive interaction between lecithin and Fluorad FC-135. To take just one example for illustration, glyphosate alone (Formulation B) at 200 g a.e./ha gave 22% inhibition of ABUTH, 29% inhibition of ECHCF and 49% inhibition of SIDSP. Adding 0.02% Fluorad FC-135 brought these percentage inhibitions to 64%, 40% and 46% respectively. Alternatively, adding the 45% grade of lecithin at 0.02% (composition 30-05) resulted in percentage inhibitions of 32%, 35% and 36% respectively. Adding both these excipients, each at 0.02% (composition 30-14) gave percentage inhibitions of 90%, 49% and 72% respectively. Even adding both excipients so that the total excipient concentration was 0.02% (composition 30-17) resulted in percentage inhibitions of 92%, 27% and 73% respectively. Thus at least on the broadleaf species (ABUTH and SIDSP) there is strong evidence of a synergistic interaction between these two excipient substances.




Example 31




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 31 a. Process (iii) was followed for all compositions, using lecithin (20% or 95% phospholipid from soybean, or 95% phospholipid from egg yolk, all sourced from Avanti). The pH of all compositions was adjusted to approximately 7.
















TABLE 31a













Lecithin




% w/w

















Spray





phospho-





Fluorad




Fluorad






composition




g/l




lipid %




source




FC-135




FC-754









31-01




0.05




95




egg yolk








31-02




0.02




95




egg yolk






31-03




0.01




95




egg yolk






31-04




0.05




95




soybean






31-05




0.02




95




soybean






31-06




0.01




95




soybean






31-07




0.05




95




egg yolk




0.05






31-08




0.02




95




egg yolk




0.02






31-09




0.01




95




egg yolk




0.01






31-10




0.05




95




soybean




0.05






31-11




0.02




95




soybean




0.02






31-12




0.01




95




soybean




0.01






31-13




0.05




20




soybean





0.05






31-14




0.02




20




soybean





0.02














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 19 days after planting ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




In addition to compositions 31-01 to 31-14, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 or Fluorad FC-754 at various concentrations. Formulations B and C alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 31b.
















TABLE 31b













Glyphosate rate




% Inhibition















Spray composition




g a.e./ha




ABUTH




ECHCF









Formulation B




100




 1




27







200




 6




28







300




21




35







400




31




46






Formulation C




100




10




31







200




28




36







300




62




66







400




77




74






Formulation B +




100




19




24






Fluorad FC-135 0.05% w/v




200




37




40







300




62




52






Formulation B +




100




 7




13






Fluorad FC-135 0.02% w/v




200




42




27







300




56




57






Formulation B +




100




23




19






Fluorad FC-135 0.01% w/v




200




43




24







300




60




40






Formulation B +




100




19




23






Fluorad FC-754 0.05% w/v




200




41




33







300




67




62






Formulation B +




100




12




19






Fluorad FC-754 0.02% w/v




200




31




44







300




61




45






Formulation C +




100




37




39






Fluorad FC-135 0.05% w/v




200




49




43







300




66




62






Formulation C +




100




18




31






Fluorad FC-135 0.02% w/v




200




47




44







300




68




49






Formulation C +




100




26




27






Fluorad FC-135 0.01% w/v




200




36




44







300




54




82






Formulation C +




100




34




32






Fluorad FC-754 0.05% w/v




200




47




37







300




62




62






Formulation C +




100




28




32






Fluorad FC-754 0.02% w/v




200




45




60







300




43




75






31-01




100




16




36







200




54




56







300




66




61






31-02




100




23




43







200




45




45







300




65




51






31-03




100




31




35







200




37




45







300




53




60






31-04




100




24




35







200




43




43







300




78




50






31-05




100




24




36







200




45




44







300




58




66






31-06




100




31




24







200




46




34







300




52




51






31-07




100




49




33







200




65




39







300




73




63






31-08




100




48




25







200




70




49







300




73




69






31-09




100




45




27







200




59




53







300




71




84






31-10




100




60




30







200




64




89







300




75




99






31-11




100




47




51







200




66




65







300




80




78






31-12




100




49




39







200




60




59







300




67




84






31-13




100




50




30







200




70




51







300




68




66






31-14




100




54




33







200




61




44







300




79




66














In this test, glyphosate compositions containing egg yolk lecithin (31-01 to 31-03) performed similarly to those containing soybean lecithin (31-04 to 31-06) on ABUTH but were generally more effective than those containing soybean lecithin on ECHCF, at least in the absence of Fluorad FC-135. Addition of Fluorad FC-135, as in compositions 31-07 to 31-12, enhanced effectiveness of all compositions.




Example 32




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 32a. Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.















TABLE 32a









Spray




Lecithin




% w/w




Type of






composition




g/l




fluoro-organic




fluoro-organic











32-01




0.20





none






32-02




0.20




0.02




Fluorad FC-135






32-03




0.20




0.02




Fluorad FC-431






32-04




0.20




0.02




Fluorad FC-751






32-05




0.20




0.02




Fluorad FC-170C






32-06




0.20




0.02




Fluorad FC-171






32-07




0.20




0.02




Fluorad FC-754






32-08




0.50





none






32-09




0.10





none






32-10




0.04





none






32-11




0.02





none














Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and prickly sida (Sida spinosa, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and ECHCF, and 27 days after planting SIDSP. Evaluation of herbicidal inhibition was done 15 days after application.




In addition to compositions 32-01 to 32-11, spray compositions were prepared by tank mixing Formulations B and C with various fluoro-organic surfactants of the Fluorad is range, all at 0.02%. Formulations B and C alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 32b.















TABLE 32b













Glypho-








sate rate




% Inhibition















Spray composition




g a.e./ha




ABUTH




ECHCF




SIDSP









Formulation B




150




 8




35




35







250




21




47




37







350




31




36




56







450




57




52




64






Formulation C




150




29




69




49







250




55




90




67







350




75




91




75







450




82




91




85






Formulation B +




150




17




43




36






Fluorad FC-135 0.02% w/v




250




39




58




53







350




52




53




68






Formulation B +




150




13




25




32






Fluorad FC-170C 0.02% w/v




250




31




47




36







350




31




85




61






Formulation B +




150




 8




52




15






Fluorad FC-171 0.02% w/v




250




10




47




44







350




15




58




55






Formulation B +




150




14




36




34






Fluorad FC-431 0.02% w/v




250




23




53




53







350




37




61




62






Formulation B +




150




12




29




29






Fluorad FC-751 0.02% w/v




250




30




38




41







350




43




36




58






Formulation B +




150




21




27




33






Fluorad FC-754 0.02% w/v




250




31




36




49







350




38




51




59






Formulation C +




150




35




31




46






Fluorad FC-135 0.02% w/v




250




66




87




58







350




78




99




80






Formulation C +




150




29




68




41






Fluorad FC-170C 0.02% w/v




250




54




78




61







350




59




86




78






Formulation C +




150




20




96




35






Fluorad FC-171 0.02% w/v




250




37




99




62







350




55




100 




65






Formulation C +




150




20




94




41






Fluorad FC-431 0.02% w/v




250




51




85




68







350




66




97




74






Formulation C +




150




15




67




38






Fluorad FC-751 0.02% w/v




250




36




85




56







350




60




100 




72






Formulation C +




150




33




78




37






Fluorad FC-754 0.02% w/v




250




75




85




66







350




82




94




80






32-01




150




25




35




45







250




43




52




63







350




60




90




77






32-02




150




65




37




58







250




69




69




67







350




66




69




78






32-03




150




14




40




41







250




45




78




63







350




55




92




75






32-04




150




19




48




48







250




36




51




63







350




65




69




70






32-05




150




47




34




45







250




55




43




55







350




63




58




75






32-06




150




23




36




46







250




57




52




59







350




61




73




67






32-07




150




67




59




58







250




81




73




72







350




80




76




76






32-08




150




37




49




60







250




60




83




69







350




67




93




49






32-09




150




19




63




51







250




53




71




62







350




55




74




82






32-10




150




19




70




51







250




39




94




61







350




63




87




73






32-11




150




16




51




50







250




58




67




66







350




69




92




73














Composition 32-07, containing 0.02% and 0.02% Fluorad FC-754, was equal or superior to composition 32-02, containing 0.02% lecithin and 0.02% Fluorad FC-135, in herbicidal effectiveness. This indicated that Fluorad FC-754 is an acceptable substitute for Fluorad FC-135 in such compositions. The other fluoro-organic surfactants tested in this Example, none of which is cationic, were less effective than the cationic fluoro-organics Fluorad FC-135 and Fluorad FC-754 as excipients in combination with lecithin. A possible exception was Fluorad FC-170C which gave good enhancement of glyphosate effectiveness on ECHCF only.




Example 33




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 33a. Process (v) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was approximately 5.














TABLE 33a













% w/w
















Concentrate




Glyphosate






Agrimul




Fluorad






composition




a.e.




Lecithin




MON 0818




PG-2069




FC-135









33-01




30




3.0





0.25




3.0






33-02




30




3.0





0.25




1.0






33-03




30




3.0




0.25





3.0






33-04




30




1.0




0.50





3.0






33-05




30




1.0





0.50




3.0






33-06




30




1.0






1.0






33-07




30




1.0





0.25




1.0






33-08




30




3.0





0.50




2.0






33-09




30




2.0






3.0






33-10




30




3.0




0.50














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and 17 days after planting ECHCF, and evaluation of herbicidal inhibition was done 19 days after application.




Formulations C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 33b.
















TABLE 33b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF









Formulation C




 56




 3




 5







112




49




48







224




79




83







448




99




99






Formulation J




 56




16




20







112




40




43







224




80




81







448




97




99






33-01




 56




 4




 5







112




35




20







224




81




51







448




99




80






33-02




 56




 0




 5







112




 4




20







224




66




55







448




94




80






33-03




 56




 1




 5







112




 6




20







224




78




74







448




93




80






33-04




 56




 1




 5







112




 1




15







224




75




65







448




95




80






33-05




 56




 0




 5







112




 1




15







224




75




65







448




91




80






33-06




 56




 0




 5







112




 3




15







224




55




63







448




91




79






33-07




 56




 1




 5







112




 3




15







224




48




55







448




88




81






33-08




 56




 3




 9







112




 3




20







224




66




60







448




89




80






33-09




 56




 0




 5







112




 5




10







224




78




55







448




97




80






33-10




 56




 0




 5







112




 4




15







224




21




55







448




88




79














Concentrate compositions containing lecithin and Fluorad FC-135 did not exhibit herbicidal effectiveness superior to commercial standard Formulations C and J in this test.




Example 34




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 34a. Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.














TABLE 34a









Spray




Lecithin




% w/w






composition




g/l




Fluorad FC-135











34-01




0.25







34-02




0.05






34-03




0.02






34-04




0.01






34-05




0.25




0.25






34-06




0.05




0.05






34-07




0.02




0.02






34-08




0.01




0.01














Guineagrass (


Panicum maximum


, PANMA) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 78 days after planting PANMA, and evaluation of herbicidal inhibition was done 20 days after application.




In addition to compositions 34-01 to 34-08, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 34b.
















TABLE 34b












Glyphosate rate




% Inhibition







Spray composition




g a.e./ha




PANMA













Formulation B




400




61








800




89








1500 




93








2000 




97







Formulation C




400




85








800




94








1500 




100 








2000 




100 







Formulation B +




400




76







Fluorad FC-135 0.25% w/v




800




78








1500 




97







Formulation B +




400




45







Fluorad FC-135 0.05% w/v




800




69








1500 




89







Formulation B +




400




39







Fluorad FC-135 0.02% w/v




800




71








1500 




95







Formulation B +




400




52







Fluorad FC-135 0.01% w/v




800




78








1500 




99







Formulation C +




400




82







Fluorad FC-135 0.25% w/v




800




97








1500 




100 







Formulation C +




400




63







Fluorad FC-135 0.05% w/v




800




93








1500 




100 







Formulation C +




400




73







Fluorad FC-135 0.02% w/v




800




98








1500 




100 







Formulation C +




400




66







Fluorad FC-135 0.01% w/v




800




97








1500 




100 







34-01




400




38








800




73








1500 




92







34-02




400




64








800




83








1500 




90







34-03




400




50








800




75








1500 




99







34-04




400




48








800




88








1500 




98







34-05




400




60








800




79








1500 




99







34-06




400




58








800




86








1500 




99







34-07




400




55








800




86








1500 




93







34-08




400




60








800




91








1500 




98















Exceptionally high glyphosate activity was seen in this test even with Formulation B and no firm conclusions can be drawn. However, none of the compositions containing lecithin and Fluorad FC-135 exceeded the effectiveness of commercial standard Formulation C on PANMA under the conditions of this test.




Example 35




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 35a. Process (v) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was approximately 5.













TABLE 35a











Con-




% w/w

















centrate




Glypho-











com-




sate





Fluorad




Fluorad





Agrimul






position




a.e.




Lecithin




FC-135




FC-754




MON 0818




PG-2069




















35-01




30




3.0




3.0






0.25






35-02




30




3.0




1.0






0.25






35-03




30




3.0




3.0





0.25






35-04




30




1.0




3.0





0.50






35-05




30




1.0




3.0






0.50






35-06




30




1.0




1.0






35-07




30




1.0




1.0






0.25






35-08




30




3.0




2.0






0.50






35-09




30




2.0




3.0






35-10




30




3.0






0.50






35-11




30




3.0





3.0





0.50






35-12




30




2.0





1.0





0.375






35-13




30




1.0





2.0





0.25






35-14




30




3.0





3.0




0.50






35-15




30




3.0





3.0





0.50






35-16




30




2.0





1.0





0.375






35-17




30




1.0





2.0





0.25






35-18




30




3.0





3.0




0.50














Quackgrass (


Elymus repens


, AGRRE) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 56 days after planting AGRRE, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment. are shown in Table 35b.
















TABLE 35b












Glyphosate rate




% Inhibition







Concentrate composition




g a.e./ha




AGRRE













Formulation B




400




41








800




46








1000 




55








1200 




70







Formulation C




400




38








800




47








1000 




77








1200 




77







Formulation J




400




60








800




84








1000 




77








1200 




85







35-01




400




27








800




76








1000 




79







35-02




400




49








800




66








1000 




78







35-03




400




42








800




80








1000 




83







35-04




400




31








800




71








1000 




64







35-05




400




32








800




53








1000 




59







35-06




400




27








800




39








1000 




65







35-07




400




29








800




54








1000 




61







35-08




400




38








800




65








1000 




81







35-09




400




31








800




55








1000 




67







35-10




400




43








800




38








1000 




58







35-11




400




34








800




56








1000 




75







35-12




400




29








800




51








1000 




65







35-13




400




51








800




69








1000 




83







35-14




400




39








800




63








1000 




65







35-15




400




53








800




65








1000 




77







35-16




400




43








800




65








1000 




82







35-17




400




69








800




84








1000 




94







35-18




400




69








800




92








1000 




92















Compositions of the invention exhibiting superior herbicidal effectiveness to commercial standard Formulation C in this test on AGRRE included 35-01, 35-02, 35-03, 35-13 and 35-15 to 35-18. Compositions 35-17 and 35-18 were the most effective in this test, outperforming commercial standard Formulation J as well as Formulation C.




Example 36




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 36a. Process (v) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The order of addition of ingredients was varied in compositions 36-15 to 36-20 as shown below. The pH of all compositions was approximately 5.
















TABLE 36a














Lecithin




order







% w/w




phos-




of


















Conc.




Glypho-




Leci-




Fluorad




Agrimul




MON




pholipid




addition






comp.




sate a.e.




thin




FC-135




PG-2069




0818




%




(*)









36-01




30




3.0




2.0




0.50





45




A 






36-02




30




3.0




3.0




0.50





45




A 






36-03




30




3.0




3.0




0.75





45




A 






36-04




30




3.0




3.0




0.75




0.5




45






   


A(**)






36-05




30




3.0




3.0




1.00





45




A 






36-06




30




3.0




3.0




2.00





45




A 






36-07




30




3.0




3.0




3.00





45




A 






36-08




30




3.0




3.0




4.00





45




A 






36-09




30




3.0




2.0




0.50





20




A 






36-10




30




3.0




2.0




0.50





20




B 






36-11




30




3.0




2.0




0.50





20




C 






36-12




30




3.0




2.0




0.50





20




D 






36-13




30




3.0




2.0




0.50





20




E 






36-14




30




3.0




2.0




0.50





20




F 






36-15




30




3.0




3.0




0.50





20




A 






36-16




30




3.0




3.0




0.50





20




B 






36-17




30




3.0




3.0




0.50





20




C 






36-18




30




3.0




3.0




0.50





20




D 






36-19




30




3.0




3.0




0.50





20




E 






36-20




30




3.0




3.0




0.50





20




F 














(*)Order of addition:

















1st




2nd




3rd




4th




5th






A




lecithin




PG-2069




FC-135




water




glyphosate






B




lecithin




FC-135




PG-2069




water




glyphosate






C




glyphosate




water




FC-135




PG-2069




lecithin






D




glyphosate




water




PG-2069




FC-135




lecithin






E




glyphosate




lecithin




PG-2069




FC-135




water






F




glyphosate




lecithin




FC-135




PG-2069




water











(**)where MON 0818 included, added with Agrimul PG-2069











Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 22 days after planting ECHCF, and evaluation of herbicidal inhibition was done 17 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 36b.















TABLE 36b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




200




38




73







400




51




64







600




67




89







800




72




86






Formulation C




200




57




75







400




77




98







600




92




97







800




100




100






Formulation J




200




50




52







400




73




99







600




88




99







800




98




98






36-01




200




49




64







400




72




59







600




78




87






36-02




200




54




72







400




78




71







600




97




90






36-03




200




57




62







400




80




78







600




89




87






36-04




200




46




39







400




74




64







600




86




78






36-05




200




49




29







400




74




79







600




83




90






36-06




200




49




65







400




70




88







600




87




88






36-07




200




49




51







400




67




77







600




81




83






36-08




200




42




59







400




70




67







600




78




80






36-09




200




45




28







400




73




85







600




87




98






36-10




200




57




82







400




76




89







600




87




98






36-11




200




56




80







400




84




84







600




85




100






36-12




200




57




81







400




78




98







600




87




94






36-13




200




54




86







400




73




72







600




96




97






36-14




200




56




73







400




69




98







600




85




94






36-15




200




40




41







400




85




88







600




83




96






36-16




200




53




59







400




73




76







600




84




73






36-17




200




39




53







400




65




86







600




86




81






36-18




200




49




31







400




69




52







600




73




75






36-19




200




47




50







400




74




86







600




88




98






36-20




200




51




42







400




68




94







600




90




98














Order of addition of ingredients apparently had some influence on herbicidal effectiveness of compositions 36-09 to 36-20. However, as most of these compositions showed poor short-term stability, it is likely that in at least some cases the uniformity of spray application was affected and the results are therefore difficult to interpret.




Example 37




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 37a. Process (iv) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was approximately 5.















TABLE 37a













Glypho-




% w/w


















Concentrate




sate




Leci-




Aerosol




MON




Fluorad




Methyl







composition




g a.e./l




thin




OT




0818




FC-754




caprate




PVA









37-01




200




2.0





0.25









37-02




300




3.0





0.50









37-03




300




3.0





0.50






2.0






37-04




200




2.0





0.25






1.5






37-05




200




2.0





0.25





1.0




1.0






37-06




200




2.0





0.25





1.0




1.0






37-07




200




2.0





0.25




2.0








37-08




200





2.0




0.25









37-09




300





3.0




0.50









37-10




300





3.0




0.50






2.0






37-11




200





2.0




0.25






1.5






37-12




200





2.0




0.25





1.0







37-13




200





2.0




0.25





1.0







37-14




200





2.0




0.25





1.0




1.5






37-15




200





2.0




0.25




2.0














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and 13 days after planting ECHCF, and evaluation of herbicidal inhibition was done 20 days after application.




Compositions containing PVA were too viscous to spray and were not tested for herbicidal effectiveness. Formulations B,C and were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 37b.















TABLE 37b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




112




5




4







224




48




8







336




73




20







448




94




50






Formulation C




112




30




45







224




91




81







336




98




81







448




100




99






Formulation J




112




50




35







224




80




65







336




97




88







448




100




90






37-01




112




11




8







224




50




40







336




71




61







448




93




78






37-02




112




5




6







224




64




58







336




78




60







448




84




65






37-07




112




5




3







224




46




38







336




73




83







448




93




66






37-08




112




8




13







224




43




46







336




73




65







448




83




70






37-09




112




1




5







224




23




25







336




65




33







448




91




58






37-12




112




0




5







224




58




48







336




73




63







448




91




63






37-13




112




0




10







224




53




38







336




73




45







448




88




50






37-15




112




28




10







224




50




53







336




80




63







448




88




91














Concentrate compositions containing lecithin and Fluorad FC-754 or methyl caprate did not exhibit herbicidal effectiveness equal to that of the commercial standards in this test.




Example 38




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 38a. Process (iii) was followed for all compositions, using soybean lecithin (20% phospholipid, Avanti). The pH of all compositions was approximately 5.














TABLE 38a












% w/w
















Concentrate




Glyphosate





Fluorad







composition




a.e.




Lecithin




FC-135




MON 0818









38-01




30




3.0




3.0




0.75






38-02




25




2.5




2.5




0.63






38-03




20




2.0




2.0




0.50






38-04




15




1.5




1.5




0.38






38-05




10




1.0




1.0




0.25






38-06




 5




0.5




0.5




0.13






38-07




30




3.0




3.0




1.50






38-08




25




2.5




2.5




0.63






38-09




20




2.0




2.0




0.50






38-10




15




1.5




1.5




0.38






38-11




10




1.0




1.0




0.25






38-12




 5




0.5




0.5




0.13






38-13




25




2.5




2.5




0.94






38-14




20




2.0




2.0




0.75






38-15




15




1.5




1.5




0.56






38-16




10




1.0




1.0




0.38






38-17




 5




0.5




0.5




0.19














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicidal inhibition was done 14 days after application.




In addition to compositions 38-01 to 38-17, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at two concentrations. Formulations B and C alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 38b.















TABLE 38b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation C




200




59




98







400




96




96







600




70




93







800




100




97






Formulation C +




200




59




92






Fluorad FC-135 0.1%




400




93




93







600




95




100







800




100




97






Formulation C +




200




54




73






Fluorad FC-135 0.05%




400




95




76







600




100




82







800




100




95






Formulation J




200




55




87







400




92




98







600




97




94







800




99




96






Formulation J +




200




67




88






FIuorad FC-135 0.1%




400




89




89







600




94




87







800




96




91






Formulation J +




200




71




81






Fluorad FC-135 0.05%




400




75




95







600




96




99







800




100




100






38-01




200




53




71







400




74




87







600




98




87






38-02




200




51




70







400




88




96







600




89




99






38-03




200




51




85







400




81




97







600




96




94






38-04




200




51




63







400




81




82







600




96




97






38-05




200




47




60







400




73




91







600




94




94






38-06




200




54




43







400




73




88







600




92




87






38-07




200




60




70







400




84




93







600




90




98






38-08




200




49




55







400




76




92







600




88




83






38-09




200




57




53







400




79




95







600




91




87






38-10




200




55




85







400




90




97







600




94




96






38-11




200




64




43







400




77




87







600




93




96






38-12




200




54




72







400




85




98







600




96




100






38-13




200




61




61







400




84




90







600




95




99






38-14




200




57




86







400




82




90







600




99




98






38-15




200




59




89







400




78




96







600




93




97






38-16




200




53




87







400




81




98







600




96




98






38-17




200




48




87







400




81




100







600




91




100














As concentrate compositions in previous Examples have tended to exhibit weaker herbicidal effectiveness than has been seen with ready-made spray compositions, this test was conducted to determine if the degree of concentration at which a composition is prepared before dilution for spraying had an influence on effectiveness. No consistent trend was seen in this test.




Example 39




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 39a. Process (iii) was followed for all compositions, using soybean lecithin (45% phospholipid, Avanti). The pH of all compositions was approximately 5.














TABLE 39a












% w/w


















Gly-





Fluorad








Conc.




phosate





FC-135




Amine




Type of






comp.




a.e.




Lecithin




or FC-754




surfactant




amine surfactant









39-01




20




2.0





0.25




MON 0818






39-02




20




3.0





0.25




MON 0818






39-03




20




3.0




3.0(135)




0.25




MON 0818






39-04




20




3.0




3.0(754)




0.25




MON 0818






39-05




20




2.0





2.00




Triton RW-20






39-06




20




2.0





2.00




Triton RW-50






39-07




20




2.0





2.00




Triton RW-75






39-08




20




2.0





2.00




Triton RW-100






39-09




20




2.0





2.00




Triton RW-150






39-10




20






2.00




Triton RW-20






39-11




20






2.00




Triton RW-50






39-12




20






2.00




Triton RW-75






39-13




20






2.00




Triton RW-100






39-14




20






2.00




Triton RW-150














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and 17 days after planting ECHCF, and evaluation of herbicidal inhibition was done 21 days after application.




Formulation C was applied as a comparative treatment. Results, averaged for all replicates of each treatment, are shown in Table 39b.















TABLE 39b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation C




112




0




10







224




10




20







336




47




30







448




63




40






39-01




112




8




15







224




25




35







336




55




56







448




63




65






39-02




112




5




10







224




23




33







336




55




64







448




66




60






39-03




112




28




15







224




55




35







336




74




58







448




76




65






39-04




112




15




8







224




53




45







336




73




55







448




75




64






39-05




112




0




8







224




14




45







336




45




70







448




65




66






39-06




112




1




13







224




5




43







336




58




64







448




66




75






39-07




112




0




15







224




1




53







336




45




78







448




60




83






39-08




112




0




10







224




25




45







336




50




79







448




68




88






39-09




112




0




13







224




13




45







336




50




75







448




70




81






39-10




112




0




18







224




18




35







336




48




65







448




66




76






39-11




112




1




0







224




35




25







336




38




55







448




50




78






39-12




112




8




25







224




10




38







336




48




70







448




73




81






39-13




112




0




25







224




5




33







336




30




70







448




74




75






39-14




112




0




12







224




0




30







336




12




70







448




40




80














No difference in herbicidal effectiveness was seen between compositions 39-03 and 39-04. The only difference between these compositions is that 39-03 contained Fluorad FC-135 and 39-04 contained Fluorad FC-754.




Example 40




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 40a. Process (iii) was followed for all compositions, using soybean lecithin (20% or 45% phospholipid as indicated below, both sourced from Avanti). The pH of all compositions was adjusted to approximately 7.















TABLE 40a













% w/w
















Spray




Lecithin




Lecithin




Fluorad




Fluorad






composition




g/l




% purity




FC-135




FC-754









40-01




1.0




20








40-02




0.5




20






40-03




0.2




20






40-04




1.0




20




0.10






40-05




0.5




20




0.05






40-06




0.2




20




0.02






40-07




1.0




20





0.10






40-08




0.5




20





0.05






40-09




0.2




20




0.02




0.02






40-10




0.5




45




0.05






40-11




0.5




45





0.05














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grosser and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




In addition to compositions 40-01 to 40-11, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 or FC-754 at various concentrations. Formulations B and C alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 40b.















TABLE 40b













Glyphosate rate




% Inhibition
















Spray composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




49




100








300




66




92








500




80




76








700




93




96







Formulation C




200




57




79








400




93




98








600




100




100








800




100




100







Formulation B +




200




58




80







Fluorad FC-135 0.1%




400




63




100








600




82




100







Formulation B +




200




37




49







Fluorad FC-135 0.05%




400




67




84








600




74




100







Formulation B +




200




33




82







Fluorad FC-135 0.02%




400




58




94








600




81




87







Formulation B +




200




50




45







Fluorad FC-754 0.1%




400




77




82








600




77




94







Formulation B +




200




44




45







Fluorad FC-754 0.05%




400




71




65








600




74




90







Formulation B +




200




31




57







Fluorad FC-754 0.02%




400




67




83








600




68




93







Formulation C +




200




69




65







Fluorad FC-135 0.1%




400




91




99








600




97




100







Formulation C +




200




73




87







Fluorad FC-135 0.05%




400




89




100








600




98




100







Formulation C +




200




51




60







Fluorad FC-135 0.02%




400




91




100








600




98




100







Formulation C +




200




70




81







Fluorad FC-754 0.1%




400




85




99








600




98




95







Formulation C +




200




68




54







Fluorad FC-754 0.05%




400




78




88








600




91




88







Formulation C +




200




50




41







Fluorad FC-754 0.02%




400




89




91








600




99




100







40-01




200




41




37








400




78




84








600




83




100







40-02




200




38




82








400




74




94








600




82




98







40-03




200




38




62








400




69




85








600




86




100







40-04




200




63




69








400




79




75








600




93




89







40-05




200




69




66








400




85




81








600




84




86







40-06




200




64




38








400




79




74








600




93




99







40-07




200




61




43








400




76




71








600




85




85







40-08




200




71




52








400




82




85








600




82




100







40-09




200




63




55








400




83




73








600




79




97







40-10




200




65




54








400




78




80








600




85




99







40-11




200




55




33








400




77




74








600




91




97















There was a tendency, although not consistently so, for compositions of this Example containing Fluorad FC-754 to show slightly weaker herbicidal effectiveness than corresponding compositions containing Fluorad FC-135.




Example 41




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 41a. Process (v) was followed for all compositions, using soybean lecithin (45% phospholipid, Avanti). The pH of all compositions was approximately 5.














TABLE 41a













% w/w
















Concentrate




Glyphosate





Fluorad




Fluorad







composition




a.e.




Lecithin




FC-135




FC-754




MON 0818



















41-01




15.0




4.0




8.0





0.5






41-02




15.0




6.0




8.0




0.5






41-03




15.0




8.0




8.0




0.5






41-04




10.0




4.0




8.0




0.5






41-05




10.0




6.0




8.0




0.5






41-06




10.0




8.0




8.0




0.5






41-07




5.0




4.0




8.0




0.5






41-08




5.0




6.0




8.0




0.5






41-09




5.0




8.0




8.0




0.5






41-10




15.0




4.0





8.0




0.5






41-11




15.0




6.0





8.0




0.5






41-12




15.0




8.0





8.0




0.5






41-13




10.0




4.0





8.0




0.5






41-14




10.0




6.0





8.0




0.5






41-15




10.0




8.0





8.0




0.5






41-16




5.0




4.0





8.0




0.5






41-17




5.0




6.0





8.0




0.5






41-18




5.0




8.0





8.0




0.5














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 20 days after planting ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




In addition to compositions 41-01 to 41-18, spray compositions were prepared by tank mixing Formulations B and J with Fluorad FC-135 at two concentrations. Formulations B and J alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 41b.















TABLE 41b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




49




41







300




41




55







500




76




98







700




82




100






Formulation J




150




59




66







300




79




99







500




93




99







700




98




100






Formulation B +




150




52




85






Fluorad FC-135 0.1%




300




69




93







500




89




97






Formulation B +




150




9




61






Fluorad FC-135 0.05%




300




71




77







500




77




100






Formulation J +




150




52




99






Fluorad FC-135 0.1%




300




74




100







500




82




99






Formulation J +




150




41




52






Fluorad FC-135 0.05%




300




77




83







500




91




100






41-01




150




66




51







300




86




91







500




93




100






41-02




150




72




88







300




89




93







500




96




92






41-03




150




71




91







300




89




95







500




91




100






41-04




150




63




90







300




89




89







500




96




99






41-05




150




70




79







300




84




94







500




88




98






41-06




150




69




76







300




89




84







500




94




100






41-07




150




71




87







300




77




82







500




99




92






41-08




150




81




87







300




88




94







500




92




98






41-09




150




72




83







300




87




83







500




94




94






41-10




150




72




70







300




81




80







500




89




93






41-11




150




74




85







300




87




96







500




91




98






41-12




150




66




92







300




78




98







500




93




100






41-13




150




71




76







300




86




95







500




94




99






41-14




150




72




75







300




90




97







500




91




99






41-15




150




69




82







300




85




98







500




94




100






41-16




150




76




87







300




86




100







500




90




99






41-17




150




71




83







300




87




94







500




96




100






41-18




150




70




81







300




77




98







500




89




98














Good herbicidal effectiveness was obtained with the concentrate compositions of this Example containing lecithin and Fluorad FC-135 or Fluorad FC-754. No great or consistent difference was seen between compositions containing Fluorad FC-135 and their counterparts containing Fluorad FC-754.




Example 42




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 42a. Process (v) was followed for all compositions, using soybean lecithin (95% phospholipid. Avanti). The pH of all compositions was approximately 5.














TABLE 42a













% w/w



















Gly-









West-






Conc.




phosate




Leci-




MON




Agrimul




Fluorad




Fluorad




vaco






comp.




a.e.




thin




0818




PG-2069




FC-135




FC-754




H-240









42-01




30




3.0





0.25




3.0





9.0






42-02




30




3.0





0.25




1.0





9.0






42-03




30




3.0




0.25





3.0





9.0






42-04




30




1.0




0.50





3.0





9.0






42-05




30




1.0





0.50




3.0





9.0






42-06




30




1.0






1.0





9.0






42-07




30




1.0





0.25




1.0





9.0






42-08




30




3.0





0.50




2.0





9.0






42-09




30




2.0






3.0





9.0






42-10




30




3.0








5.0






42-11




30




3.0





0.50





3.0




9.0






42-12




30




2.0





0.38





2.0




9.0






42-13




30




1.0





0.25





1.0




9.0






42-14




30




3.0




0.50






3.0




9.0






42-15




15




6.0




2.00





8.3






42-16




15




6.0




4.00





8.3














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and 20 days after planting ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




In addition to compositions 42-01 to 42-16, spray compositions were prepared by tank mixing Formulations B and J with Fluorad FC-135 at two concentrations. Formulations B and J alone were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 42b.














TABLE 42b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e/ha




ABUTH




ECHCF

















Formulation B




150




3




33







300




12




90







500




65




98







700




79




100






Formulation J




150




2




46







300




76




100







500




98




100







700




98




100






Formulation B




150




10




38






+Fluorad FC-135 0.1%




300




50




85







500




65




68






Formulation B




150




3




27






+Fluorad FC-135 0.05%




300




36




82







500




68




99






Formulation J




150




18




79






+Fluorad FC-135 0.1%




300




57




98







500




79




100






Formulation J




150




2




37






+Fluorad FC-135 0.05%




300




56




97







500




96




98






42-01




150




2




27







300




2




74







500




46




78






42-02




150




2




52







300




41




64







500




40




85






42-03




150




3




38







300




39




47







500




73




98






42-04




150




3




38







300




42




63







500




78




84






42-05




150




5




29







300




37




89







500




70




99






42-06




150




8




37







300




30




89







500




69




97






42-07




150




5




53







300




32




80







500




83




99






42-08




150




3




26







300




10




40







500




12




55






42-09




150




7




21







300




57




86







500




91




97






42-10




150




21




61







300




73




89







500




85




98






42-11




150




6




23







300




53




70







500




85




83






42-12




150




33




25







300




34




43







500




83




97






42-13




150




7




34







300




62




39







500




77




73






42-14




150




10




27







300




59




40







500




84




73






42-15




150




71




48







300




97




65







500




99




92






42-16




150




83




40







300




98




89







500




100




95














The only concentrate compositions in this test exhibiting excellent performance, at least on ABUTH, were 42-15 and 42-16.




Example 43




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 43a. Process (viii) was followed for composition 43-02 and process (ix) for compositions 43-03 to 43-13 which contain a colloidal particulate together with surfactant. Composition 43-01 contains colloidal particulate but no surfactant. The pH of all compositions was approximately 5.














TABLE 43a












% w/w
















Concentrate




Glyphosate




Fluorad





Emphos






composition




a.e.




FC-135




Aerosil 90




PS-21A









43-01




20





3.3







43-02




20




3.3






43-03




31




1.1




3.3




1.1






43-04




31




1.1




3.3




2.2






43-05




31




1.1




3.3




3.3






43-06




31




2.2




3.3




1.1






43-07




31




2.2




3.3




2.2






43-08




31




2.2




3.3




3.3






43-09




31




3.3




3.3




1.1






43-10




31




3.3




3.3




2.2






43-11




31




3.3




3.3




3.3






43-12




31




3.3




3.3






43-13




31





3.3




3.3














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and 17 days after planting ECHCF, and evaluation of herbicidal inhibition was done 23 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 43b.














TABLE 43b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




0




8







250




18




25







350




35




40







450




75




50






Formulation C




150




30




85







250




92




95







350




100




100







450




100




100






Formulation J




150




40




70







250




70




83







350




93




92







450




100




98






43-01




150




20




25







250




35




30







350




65




43







450




73




35






43-02




150




5




5







250




20




25







350




45




35







450




66




83






43-03




150




20




11







250




40




30







350




73




64







450




88




83






43-04




150




15




3







250




30




25







350




40




35







450




71




75






43-05




150




15




10







250




33




30







350




69




45







450




78




65






43-06




150




11




8







250




28




30







350




30




35







450




69




61






43-07




150




5




8







250




13




20







350




51




30







450




74




43






43-08




150




15




8







250




30




15







350




35




30







450




56




45






43-09




150




15




15







250




28




20







350




43




33







450




45




40






43-10




150




5




3







250




25




20







350




50




40







450




48




58






43-11




150




14




6







250




25




40







350




64




76







450




78




79






43-12




150




9




20







250




20




33







350




46




73







450




59




80






43-13




150




15




11







250




20




28







350




30




59







450




68




48














Most concentrate compositions containing Fluorad FC-135 showed enhanced herbicidal effectiveness by comparison with Formulation B but did not equal the performance of commercial standard Formulations C and J under the conditions of this test.




Example 44




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 44a. Process (viii) was followed for compositions 44-01, 44-03, 44-06, 44-07, 44-10, 44-14, 44-15, 44-18 and 44-19 process (ix) for compositions 44-02, 44-08, 44-09, 44-16 and 44-17 which contain a colloidal particulate together with surfactant. Compositions 44-04, 44-05, 44-12 and 44-13 contain colloidal particulate but no surfactant. The pH of all compositions was approximately 5.














TABLE 44a













% w/w


















Gly-





Etho-




Alum-




Titanium







Concentrate




phosate




Fluorad




meen




inum




dioxide




Aerosol






composition




a.e.




FC-135




T/25




oxide C




P25




OT









44-01




20





3.30









44-02




20








3.30






44-03




20




3.30






44-04




20






3.30






44-05




20






0.67






44-06




20





3.30




3.30






44-07




20





3.30




0.67






44-08




20






3.30





3.30






44-09




20






0.67





3.30






44-10




20




3.30





3.30






44-11




20




3.30





0.67






44-12




20







3.30






44-13




20







0.67






44-14




20





3.30





3.30






44-15




20





3.30





0.67






44-16




20







3.30




3.30






44-17




20







0.67




3.30






44-18




20




3.30






3.30






44-19




20




3.30






0.67














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 20 days after planting ECHCF, and evaluation of herbicidal inhibition was done 25 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment. are shown in Table 44b.














TABLE 44b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




8




45







250




37




55







350




40




60







450




50




70






Formulation C




50




27




72







250




73




92







350




90




99







450




92




99






Formulation J




150




25




66







250




45




88







350




78




99







450




91




100






44-01




150




40




82







250




55




93







350




74




100







450




83




100






44-02




150




9




20







250




30




73







350




38




73







450




55




97






44-03




150




13




23







250




35




79







350




45




78







450




75




100






44-04




150




18




45







250




35




65







350




35




70







450




68




81






44-05




150




11




43







250




35




50







350




50




55







450




59




78






44-06




150




25




75







250




58




93







350




88




100







450




95




100






44-07




150




15




88







250




68




100







350




79




100







450




90




100






44-08




150




28




38







250




25




38







350




35




55







450




71




79






44-09




112




5




13







224




23




48







336




25




70







448




45




64






44-10




150




1




20







250




40




74







350




65




55







450




84




96






44-11




150




25




25







250




35




65







350




45




61







450




76




92






44-12




150




14




28







250




40




43







350




45




70







450




65




79






44-13




150




20




45







250




48




33







350




60




55







450




80




79






44-14




150




23




79







250




73




100







350




76




99







450




85




99






44-15




150




25




83







250




69




99







350




75




99







450




69




100






44-16




150




14




28







250




23




40







350




30




79







450




69




86






44-17




150




1




20







250




23




33







350




16




45







450




40




68






44-18




150




8




15







250




49




56







350




55




58







450




83




83






44-19




150




6




15







250




35




60







350




61




63







450




63




70














Concentrate compositions containing Fluorad FC-135 showed enhanced herbicidal effectiveness by comparison with Formulation B but did not provide herbicidal effectiveness equal to commercial standard Formulations C and J in this test.




Example 45




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 45a. Process (i) was followed for compositions 45-10 to 45-12 and process (iii) for compositions 45-01 to 45-09 using soybean lecithin (45% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.















TABLE 45a













Spray




% w/w
















composition




Lecithin




Fluorad FC-135




SurfH1











45-01




0.10









45-02




0.05







45-03




0.02







45-04




0.10




0.10







45-05




0.05




0.05







45-06




0.02




0.02







45-07




0.10





0.10







45-08




0.05





0.05







45-09




0.02





0.02







45-10






0.10







45-11






0.05







45-12






0.02















Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 23 days after planting ABUTH and 21 days planting ECHEF, and evaluation of herbicidal inhibition was done 15 days after application.




In addition to compositions 45-01 to 45-12, spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone and Formulation J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 45b.














TABLE 45b












Glyphosate rate




% Inhibition














Spray composition




g a.e/ha




ABUTH




ECHCF

















Formulation B




150




16




21







250




68




32







350




68




63







450




67




69






Formulation C




150




29




47







250




76




74







350




98




94







450




100




85






Formulation J




150




37




31







250




79




72







350




93




82







450




97




97






Formulation B




150




55




15






+Fluorad FC-135 0.1% w/v




250




73




28







350




85




57







450




83




83






Formulation B




150




59




15






+Fluorad FC-135 0.05% w/v




250




77




41







350




81




72







450




77




51






Formulation B




150




25




12






+Fluorad FC-135 0.02% w/v




250




54




27







350




82




38







450




75




47






Formulation C




150




51




26






+Fluorad FC-135 0.1% w/v




250




78




63







350




86




71







450




89




79






Formulation C




150




58




23






+Fluorad FC-135 0.05% w/v




250




74




89







350




93




78







450




89




91






45-01




150




29




26







250




61




47







350




73




48







450




82




62






45-02




150




34




34







250




67




34







350




73




54







450




85




43






45-03




150




20




29







250




60




49







350




68




84







450




74




64






45-04




150




78




24







250




83




33







350




96




64







450




97




59






45-05




150




81




21







250




89




27







350




82




34







450




99




31






45-06




150




92




14







250




85




64







350




86




31







450




90




60






45-07




150




71




27







250




81




46







350




84




66







450




88




62






45-08




150




46




29







250




70




43







350




78




61







450




86




58






45-09




150




55




25







250




76




33







350




80




50







450




78




62






45-10




150




65




26







250




85




28







350




91




37







450




89




53






45-11




150




73




27







250




77




28







350




92




41







450




92




49






45-12




150




71




20







250




74




31







350




79




39







450




93




53














Extremely high herbicidal effectiveness was noted on ABUTH with compositions 45-04 to 45-06, containing lecithin and Fluorad FC-135. Replacement of Fluorad FC-135 by “Surf H1 ” a hydrocarbon-based surfactant of formula C


12


H


25


SO


2


NH(CH


2


)


3


N


+


(CH


3


)


3


I





, gave (in compositions 45-07 to 45-09) effectiveness on ABUTH still superior at low glyphosate rates to commercial standard Formulations C and J but not quite as great as that of compositions 45-04 to 45-06. Performance of compositions 45-04 to 45-12 on ECHCF was relatively low in this test but performance on ABUTH was remarkably high considering the very low surfactant concentrations present.




Example 46




Aqueous spray compositions were prepared containing glyphosate IPA or tetrabutylammonium salt and excipient ingredients as shown in Table 46a. Process (i) was followed for compositions 46-10 to 46-13 and 46-15 and process (iii) for compositions 46-01 to 46-09 using soybean lecithin (45% phospholipid, Avanti). The pH of all compositions was adjusted to approximately 7.














TABLE 46a












% w/w

















Spray






Fluorad





Glyphosate






composition




Lecithin




LI-700




FC-135




SurfH1




salt









46-01




0.10







IPA






46-02




0.05







IPA






46-03




0.02







IPA






46-04




0.10





0.10





IPA






46-05




0.05





0.05





IPA






46-06




0.02





0.02





IPA






46-07




0.10






0.10




IPA






46-08




0.05






0.05




IPA






46-09




0.02






0.02




IPA






46-10





0.10






IPA






46-11





0.05






IPA






46-12





0.02






IPA






46-13








(BU)


4


N






46-14




0.05





0.05





(BU)


4


N






46-15






0.05





(BU)


4


N














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 21 days after planting ECHCF, and evaluation of herbicidal inhibition was done 14 days after application.




In addition to compositions 46-01 to 46-15. spray compositions were prepared by tank mixing Formulations B and C with Fluorad FC-135 at various concentrations. Formulations B and C alone and Formulation J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 46b.














TABLE 46b












Glyphosate rate




% Inhibition














Spray composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




33




24







300




51




27







500




68




36







700




83




43






Formulation C




150




32




30







300




78




68







500




90




81







700




96




89






Formulation J




150




16




27







300




74




56







500




88




79







700




93




92






Formulation B




150




22




18






+Fluorad FC-135 0.1% w/v




300




71




26







500




73




51






Formulation B




150




19




16






+Fluorad FC-135 0.05% w/v




300




60




28







500




72




33






Formulation B




150




14




14






+Fluorad FC-135 0.02% w/v




300




23




26







500




69




38






Formulation C




150




31




11






+Fluorad FC-135 0.1% w/v




300




73




27







500




82




48






Formulation C




150




43




23






+Fluorad FC-135 0.05% w/v




300




71




49







500




93




50






46-01




150




20




18







300




65




29







500




85




34






46-02




150




22




19







300




63




35







500




83




51






46-03




150




24




29







300




64




35







500




85




40






46-04




150




63




21







300




75




31







500




84




46






46-05




150




68




10







300




82




29







500




81




53






46-06




150




68




21







300




84




30







500




85




46






46-07




150




41




35







300




51




39







500




93




61






46-08




150




34




22







300




74




56







500




88




79







700




93




92






46-09




150




24




17







300




78




39







500




91




58






46-10




150




16




19







300




62




28







500




72




53






46-11




150




38




25







300




59




38







500




82




59






46-12




150




7




23







300




61




40







500




77




63






46-13




150




81




48







300




92




51







300




90




46






46-14




150




87




30







300




91




69







500




95




89






46-15




150




81




37







300




94




41







300




92




63














As in the previous Example, compositions containing “Surf H1” did not show as strong enhancement of glyphosate effectiveness as counterpart compositions containing Fluorad FC-135. The tetrabutylammonium salt of glyphosate (compositions 46-13 to 46-15) exhibited extremely high herbicidal effectiveness in this test.




Example 47




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 47a. Process (v) was followed for all compositions using soybean lecithin (45% phospholipid, Avanti), except that various orders of addition were tried as indicated below. The pH of all compositions was approximately 5.














TABLE 47a











Concen-




% w/w




Order


















trate




Gly-









of






compo-




phosate




Leci-




Fluorad




Fluorad




MON




Agrimul




addition






sition




a.e.




thin




FC-135




FC-754




0818




PG-2069




(*)









47-01




30




3.0




3.0





0.75





A






47-02




30




3.0




3.0





0.75





B






47-03




30




3.0




3.0





0.75





C






47-04




30




3.0




3.0





0.75





D






47-05




30




3.0




3.0





0.75





E






47-06




30




3.0




3.0





0.75





F






47-07




30




3.0





3.0




0.75





A






47-08




30




3.0





3.0




0.75





B






47-09




30




3.0





3.0




0.75





C






47-10




30




3.0





3.0




0.75





D






47-11




30




3.0





3.0




0.75





E






47-12




30




3.0





3.0




0.75





F






47-13




30




3.0




3.0






0.5




A






47-14




30




3.0




3.0






0.5




B






47-15




30




3.0




3.0






0.5




C






47-16




30




3.0




3.0






0.5




D






47-17




30




3.0




3.0






0.5




E






47-18




30




3.0




3.0






0.5




F














(*)Order of addition:

















1st




2nd




3rd




4th




5th






A




lecithin




MON/PG




FC-135/754




water




glyphosate






B




lecithin




FC-135




MON/PG




water




glyphosate






C




glyphosate




water




FC-135/754




MON/PG




lecithin






D




glyphosate




water




MON/PG




FC-135/754




lecithin






E




glyphosate




lecithin




MON/PG




FC-135/754




water






F




glyphosate




lecithin




FC-135/754




MON/PG




water











MON/PG means MON 0818 or Agrimul PG-2069











Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 15 days after planting ABUTH and 18 days after planting ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




Formulations C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 47b.
















TABLE 47b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation C




150




26




69







300




75




100







500




85




99







700




94




100






Formulation J




150




38




78







300




76




87







500




87




100







700




90




100






47-01




150




10




35







300




51




56







500




71




91







700




77




100






47-02




150




24




35







300




57




71







500




77




93







700




94




100






47-03




150




11




33







300




48




55







500




73




87







700




83




93






47-04




150




37




36







300




50




38







500




68




94






47-05




150




24




32







300




48




47







500




77




85







700




76




100






47-06




150




12




32







300




61




40







500




83




86







700




88




95






47-07




150




17




25







300




58




77







500




73




97







700




86




81






47-08




150




12




34







300




53




47







500




69




72







700




79




100






47-09




150




10




33







300




47




70







500




67




99







700




83




81






47-10




150




13




25







300




49




51







500




70




73







700




85




92






47-11




150




10




22







300




56




37







500




77




47







700




85




85






47-12




150




13




27







300




61




68







500




78




52







700




86




85






47-13




150




14




27







300




62




35







500




72




46







700




87




67






47-14




150




15




27







300




59




37







500




76




63







700




85




61






47-15




150




10




25







300




40




46







500




72




88







700




79




51






47-16




150




12




27







300




53




41







500




63




49







700




71




85






47-17




150




23




25







300




59




35







500




70




79







700




75




86






47-18




150




10




27







300




56




39







500




69




57







700




74




93














No great or consistent differences in herbicidal effectiveness were seen with different orders of addition of ingredients.




Example 48




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 48a. Process (v) was followed for all compositions using soybean lecithin (45% phospholipid, Avanti). Order of addition of ingredients was varied as indicated below. The pH of all compositions was approximately 5.















TABLE 48a













% w/w

















Concentrate




Glyphosate





Fluorad




MON




Order of






composition




a.e.




Lecithin




FC-135




0818




addition (*)









48-01




20




6.0




6.0




2.0




A






48-02




20




6.0




6.0




2.0




B






48-03




20




6.0




6.0




2.0




C






48-04




20




6.0




3.0




2.0




A






48-05




20




6.0




3.0




2.0




B






48-06




20




6.0




3.0




2.0




C






48-07




20




6.0




1.0




2.0




A






48-08




20




6.0




1.0




2.0




B






48-09




20




6.0




1.0




2.0




C






48-10




20




6.0




0.0




2.0




A






48-11




20




6.0




0.0




2.0




B






48-12




20




6.0




0.0




2.0




C






48-13




20




2.0




2.0




0.5




A






48-14




20




2.0




2.0




0.5




B






48-15




20




2.0




2.0




0.5




C




















1st




2nd




3rd




4th




5th









A




lecithin




MON 0818




FC-135




water




glyphosate






B




lecithin




MON 0818




water




FC-135




glyphosate






C




lecithin




water




MON 0818




FC-135




glyphosate











(*) Order of addition:













Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and 16 days after planting ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 48b.
















TABLE 48b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




0




3







200




17




28







300




38




37







500




78




68






Formulation C




100




8




63







200




43




96







300




88




96







500




99




98






Formulation J




100




12




10







200




35




60







300




85




90







500




98




92






48-01




100




10




0







200




38




13







300




73




28







500




90




75






48-02




100




8




0







200




40




23







300




87




43







500




98




62






48-03




100




12




0







200




40




25







300




83




47







500




95




73






48-04




100




5




5







200




45




38







300




83




65







500




98




83






48-05




100




10




3







200




42




48







300




82




53







500




97




91






48-06




100




28




0







200




67




43







300




85




68







500




97




93






48-07




100




8




8







200




37




35







300




75




72







500




97




90






48-08




100




0




1







200




37




45







300




57




68







500




96




97






48-09




100




0




7







200




35




40







300




78




60







500




96




93






48-10




100




0




3







200




33




57







300




82




72







500




96




94






48-11




100




0




5







200




35




50







300




78




82







500




97




87






48-12




100




3




5







200




40




37







300




77




78







500




97




85






48-13




100




3




0







200




45




33







300




83




38







500




95




75






48-14




100




0




0







200




43




33







300




77




50







500




96




68






48-15




100




0




0







200




42




30







300




78




47







500




88




73














No great or consistent differences were seen with different orders of addition of ingredients.




Example 49




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 49a. Process (v) was followed for all compositions using soybean lecithin (45% phospholipid, Avanti). The pH of all compositions was approximately 5.















TABLE 49a













% w/w

















Concentrate




Glyphosate





Fluorad




Fluorad







composition




a.e.




Lecithin




FC-135




FC-754




MON 0818









49-01




15




4.0





8.0




0.5






49-02




15




6.0





8.0




0.5






49-03




15




8.0





8.0




0.5






49-04




10




4.0





8.0




0.5






49-05




10




6.0





8.0




0.5






49-06




10




8.0





8.0




0.5






49-07




15




4.0




8.00





0.5






49-08




15




6.0




8.00





0.5






49-09




15




8.0




8.00





0.5






49-10




15




6.0




8.25





0.5






49-11




15




6.0




8.25





4.0






49-12




15




8.0




4.00




4.0




0.5






49-13




10




8.0




8.00





0.5






49-14




10




8.0




4.00




4.0




0.5














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were groan and treated by the standard procedures given above. Applications of spray compositions were made 22 days after planting ABUTH and 23 days after planting ECHCF, and evaluation of herbicidal inhibition was done 17 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 49b.
















TABLE 49b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




0




20







250




17




37







350




47




47







450




53




60






Formulation J




150




27




38







250




68




80







350




78




95







450




87




95






49-01




150




15




30







250




78




68







350




97




87







450




97




78






49-02




150




47




30







250




92




80







350




97




97







450




98




85






49-03




150




30




35







250




83




45







350




97




57







450




97




67






49-04




150




47




32







250




80




57







350




95




87







450




97




96






49-05




150




32




30







250




81




89







350




94




95







450




98




94






49-06




150




60




28







250




80




96







350




92




95







450




98




96






49-07




150




50




23







250




70




72







350




92




78







450




97




60






49-08




150




45




40







250




72




72







350




90




89







450




97




77






49-09




150




53




25







250




80




78







350




89




89







450




96




93






49-10




150




72




48







250




89




83







350




98




95







450




98




80






49-11




150




50




27







250




77




63







350




93




83







450




97




72






49-12




150




52




15







250




83




57







350




94




68







450




98




63






49-13




150




50




30







250




75




32







350




88




84







450




97




77






49-14




150




67




23







250




84




77







350




97




73







450




97




72














In this test compositions prepared with Fluorad FC-754 tended to provide greater herbicidal effectiveness on ECHCF than their counterparts prepared with Fluorad FC-135.




Example 50




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 50a. Process (v) was followed for all compositions using soybean lecithin (45% phospholipid, Avanti). The pH of all compositions was approximately 5.














TABLE 50a













% w/w

















Concentrate




Glyphosate




Leci-




Fluorad




Fluorad




MON




Iso-






composition




a.e.




thin




FC-135




FC-754




0818




propanol




















50-01




15




6.0




8.25





4.0







50-02




15




6.0





8.25




4.0






50-03




10




8.0




8.00





0.5






50-04




10




8.0





8.00




0.5






50-05




20




2.0




2.00





0.5






50-06




20




2.0





2.00




0.5






50-07




30




3.0




3.00





0.5






50-08




30




3.0





3.00




0.5






50-09




30




1.0




1.00





0.5






50-10




30




1.0




1.00





0.5






50-11




15




6.0




8.25





4.0




5.0






50-12




15




6.0





8.25




4.0




5.0






50-13




10




8.0




8.00





2.0




5.0






50-14




10




8.0





8.00




2.0




5.0






50-15




30




3.0





3.00




0.8






50-16




30




3.0




3.00





0.8






50-17




10




8.0




8.00





2.0




7.5






50-18




10




8.0





8.00




2.0




7.5






50-19




10




8.0




8.00





2.0




10.0






50-20




10




8.0





8.00




2.0




10.0






50-21




10




8.0




8.00





4.0




5.0






50-22




10




8.0





8.00




4.0




5.0














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grow-n and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and 19 days after planting ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 50b.
















TABLE 50b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




2








250




25




28







350




63




38







450




70




58






Formulation C




150




30




47







250




75




82







350




97




97







450




100




99






Formulation J




150




10




43







250




58




88







350




87




96







450




98




93






50-01




150




63




15







250




78




32







350




83




70






50-02




150




60




28







250




80




32







350




88




65






50-03




150




53




37







250




80




42







350




91




27






50-04




150




72




18







250




83




50







350




96




80






50-05




150




50




2







250




77




25







350




78




43






50-06




150




22




25







250




77




27







350




87




40






50-07




150




27




20







250




58




32







350




87




37






50-08




150




32




3







250




78




30







350




82




52






50-09




150




5




0







250




42




28







350




68




43






50-10




150




2




23







250




52




28







350




75




42






50-11




150




72




27







250




80




42







350




85




73






50-12




150




58




23







250




82




58







350




87




97






50-13




150




70




8







250




83




38







350




85




45






50-14




150




68




37







250




90




27







350




89




67






50-15




150




28




28







250




63




40







350




87




35






50-16




150




23




13







250




45




48







350




82




68






50-17




150




67




2







250




88




30







350




87




58






50-18




150




60




38







250




85




22







350




95




53






50-19




150




74




38







250




80




47







350




95




28






50-20




150




70




25







250




85




70







350




97




81






50-21




150




78




5







250




83




50







350




90




83






50-22




150




73




33







250




82




33







350




95




83














Concentrate compositions having a high (20-30% a.e.) loading of glyphosate and consequently a relatively low loading of excipients showed enhancement of herbicidal effectiveness over that obtained with Formulation B, but in this test did not provide efficacy equal to commercial standard Formulations C and J.




Example 51




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 51 a. Process (i) was followed for compositions 51-13 to 51-20 and process (v) for compositions 51-01 to 51-12 using soybean lecithin (45% phospholipid, Avanti). Compositions were stored in different conditions as indicated below before testing for herbicidal effectiveness. The pH of all compositions was approximately 5.















TABLE 51a













% w/w



















Concentrate




Glyphosate






Fluorad




Fluorad




MON







composition




a.e.




Lecithin




LI-700




FC-135




FC-754




0818




Storage conditions





















51-01




20.0




2.0






2.0




0.5




60° C., 4 d






51-02




15.0




6.0





8.25





4.0




60° C., 4 d






51-03




20.0




2.0






2.0




0.5




−10° C., 4 d






51-04




15.0




6.0





8.25





4.0




−10° C., 4 d






51-05




20.0




2.0






2.0




0.5




room temperature, 4 d






51-06




15.0




6.0





8.25





4.0




room temperature, 4 d






51-07




20.0




2.0






2.0




0.5




60° C., 8 h then −10° C., 4 d






51-08




15.0




6.0





8.25





4.0




60° C., 8 h then −10° C., 4 d






51-09




20.0




2.0






2.0




0.5




freshly made






51-10




15.0




6.0





8.25





4.0




freshly made






51-11




20.0




2.0






2.0




0.5




room temperature, 42 d






51-12




15.0




6.0





8.25





4.0




room temperature, 42 d






51-13




15.0





18.25






51-14




20.0





4.50






51-15




15.0





14.25






4.0






51-16




20.0





4.00






0.5






51-17




15.0





10.00




8.25






51-18




20.0





2.50





2.0






51-19




15.0





6.00




8.25





4.0






51-20




20.0





2.00




2.00





0.5














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and 18 days after planting ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 51b.
















TABLE 51b













Glyphosate rate




% Inhibition















Spray composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




27




30







250




37




38







350




60




42







450




60




45






Formulation J




150




45




61







250




81




92







350




93




97







450




96




97






51-01




150




45




25







250




49




41







350




66




47







450




75




63






51-02




150




49




65







250




74




67







350




83




88







450




92




87






51-03




150




32




25







250




71




70







350




75




65







450




77




67






51-04




150




54




68







250




82




82







350




91




95







450




87




96






51-05




150




39




52







250




63




65







350




83




90







450




85




93






51-06




150




67




81







250




89




97







350




94




100







450




96




100






51-07




150




39




52







250




60




88







350




87




94







450




85




96






51-08




150




54




82







250




87




98







350




93




100







450




92




100






51-09




150




45




53







250




67




88







350




84




89







450




93




93






51-10




150




56




63







250




86




97







350




94




99







450




92




98






51-11




150




48




40







250




69




55







350




74




91






51-12




150




60




41







250




86




91







350




95




98






51-13




150




30




44







250




37




76







350




59




94






51-14




150




0




40







250




49




55







350




59




85






51-15




150




42




61







250




71




90







350




83




97






51-16




150




27




42







250




49




58







350




61




86






51-17




150




37




45







250




52




70







350




76




60






51-18




150




28




32







250




53




77







350




70




71






51-19




150




47




36







250




69




97







350




83




89






51-20




150




26




20







250




56




74







350




62




82














No great or consistent effect of storage conditions on herbicidal effectiveness of compositions was seen in this test.




Example 52




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 52a. Process (v) was followed for all compositions using soybean lecithin (45% phospholipid, Avanti). The pH of all compositions was approximately 5.













TABLE 52a











Concen-







trate




% w/w


















compo-




Glypho-




Leci-




Butyl




Fluorad




MON




Ethomeen







sition




sate a.e.




thin




stearate




FC-754




0818




T/25




Ethanol









52-01




20




2.0




0.5






1.25




1.0






52-02




20




2.0




0.5





1.00




1.00




1.0






52-03




20




2.0




0.5





1.25





1.0






52-04




20




6.0




1.5






3.00




3.0






52-05




20




6.0




1.5





2.00




2.00




2.0






52-06




20




6.0




1.5





3.00





3.0






52-07




20




2.0




0.5






0.50






52-08




20




2.0




0.5






2.50






52-09




20




2.0




0.5





1.25




1.25






52-10




20




6.0




1.5






0.50






52-11




20




6.0




1.5






3.00






52-12




20




6.0




1.5






6.00






52-13




20




6.0




1.5





3.00




3.00






52-14




20




2.0





2.0




0.50






52-15




20




6.0





3.0




6.00






52-16




20




6.0





6.0




6.00














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




Formulation J was applied as a comparative treatment. Results, averaged for all replicates of each treatment, are shown in Table 52b.














TABLE 52b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation J




150




38




45







250




80




63







350




78




82







450




75




55






52-01




150




23




27







250




57




53







350




70




85







450




70




83






52-02




150




7




25







250




52




45







350




82




88







450




82




90






52-03




150




38




35







250




50




40







350




82




92







450




83




93






52-04




150




40




48







250




73




75







350




78




92







450




88




92






52-05




150




50




53







250




68




80







350




85




98







450




89




96






52-06




150




50




43







250




55




80







350




78




97







450




85




91






52-07




150




3




28







250




22




43







350




67




72







450




73




75






52-08




150




43




33







250




77




63







350




89




78







450




97




85






52-09




150




57




27







250




95




63







350




89




86







450




98




88






52-10




150




32




23







250




33




55







350




73




82







450




67




60






52-11




150




45




32







250




78




72







350




95




92







450




98




96






52-12




150




67




42







250




80




75







350




96




88







450




97




90






52-13




150




73




42







250




83




77







350




96




91







450




98




88






52-14




150




57




30







250




77




72







350




84




80







450




96




75






52-15




150




72




38







250




88




82







350




98




92







450




98




87






52-16




150




85




49







250




97




47







350




97




83







450




98




85














Very high herbicidal effectiveness was obtained in this test with concentrate compositions containing lecithin and Fluorad FC-754. Composition 52-14, containing each of these excipients at the very low weight/weight ratio to glyphosate a.e. of 1:10, was at least as effective as commercial standard Formulation J, while compositions 52-15 and 52-16 were still more effective. Also performing very well in this test, particularly on ECHCF, were a number of concentrate compositions containing lecithin and butyl stearate.




Example 53




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 53a. Process (v) was followed for all compositions using soybean lecithin (45% phospholipid, Avanti). Order of addition of ingredients was varied for certain compositions as indicated below. The pH of all compositions was approximately 5.















TABLE 53a













% w/w




Order of


















Concentrate




Glyphosate





Fluorad




Benzalkonium




Butyl




MON




addition






composition




g/l a.e.




Lecithin




FC-754/135




Cl




stearate




0818




(*)









53-01




345




4.0





0.66









53-02




345




4.0





1.00






53-03




347




3.0





3.00






53-04




347




4.0





4.00






53-05




347




4.0





5.00






53-06




345




4.6





4.60






53-07




348




4.0




2.0 (754)




1.10






53-08




351




4.0




4.0 (754)




1.00






A






53-09




346




3.9




4.2 (754)




1.00






B






53-10




350




4.0




2.0 (135)




1.10






53-11




352




4.0




4.0 (135)




1.00






A






53-12




349




4.0




4.0 (135)




1.00






B






53-13




348




4.0




4.0 (754)




0.50




0.57







53-14




347




4.0





0.50




0.52







53-15




348




3.7





0.48





3.7






53-16




348




4.0





0.58





4.0














(*)Order of addition:

















1st




2nd




3rd




4th




5th






A




lecithin




water




Benzalkonium Cl




FC-135/754




glyphosate






B




glyphosate




FC-135/754




Benzalkonium Cl




water




glyphosate











Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 21 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 53b.














TABLE 53b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




5




5







200




15




20







300




47




30







400




65




37






Formulation J




100




0




8







200




70




37







300




78




70







400




83




73






53-01




100




3




10







200




17




27







300




45




37







400




75




40






53-02




100




2




5







200




13




30







300




43




40







400




75




47






53-03




100




0




8







200




17




43







300




65




78







400




78




83






53-04




100




2




10







200




30




37







300




68




72







400




75




88






53-05




100




2




20







200




25




65







300




63




88







400




82




83






53-06




100




10




17







200




25




33







300




47




77







400




83




75






53-07




100




0




10







200




48




30







300




73




37







400




83




43






53-08




100




3




10







200




33




30







300




68




37







400




78




40






53-09




100




5




10







200




40




27







300




65




50







400




70




57






53-10




100




0




10







200




30




27







300




67




40







400




73




40






53-11




100




0




10







200




33




27







300




52




37







400




82




40






53-12




100




0




10







200




40




20







300




65




40







400




72




40






53-13




100




0




10







200




40




20







300




60




33







400




78




33






53-14




100




0




10







200




7




47







300




28




33







400




43




43






53-15




100




0




13







200




27




33







300




73




53







400




77




67






53-16




100




0




13







200




30




37







300




75




47







400




77




68














Most concentrate compositions of this Example showed enhanced glyphosate effectiveness by comparison with Formulation B but did not equal the efficacy of commercial standard Formulation J in this test.




Example 54




Aqueous spray and concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 54a. Process (i) was followed for spray compositions 54-37 to 54-60 and process (iii) for spray compositions 54-01 to 54-36 using soybean lecithin (45% phospholipid, Avanti). Process (v) was followed for concentrate compositions 54-61 to 54-63 using soybean lecithin (45% phospholipid, Avanti). The pH of all compositions was approximately 5.
















TABLE 54a













Glyphosate




% w/w




Type of















Composition




g a.e./l




Lecithin




Fluoro-organic




fluoro-organic














Spray composition















54-01




1.60




0.027




0.027




Fluorad FC-754






54-02




2.66




0.045




0.045




Fluorad FC-754






54-03




3.72




0.062




0.062




Fluorad FC-754






54-04




4.79




0.080




0.080




Fluorad FC-754






54-05




1.60




0.027




0.027




Fluorad FC-750






54-06




2.66




0.045




0.045




Fluorad FC-750






54-07




3.72




0.062




0.062




Fluorad FC-750






54-08




4.79




0.080




0.080




Fluorad FC-750






54-09




1.60




0.027




0.027




Fluorad FC-751






54-10




2.66




0.045




0.045




Fluorad FC-751






54-11




3.72




0.062




0.062




Fluorad FC-751






54-12




4.79




0.080




0.080




Fluorad FC-751






54-13




1.60




0.027




0.027




Fluorad FC-760






54-14




2.66




0.045




0.045




Fluorad FC-760






54-15




3.72




0.062




0.062




Fluorad FC-760






54-16




4.79




0.080




0.080




Fluorad FC-760






54-17




1.60




0.027




0.027




Fluorad FC-120






54-18




2.66




0.045




0.045




Fluorad FC-120






54-19




3.72




0.062




0.062




Fluorad FC-120






54-20




4.79




0.080




0.080




Fluorad FC-120






54-21




1.60




0.027




0.027




Fluorad FC-171






54-22




2.66




0.045




0.045




Fluorad FC-171






54-23




3.72




0.062




0.062




Fluorad FC-171






54-24




4.79




0.080




0.080




Fluorad FC-171






54-25




1.60




0.027




0.027




Fluorad FC-129






54-26




2.66




0.045




0.045




Fluorad FC-129






54-27




3.72




0.062




0.062




Fluorad FC-129






54-28




4.79




0.080




0.080




Fluorad FC-129






54-29




1.60




0.027




0.027




Fluorad FC-170C






54-30




2.66




0.045




0.045




Fluorad FC-170C






54-31




3.72




0.062




0.062




Fluorad FC-170C






54-32




4.79




0.080




0.080




Fluorad FC-170C






54-33




1.60





0.027




Fluorad FC-754






54-34




2.66





0.045




Fluorad FC-754






54-35




3.72





0.062




Fluorad FC-754






54-36




4.79





0.080




Fluorad FC-754






54-37




1.60





0.027




Fluorad FC-750






54-38




2.66





0.045




Fluorad FC-750






54-39




3.72





0.062




Fluorad FC-750






54-40




4.79





0.080




Fluorad FC-750






54-41




1.60





0.027




Fluorad FC-760






54-42




2.66





0.045




Fluorad FC-760






54-43




3.72





0.062




Fluorad FC-760






54-44




4.79





0.080




Fluorad FC-760






54-45




1.60





0.027




Fluorad FC-120






54-46




2.66





0.045




Fluorad FC-120






54-47




3.72





0.062




Fluorad FC-120






54-48




4.79





0.080




Fluorad FC-120






54-49




1.60





0.027




Fluorad FC-171






54-50




2.66





0.045




Fluorad FC-171






54-51




3.72





0.062




Fluorad FC-171






54-52




4.79





0.080




Fluorad FC-171






54-53




1.60





0.027




Fluorad FC-129






54-54




2.66





0.045




Fluorad FC-129






54-55




3.72





0.062




Fluorad FC-129






54-56




4.79





0.080




Fluorad FC-129






54-57




1.60





0.027




Fluorad FC-170C






54-58




2.66





0.045




Fluorad FC-170C






54-59




3.72





0.062




Fluorad FC-170C






54-60




4.79





0.080




Fluorad FC-170C











Concentrate compositions:















54-61




180




1.5




1.5




Fluorad FC-754






54-62




180




2.5




2.5




Fluorad FC-754






54-63




180




3.0




6.0




Fluorad FC-754














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and 19 days after planting ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 54b.














TABLE 54b












Glyphosate rate




% Inhibition














Spray or concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




47




88







250




68




96







350




86




98







450




93




100






Formulation J




150




68




89







250




94




97







350




98




100







450




100




99






54-01




150




94




83






54-02




250




97




99






54-03




350




97




99






54-04




450




99




100






54-05




150




93




77






54-06




250




94




96






54-07




350




97




94






54-08




450




98




99






54-09




150




53




72






54-10




250




68




86






54-11




350




73




99






54-12




450




91




96






54-13




150




58




70






54-14




250




72




94






54-15




350




89




95






54-16




450




93




92






54-17




150




50




62






54-18




250




58




78






54-19




350




85




93






54-20




450




84




96






54-21




150




53




63






54-22




250




83




85






54-23




350




89




90






54-24




450




96




86






54-25




150




53




57






54-26




250




78




85






54-27




350




90




91






54-28




450




96




93






54-29




150




62




70






54-30




250




84




92






54-31




350




97




97






54-32




450




97




98






54-33




150




94




79






54-34




250




96




97






54-35




350




97




99






54-36




450




98




99






54-37




150




90




84






54-38




250




99




96






54-39




350




98




100






54-40




450




99




100






54-41




150




68




75






54-42




250




73




88






54-43




350




83




92






54-44




450




92




98






54-45




150




48




53






54-46




250




60




88






54-47




350




82




97






54-48




450




95




95






54-49




150




50




47






54-50




250




63




89






54-51




350




83




91






54-52




450




91




90






54-53




150




48




52






54-54




250




63




75






54-55




350




91




92






54-56




450




97




97






54-57




150




50




83






54-58




250




73




94






54-59




350




91




98






54-60




450




94




98






54-61




150




63




52







250




96




96







350




97




96






54-62




150




77




77







250




93




87







350




98




98






54-63




150




83




89







250




96




96







350




98




98














Outstanding herbicidal efficacy, even by comparison with Formulation J, was obtained in this test from spray compositions containing lecithin and Fluorad FC-754 (54-01 to 54-04). Substitution of other fluoro-organic surfactants for Fluorad FC-754 gave varying results. Fluorad FC-750 (compositions 54-05 to 54-08) was an acceptable substitute; however Fluorad FC-751, Fluorad FC-760, Fluorad FC-120, Fluorad FC-171, Fluorad FC-129 and Fluorad FC-170C (compositions 54-09 to 54-32) provided less enhancement. A similar pattern was seen with spray compositions (54-33 to 54-60) containing the same fluoro-organic surfactants as above with the exception of Fluorad FC-751, but no lecithin. It is noteworthy that of all the fluoro-organic surfactants included in this test, only Fluorad FC-754 and Fluorad FC-750 are cationic. Excellent herbicidal efficacy was also noted in this test from concentrate glyphosate compositions containing lecithin and Fluorad FC-754, especially composition 54-63.




Example 55




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 55a. Concentrate compositions 55-01 to 55-07, 55-17 and 55-18 were prepared by process (v). Concentrate compositions 55-08 to 55-15 were prepared by process (x). The other concentrate compositions of this Example were included for comparison purposes.














TABLE 55a













% w/w



















Conc.




Glyphosate





Fluorad




Butyl




Ethomeen





Arcosolve







comp.




g a.e./l




Lecithin




FC-754




stearate




T/25




Ceteareth-20




DPM




Ceteareth-27






















55-01




348




3.0




3.00





0.75









55-02




348




3.8




3.75





5.00






55-03




348




3.8




3.75





7.50






55-04




348




2.0




5.00





0.75






55-05




348




5.0




5.00





0.75






55-06




348




2.0




2.00






55-07




348




1.0




1.00






55-08




220




1.5





1.5




3.00




3.0






55-09




220




1.5





1.5




3.00






3.0






55-10




220




1.5





1.5




6.00




3.0






55-11




220




1.5





1.5




6.00






3.0






55-12




220




3.0





1.5




3.00




3.0






55-13




220




3.0





1.5




3.00






3.0






55-14




348




1.5





1.5




6.00




3.0






55-15




348




3.0





1.5




3.00




3.0






55-16




348





3.00






55-17




348




3.0








3.0






55-18




348




5.0






13.00





5.0














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 55b.















TABLE 55b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




28




32







200




41




37







300




73




64







400




22




30






Formulation J




100




38




32







200




82




73







300




89




91







400




97




89






55-01




100




73




28







200




90




66







300




97




92







400




100




96






55-02




100




77




32







200




87




67







300




84




78







400




98




84






55-03




100




79




33







200




82




66







300




99




81







400




97




88






55-04




100




69




35







200




95




59







300




96




84







400




92




91






55-05




100




82




32







200




92




55







300




96




71







400




94




87






55-06




100




83




33







200




100




52







300




100




68







400




99




75






55-07




100




77




35







200




90




58







300




95




71







400




94




90






55-08




100




51




40







200




89




75







300




96




92







400




95




98






55-09




100




76




57







200




98




81







300




97




86







400




96




98






55-10




100




69




60







200




98




63







300




95




82







400




99




90






55-11




100




61




60







200




94




84







300




97




89







400




99




97






55-12




100




64




53







200




95




82







300




96




90







400




95




98






55-13




100




61




58







200




94




78







300




88




87







400




100




94






55-14




100




56




61







200




88




77







300




91




82







400




97




89






55-15




100




42




52







200




82




80







300




86




90







400




97




92






55-16




100




64




49







200




86




75







300




97




88







400




100




82






55-17




100




57




32







200




88




66







300




95




73







400




100




88






55-18




100




52




35







200




70




77







300




82




79







400




97




73














Concentrate compositions 55-01 to 55-07, containing lecithin and Fluorad FC-754, exhibited outstanding herbicidal effectiveness. On ABUTH, several of these were about as effective at 100 g a.e./ha as commercial standard Formulation J at 200 g a.e./ha. On ECHCF, all exhibited strong enhancement over Formulation B but most did not equal Formulation J on this species. The performance of composition 55-07, containing lecithin and Fluorad FC-754 each at the extremely low weight/weight ratio to glyphosate a.e. of about 1:30, was remarkably high. The inclusion of a relatively high concentration of Ethomeen T/25, as in compositions 55-02 and 55-03, was not helpful to herbicidal effectiveness in the presence of lecithin and Fluorad FC-754, and may even have been detrimental. The relatively poor performance of composition 55-18, having a high Ethomeen T/25 concentration but in this case no Fluorad FC-754, is consistent with this observation. Without being bound by theory, it is believed that the presence of such high concentrations of Ethomeen T/25 together with lecithin results in the formation of mixed micelles rather than liposomes in aqueous dispersion. Composition 55-16, containing Fluorad FC-754 at a weight/weight ratio to glyphosate a.e. of about 1:10, but no lecithin, exhibited herbicidal effectiveness similar to that of composition 55-01, suggesting that under the conditions of this test a large part of the enhancement due to the lecithin/Fluorad FC-754 combination was attributable to the Fluorad FC-754 component.




Compositions 55-08 to 55-15, containing lecithin, butyl stearate, Ethomeen T/25 and a C


16-18


alkylether surfactant (ceteareth-20 or ceteareth-27) exhibited a very high degree of herbicidal effectiveness. Not only was performance, at least of 55-08 to 55-13, on ABUTH substantially better than that of Formulation J, these compositions performed considerably better than Formulation J on ECHCF as well.




Example 56




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 56a. Process (i) was followed for compositions 56-61 to 56-64, 56-67, 56-69 and 56-71 and process (iii) for compositions 56-01 to 56-66, 56-68, 56-70 and 56-72 using soybean lecithin (45% phospholipid, Avanti). The pH of all compositions was approximately 5.














TABLE 56a













% w/w
















Spray






Fluorad




Ethomeen




Ethomeen






composition




Lecithin




MON 0818




FC-754




T/25




C/12



















56-01




0.020




0.025




0.02








56-02




0.030




0.025




0.02






56-03




0.050




0.025




0.02






56-04




0.020




0.025




0.03






56-05




0.030




0.025




0.03






56-06




0.050




0.025




0.03






56-07




0.020




0.025




0.04






56-08




0.030




0.025




0.04






56-09




0.050




0.025




0.04






56-10




0.020




0.025




0.05






56-11




0.030




0.025




0.05






56-12




0.050




0.025




0.05






56-13




0.020





0.02






56-14




0.030





0.02






56-15




0.050





0.02






56-16




0.020





0.03






56-17




0.030





0.03






56-18




0.050





0.03






56-19




0.020





0.04






56-20




0.030





0.04






56-21




0.050





0.04






56-22




0.020





0.05






56-23




0.030





0.05






56-24




0.050





0.05






56-25




0.020





0.02




0.025






56-26




0.030





0.02




0.025






56-27




0.050





0.02




0.025






56-28




0.020





0.03




0.025






56-29




0.030





0.03




0.025






56-30




0.050





0.03




0.025






56-31




0.020





0.04




0.025






56-32




0.030





0.04




0.025






56-33




0.050





0.04




0.025






56-34




0.020





0.05




0.025






56-35




0.030





0.05




0.025






56-36




0.050





0.05




0.025






56-37




0.020





0.02





0.025






56-38




0.030





0.02





0.025






56-39




0.050





0.02





0.025






56-40




0.020





0.03





0.025






56-41




0.030





0.03





0.025






56-42




0.050





0.03





0.025






56-43




0.020





0.04





0.025






56-44




0.030





0.04





0.025






56-45




0.050





0.04





0.025






56-46




0.020





0.05





0.025






56-47




0.030





0.05





0.025






56-48




0.050





0.05





0.025






56-49




0.020





0.02




0.050






56-50




0.025





0.03




0.050






56-51




0.050





0.02




0.050






56-52




0.020





0.03




0.050






56-53




0.030





0.03




0.050






56-54




0.050





0.03




0.050






56-55




0.020




0.050




0.02






56-56




0.025




0.050




0.03






56-57




0.050




0.050




0.02






56-58




0.020




0.050




0.03






56-59




0.030




0.050




0.03






56-60




0.050




0.050




0.03






56-61





0.050






56-62







0.050






56-63








0.025






56-64





0.025






56-65




0.050





0.08




0.025






56-66




0.025





0.03





0.025






56-67






0.05






56-68




0.050






56-69






0.05




0.050






56-70




0.050






0.050






56-71





0.050




0.05






56-72




0.050




0.050














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




Formulation J was applied as a comparative treatment. Results, averaged for all replicates of each treatment, are shown in Table 56b.
















TABLE 56b













Glyphosate rate




% Inhibition

















Spray composition




g a.e./ha




ABUTH




ECHCF




















Formulation J




100




14




42








187




44




87








300




71




90








400




92




97







56-01




187




80




80







56-02




187




80




97







56-03




187




79




94







56-04




187




79




91







56-05




187




81




80







56-06




187




73




88







56-07




187




86




90







56-08




187




88




91







56-09




187




77




85







56-10




187




81




80







56-11




187




88




68







56-12




187




87




72







56-13




187




85




61







56-14




187




83




47







56-15




187




86




61







56-16




187




86




57







56-17




187




85




44







56-18




187




81




62







56-19




187




82




63







56-20




187




87




62







56-21




187




84




48







56-22




187




80




67







56-23




187




86




89







56-24




187




78




64







56-25




187




84




87







56-26




187




81




81







56-27




187




74




85







56-28




187




71




90







56-29




187




76




74







56-30




187




81




89







56-31




187




78




80







56-32




187




79




84







56-33




187




82




84







56-34




187




74




87







56-35




187




81




89







56-36




187




85




79







56-37




187




68




89







56-38




187




69




85







56-39




187




86




85







56-40




187




83




89







56-41




187




77




76







56-42




187




83




76







56-43




187




74




83







56-44




187




84




69







56-45




187




85




71







56-46




187




80




86







56-47




187




83




96







56-48




187




81




87







56-49




187




75




99







56-50




187




78




97







56-51




187




76




97







56-52




187




77




92







56-53




187




74




88







56-54




187




73




81







56-55




187




70




87







56-56




187




79




88







56-57




187




72




89







56-58




187




72




79







56-59




187




53




80







56-60




187




80




73







56-61




187




46




78







56-62




187




54




94







56-63




187




48




98







56-64




187




59




97







56-65




187




87




84







56-66




187




89




96







56-67




187




86




69







56-68




187




46




43







56-69




187




75




90







56-70




187




55




83







56-71




187




79




80







56-72




187




55




82















All compositions of this Example containing Fluorad FC-754 showed much greater herbicidal effectiveness on ABUTH at 187 g a.e./ha than did Formulation J at the same rate, in many cases giving inhibition of ABUTH equal to or greater than provided by Formulation J at 300 g a.e./ha. The only compositions of the Example not showing strong improvement over Formulation J on ABUTH were 56-61 to 56-64, 56-68, 56-70 and 56-72. These are the only formulations of the Example not containing Fluorad FC-754.




Example 57




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 57a. Process (i) was followed for compositions 57-02, 57-04, 57-06, 57-08, 57-10, 57-12. 57-14 and 57-16 to 57-18, and compositions 57-01, 57-03, 57-05, 57-07, 57-09, 57-11 and 57-13 using soybean lecithin (45% phospholipid, Avanti). The pH of all compositions was approximately 5.















TABLE 57a











Spray




% w/w





Type of














composition




Lecithin




Surfactant




surfactant

















57-01




0.05




0.05




Surf H2






57-02





0.05




Surf H2






57-03




0.05




0.05




Surf H3






57-04





0.05




Surf H3






57-05




0.05




0.05




Surf H4






57-06





0.05




Surf H4






57-07




0.05




0.05




Surf H5






57-08





0.05




Surf H5






57-09




0.05




0.05




Fluorad FC-754






57-10





0.05




Fluorad FC-754






57-11




0.05




0.05




Surf H1






57-12





0.05




Surf H1






57-13




0.05




0.05




MON 0818






57-14





0.05




MON 0818






57-15




0.05




0.05




Ethomeen T/25






57-16





0.05




Ethomeen T/25






57-17





0.10




MON 0818






57-18





0.10




Ethomeen T/25














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 57b.
















TABLE 57b













Glyphosate rate




% Inhibition

















Spray composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




100




12




22








200




43




43








300




63




78








400




75




82







Formulation J




100




47




27








200




89




83








300




98




98








400




99




97







57-01




100




65




60








200




94




84








300




99




97








400




100




98







57-02




100




40




45








200




77




75








300




91




90








400




94




98







57-03




100




63




37








200




82




82








300




97




99








400




99




97







57-04




100




52




38








200




79




73








300




95




98








400




99




97







57-05




100




73




68








200




85




94








300




98




99








400




100




99







57-06




100




38




58








200




73




92








300




85




100








400




100




98







57-07




100




50




43








200




80




78








300




94




86








400




94




95







57-08




100




50




48








200




75




62








300




89




77








400




90




79







57-09




100




91




47








200




98




75








300




99




97








400




99




94







57-10




100




87




38








200




89




73








300




99




83








400




100




94







57-11




100




77




73








200




93




79








300




98




96








400




99




98







57-12




100




55




52








200




82




89








300




96




99








400




99




100







57-13




100




75




63








200




93




92








300




98




99








400




99




99







57-14




100




78




82








200




88




86








300




96




99








400




99




100







57-15




100




77




68








200




94




95








300




98




97








400




99




98







57-16




100




75




75








200




88




99








300




98




99








400




99




100







57-17




100




72




77








200




85




98








300




98




100








400




99




99







57-18




100




77




77








200




90




96








300




97




99








400




99




100















Herbicidal activity with compositions 57-13 to 57-18, based on alkylamine based surfactants known in the art, was very high in this test. Compositions 57-01 to 57-12 of the present invention also exhibited excellent herbicidal effectiveness. Overall, surfactants “Surf H1” to “Surf H5” having hydrocarbon hydrophobes were not quite as effective as Fluorad FC-754 having a fluorocarbon hydrophobe, either when used as sole excipient substance or together with lecithin.




Example 58




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 58a. These compositions are water-in-oil-in-water multiple emulsions and were prepared by process (vi) described above.















TABLE 58a













% w/w



















Conc.




Glyphosate




Butyl




Emulsifier




Emulsifier




% in inner aq. phase




Emulsifier




Emulsifier



















comp.




a.e.




stearate




#1




#2




Water




Glyphosate




#1




#2






















58-01




10




18.0




3.0




5.0




9.0




20 




Span 80




Tween 20






58-02




10




7.5




3.0




5.0




4.5




20 




Span 80




Tween 20






58-03




10




7.5




3.0




10.0




4.5




0




Surfynol 104




Neodol 25-12






58-04




10




7.5




3.0




10.0




4.5




0




Surfynol 104




Neodol 25-20






58-05




10




7.5




3.0




10.0




4.5




0




Surfynol 104




Tergitol 15-S-15






58-06




10




7.5




3.0




10.0




4.5




0




Surfynol 104




Tergitol 15-S-20






58-07




10




7.5




3.0




10.0




4.5




0




Surfynol 104




Tween 20






58-08




10




7.5




3.0




10.0




4.5




0




Surfynol 104




ceteareth-55






58-09




10




7.5




3.0




10.0




4.5




0




Surfynol 104




Tergitol 15-S-30






58-10




10




7.5




3.0




10.0




4.5




0




Neodol 25-3




ceteareth-55






58-11




10




7.5




3.0




10.0




4.5




0




Neodol 25-3




Tergitol 15-S-30






58-12




10




7.5




3.0




10.0




4.5




0




Span 60




ceteareth-55






58-13




10




7.5




3.0




10.0




4.5




0




Span 60




Tergitol 15-S-30






58-14




10




7.5




3.0




10.0




4.5




0




oleth-2




ceteareth-55






58-15




10




7.5




3.0




10.0




4.5




0




oleth-2




Tergitol 15-S-30






58-16




10




7.5




3.0




10.0




4.5




0




Emid 6545




ceteareth-55






58-17




10




7.5




3.0




10.0




4.5




0




Emid 6545




Tergitol 15-S-30














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 35 days after planting ABUTH and 33 days after planting ECHCF, and evaluation of herbicidal inhibition was done 17 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 58b.















TABLE 58b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




0




0







250




35




40







350




50




63







450




60




43






Formulation C




150




63




63







250




80




96







350




92




98







450




98




87






Formulation J




150




43




30







250




75




85







350




82




98







450




96




95






58-01




150




65




53







250




85




70







350




90




87







450




98




73






58-02




150




63




5







250




78




53







350




88




80







450




97




87






58-03




150




75




0







250




87




22







350




88




72







450




97




17






58-04




150




84




0







250




90




10







350




95




70







450




98




60






58-05




150




77




0







250




83




3







350




93




30







450




95




10






58-06




150




72




0







250




83




47







350




94




60







450




98




20






58-07




150




75




0







250




77




40







350




96




47







450




96




50






58-08




150




87




40







250




97




82







350




99




83







450




100




77






58-09




150




82




10







250




82




40







350




96




67







450




97




67






58-10




150




82




13







250




94




83







350




99




85







450




99




83






58-11




150




73




17







250




83




60







350




88




73







450




96




63






58-12




150




80




20







250




93




85







350




96




82







450




96




82






58-13




150




78




20







250




83




50







350




92




90







450




92




85






58-14




150




80




30







250




97




85







350




99




99







450




97




96






58-15




150




82




30







250




87




75







350




99




92







450




99




93






58-16




150




82




53







250




96




82







350




96




97







450




87




82






58-17




150




72




20







250




80




63







350




92




75







450




95




87














Considerable variation was seen in herbicidal effectiveness of water-in-oil-in-water multiple emulsions of this Example, especially on ECHCF. Among the most efficacious were 58-08, 58-10, 58-12, 58-14 and 58-16. All of these contained a C


16-18


alkylether surfactant, ceteareth-55. When Tergitol 15-S-30, a C


12-15


secondary alkylether surfactant, replaced ceteareth-55, as in 58-09, 58-11, 58-13, 58-15 and 58-17, herbicidal effectiveness, at least on ECHCF, was in most cases markedly reduced.




Example 59




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 59a. Concentrate compositions 59-01 and 59-02 are water-in-oil-in-water multiple emulsions and were prepared by process (vi), using Span 80 as emulsifier #1. Concentrate compositions 59-03 to 59-12 and 59-14 to 59-17 are oil-in-water emulsions and were prepared by process (vii). Concentrate composition 59-13 is an aqueous solution concentrate and was prepared by process (viii), the component indicated below as “emulsifier #2” being the surfactant component.















TABLE 59a













% w/w


















Conc.




Glyphosate




Butyl





Emulsifier




% in inner aq. Phase




Emulsifier


















comp.




a.e.




stearate




Span 80




#2




Water




Glyphosate




#2





















59-01




10




18.0




3.0




5.0




12.2




20




Tween 20






59-02




10




7.5




3.0




5.0




5.3




20




Tween 20






59-03




10




1.0





10.0






Neodol 25-20






59-04




10




3.0





10.0






Neodol 25-20






59-05




10




1.0





5.0






Neodol 25-20






59-06




10




3.0





5.0






Neodol 25-20






59-07




15




1.0





10.0






Neodol 25-20






59-08




15




3.0





10.0






Neodol 25-20






59-09




15




1.0





5.0






Neodol 25-20






59-10




15




3.0





5.0






Neodol 25-20






59-11




20




1.0





5.0






Neodol 25-20






59-12




20




1.0





10.0






Neodol 25-20






59-13




10






10.0






Neodol 25-20






59-14




10




7.5





10.0






Neodol 25-20






59-15




10




7.5





10.0






Neodol 25-12






59-16




10




7.5





10.0






steareth-20






59-17




10




7.5





10.0






oleth-20














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and 19 days after planting ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulation B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 59b.















TABLE 59b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




0




30







250




10




40







350




37




73







450




58




68






Formulation C




150




42




79







250




77




98







350




99




97







450




97




93






Formulation J




150




43




67







250




73




90







350




94




98







450




77




78






59-01




150




58




76







250




75




77







350




88




93







450




95




83






59-02




150




27




63







250




60




87







350




82




98







450




77




92






59-03




150




47




76







250




65




92







350




94




99







450




95




91






59-04




150




70




86







250




86




95







350




97




98







450




99




90






59-05




150




42




80







250




72




90







350




90




93







450




99




96






59-06




150




48




57







250




78




92







350




94




99







450




96




92






59-07




150




78




95







250




96




96







350




98




98







450




100




97






59-08




150




88




96







250




98




98







350




100




99







450




100




99






59-09




150




82




93







250




94




96







350




99




97







450




99




93






59-10




150




72




83







250




97




93







350




99




100







450




100




98






59-11




150




87




83







250




98




97







350




100




99







450




100




99






59-12




150




93




99







250




99




99







350




99




97







450




100




99






59-13




150




70




90







250




91




88







350




97




94







450




99




86






59-14




150




67




76







250




93




80







350




98




95







450




95




78






59-15




150




68




65







250




90




87







350




97




80







450




98




93






59-16




150




83




73







250




90




93







350




99




100







450




100




100






59-17




150




80




66







250




98




77







350




99




83







450




100




85














Very high herbicidal activity was evident in compositions 59-13 to 59-17, which have a very high ratio of surfactant to glyphosate a.e. of 1:1. Activity was too high to clearly distinguish among these compositions, but 59-16 and 59-17, containing steareth-20 and oleth-20 respectively, exbited greater effectiveness on ABUTH at the lowest glyphosate rate than 59-14 and 59-15, containing Neodol 25-20 and Neodol 25-12 respectively.




Example 60




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 60a. Concentrate compositions 60-01 and 60-02 are water-in-oil-in-water multiple emulsions and were prepared by process (vi), using Span 80 as emulsifier #1. Concentrate compositions 60-03 to 60-12 and 60-14 to 60-17 are oil-in-water emulsions and were prepared by process (vii). Concentrate composition 60-13 is an aqueous solution concentrate and was prepared by process (viii), the component indicated below as “emulsifier #2” being the surfactant component.
















TABLE 60a














% in inner








% w/w




aq. phase



















Gly-






Emul-





Gly-







Conc.




phosate




Butyl




Span




sifier




Wa-




phos-




Emulsifier






comp




a.e.




stearate




80




#2




ter




ate




#2





















60-01




10




18.0




3.0




5.0




12.2




20




Tween 20






60-02




10




7.5




3.0




5.0




5.3




20




Tween 20






60-03




10




1.0





10.0






Tween 80






60-04




10




3.0





10.0






Tween 80






60-05




10




1.0





5.0






Tween 80






60-06




10




3.0





5.0






Tween 80






60-07




15




1.0





10.0






Tween 80






60-08




15




3.0





10.0






Tween 80






60-09




15




1.0





5.0






Tween 80






60-10




15




3.0





5.0






Tween 80






60-11




20




1.0





5.0






Tween 80






60-12




20




1.0





10.0






Tween 80






60-13




10






10.0






Tween 80






60-14




10




7.5





10.0






Tween 80






60-15




10




7.5





10.0






Neodol 25-20






60-16




10




7.5





10.0






steareth-20






60-17




10




7.5





10.0






oleth-20














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and 19 days after planting ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 60b.
















TABLE 60b













Glyphosate rate




% Inhibition

















Composition applied




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




0




0








250




3




10








350




17




20








450




20




30







Formulation C




150




70




33








250




80




70








350




85




80








450




97




77







Formulation J




150




7




20








250




70




80








350




78




80








450




83




80







60-01




150




40




7








250




48




20








350




73




23








450




75




30







60-02




150




3




0








250




10




17








350




47




23








450




50




30







60-03




150




0




2








250




33




13








350




63




40








450




68




43







60-04




150




17




7








250




43




20








350




78




63








450




78




63







60-05




150




10




3








250




20




13








350




58




40








450




75




40







60-06




150




3




0








250




27




20








350




60




23








450




72




23







60-07




150




32




10








250




68




20








350




75




50








450




86




60







60-08




150




27




20








250




68




30








350




82




40








450




90




73







60-09




150




43




10








250




60




33








350




72




63








450




75




73







60-10




150




33




10








250




62




30








350




77




60








450




83




70







60-11




150




48




13








250




72




63








350




83




80








450




87




80







60-12




150




23




13








250




60




50








350




75




80








450




86




78







60-13




150




32




13








250




47




40








350




75




50








450




78




70







60-14




150




27




20








250




75




53








350




82




70








450




92




67







60-15




150




70




20








250




78




30








350




92




80








450




93




80







60-16




150




68




40








250




73




30








350




93




80








450




93




77







60-17




150




73




20








250




85




30








350




93




60








450




95




63















Compositions 60-16 and 60-17, containing steareth-20 and oleth-20 respectively, exhibited very high herbicidal activity on ABUTH. At the very high surfactant to glyphosate a.e. ratio (1:1) of these compositions, no difference was evident between these compositions and an otherwise similar composition (60-15) containing Neodol 25-20 in place of steareth-20 or oleth-20.




Example 61




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 61a. All are oil-in-water emulsions and were prepared by process (vii).















TABLE 61a













% w/w
















Concentrate




Glyphosate




Butyl





Type of






composition




g a.e./1




stearate




Surfactant




surfactant


















61-01




163




1.00




10.0




Tween 80






61-02




163




1.00




10.0




Neodol 25-12






61-03




163




1.00




10.0




Neodol 25-20






61-04




163




1.00




10.0




steareth-20






61-05




163




1.00




10.0




oleth-20






61-06




163




1.00




10.0




Tergitol 15-S-40






61-07




163




1.00




10.0




Tergitol 15-S-15






61-08




163




1.00




10.0




Tergitol 15-S-20






61-09




163




0.50




10.0




Tergitol 15-S-40






61-10




163




0.50




10.0




Tergitol 15-S-15






61-11




163




0.50




10.0




Tergitol 15-S-20






61-12




163




0.50




5.0




Tergitol 15-S-40






61-13




163




0.50




5.0




Tergitol 15-S-15






61-14




163




0.50




5.0




Tergitol 15-S-20






61-15




163




0.25




10.0




Tergitol 15-S-40














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 19 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment. are shown in Table 61b.















TABLE 61b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




2




20







250




2




30







350




5




53







450




45




75






Formulation C




150




45




63







250




77




93







350




83




99







450




93




100






Formulation J




150




15




40







250




70




73







350




78




98







450




92




99






61-01




150




42




50







250




72




89







350




80




96







450




93




98






61-02




150




45




80







250




72




83







350




85




91







450




97




98






61-03




150




60




80







250




75




87







350




82




96







450




86




99






61-04




150




65




60







250




82




70







350




93




80







450




98




87






61-05




150




72




60







250




83




87







350




95




93







450




98




97






61-06




150




50




45







250




68




70







350




77




85







450




83




90






61-07




150




25




40







250




65




50







350




80




77







450




83




80






61-08




150




37




33







250




72




80







350




77




87







450




80




90






61-09




150




32




47







250




65




73







350




77




75







450




80




94






61-10




150




17




30







250




65




70







350




75




70







450




78




89






61-11




150




35




33







250




68




68







350




77




77







450




92




75






61-12




150




13




35







250




57




40







350




75




57







450




77




83






61-13




150




35




40







250




63




43







350




77




77







450




83




75






61-14




150




30




25







250




67




53







350




78




85







450




83




77






61-15




150




13




37







250




65




50







350




77




57







450




87




82














At a surfactant to glyphosate a.e. weight/weight ratio of about 1:1.5, compositions containing steareth-20 or oleth-20 (61-04 and 61-05 respectively) exhibited herbicidal effectiveness on ABUTH similar to one containing Neodol 25-20 (61-03).




Example 62




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 62a. All are oil-in-water emulsions and were prepared by process (vii).















TABLE 62a













% w/w
















Concentrate




Glyphosate




Butyl





Type of






composition




g a.e./l




stearate




Surfactant




surfactant


















62-01




163




1.0




10.0




Tween 80






62-02




163




1.0




10.0




Neodol 25-12






62-03




163




1.0




10.0




Neodol 25-20






62-04




163




1.0




10.0




steareth-20






62-05




163




1.0




10.0




oleth-20






62-06




163




1.0




10.0




Tergitol 15-S-40






62-06




163




1.0




10.0




Tergitol 15-S-15






62-08




163




1.0




10.0




Tergitol 15-S-20






62-09




163




0.5




10.0




Tergitol 15-S-40






62-10




163




0.3




10.0




Tergitol 15-S-15






62-11




163




0.3




10.0




Tergitol 15-S-20






62-12




163




0.3




10.0




Tergitol 15-S-40






62-13




163




0.3




5.0




Tergitol 15-S-15






62-14




163




0.3




5.0




Tergitol 15-S-20






62-15




163




0.3




5.0




Tergitol 15-S-40














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 21 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 62b.















TABLE 62b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




0




23







250




0




40







350




5




53







450




13




57






Formulation C




150




0




47







250




28




87







350




72




98







450




97




97






Formulation J




150




5




40







250




20




63







350




67




93







450




82




92






62-01




150




2




40







250




30




50







350




50




70







450




57




85






62-02




150




10




50







250




33




50







350




75




72







450




75




88






62-03




150




17




53







250




60




60







350




70




92







450




78




94






62-04




150




57




45







250




70




70







350




82




93







450




83




95






62-05




150




47




45







250




70




80







350




80




88







450




88




92






62-06




150




2




42







250




20




60







350




35




75







450




58




89






62-07




150




0




42







250




30




68







350




40




75







450




77




82






62-08




150




2




40







250




25




60







350




50




83







450




75




86






62-09




150




2




43







250




27




83







350




40




73







450




70




78






62-10




150




2




42







250




32




47







350




43




63







450




70




82






62-11




150




0




30







250




25




53







350




35




75







450




70




75






62-12




150




2




40







250




13




57







350




25




75







450




40




83






62-13




150




5




42







250




23




62







350




38




63







450




67




60






62-14




150




2




33







250




13




48







350




30




53







450




70




88






62-15




150




2




33







250




18




48







350




30




75







450




43




65














In this test, herbicidal effectiveness overall was lower than in the previous Example, particularly on ABUTH. In these circumstances, at a surfactant to glyphosate a.e. weight/weight ratio of about 1:1.5, compositions containing steareth-20 or oleth-20 (62-04 and 62-05 respectively) exhibited greater herbicidal effectiveness on both ABUTH and ECHCF than one containing Neodol 25-20 (62-03).




Example 63




Aqueous concentrate compositions were prepared containing glyphosate ammonium or IPA salt and excipient ingredients as shown in Table 63a. Concentrate composition 63-01 is a water-in-oil-in-water multiple emulsion and was prepared by process (vi), using Span 80 as emulsifier #1. Concentrate compositions 63-02 to 63-11 and 63-17 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 63-12 to 63-16 are aqueous solution concentrates and were prepared by process (viii), the component indicated below as “emulsifier #2” being the surfactant component.















TABLE 63a













% w/w



















Conc.




Glyphosate




Butyl





Emulsifier




% in inner aq. phase




Emulsifier




Glyphosate



















comp.




a.e.




stearate




Span 80




#2




Water




Glyphosate




#2




salt






















63-01




10




18.0




3.0




5.0




9.0




20




Tween 20




IPA






63-02




15




1.0





10.0






Tween 80




IPA






63-03




15




1.0





10.0






Neodol 25-12




IPA






63-04




15




1.0





10.0






Neodol 25-20




IPA






63-05




15




1.0





10.0






steareth-20




IPA






63-06




15




1.0





10.0






oleth-20




IPA






63-07




15




1.0





10.0






Tween 80




ammonium






63-08




15




1.0





10.0






Neodol 25-12




ammonium






63-09




15




1.0





10.0






Neodol 25-20




ammonium






63-10




15




1.0





10.0






steareth-20




ammonium






63-11




15




1.0





10.0






oleth-20




ammonium






63-12




15






10.0






Tween 80




IPA






63-13




15






10.0






Neodol 25-12




IPA






63-14




15






10.0






Neodol 25-20




IPA






63-15




15






10.0






steareth-20




IPA






63-16




15






10.0






oleth-20




IPA






63-17




15




1.0





10.0






Emerest 2661




IPA














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 20 days after application. Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 63b.















TABLE 63b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




2




5







250




3




25







350




28




30







450




53




50






Formulation C




150




5




25







250




60




50







350




85




83







450




88




88






Formulation J




150




2




10







250




70




40







350




82




53







450




87




83






63-01




150




23




20







250




72




30







350




80




80







450




85




69






63-02




150




5




18







250




72




38







350




82




63







450




85




83






63-03




150




25




20







250




70




57







350




85




68







450




90




83






63-04




150




25




27







250




77




67







350




85




62







450




88




70






63-05




150




60




25







250




82




62







350




87




73







450




85




80






63-06




150




50




32







250




78




78







350




91




91







450




98




98






63-07




150




5




25







250




55




77







350




77




86







450




83




99






63-08




150




0




13







250




58




78







350




80




85







450




85




87






63-09




150




7




25







250




57




72







350




77




83







450




91




92






63-10




150




50




25







250




80




55







350




86




87







450




92




82






63-11




150




53




30







250




78




80







350




87




89







450




95




98






63-12




150




0




25







250




50




77







350




77




90







450




83




94






63-13




150




2




30







250




55




75







350




72




92







450




85




80






63-14




150




12




30







250




75




78







350




84




90







450




96




94






63-15




150




55




35







250




78




80







350




80




94







450




86




98






63-16




150




50




35







250




73




63







350




84




83







450




89




95






63-17




150




0




10







250




10




53







350




53




83







450




62




87














Compositions containing stearth-20 or oleth-20 (63-05, 63-06, 63-10, 63-11, 63-15, 63-16) generally exhibited superior herbicidal effectiveness to counterparts containing Neodol 25-20 (63-04, 63-09, 63-14), at least on ABUTH. The presence of a small amount of butyl stearate tended to enhance effectiveness on ABUTH (compare 63-05 and 63-06 with 63-15 and 63-16).




Example 64




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 64a. Concentrate composition 64-01 is a water-in-oil-in-water multiple emulsion and was prepared by process (vi), using Span 80 as emulsifier #1. Concentrate compositions 64-02 to 64-08, 64-14, 64-16 and 64-17 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 64-09 to 64-13 and 64-15 are aqueous solution concentrates and were prepared by process (viii), the component indicated below as “emulsifier #2” being the surfactant component.















TABLE 64a













% w/w


















Conc.




Glyphosate




Butyl





Emulsifier




% in inner aq. phase



















comp.




a.e.




stearate




Span 80




#2




Water




Glyphosate




Emulsifier #2





















64-01




10




18.0




3.0




2.5




9.0




20




Tween 20






64-02




15




1.0





10.0






Emerest 2661






64-03




15




1.0





10.0






Tween 80






64-04




15




1.0





10.0






oleth-20






64-05




15




1.0





10.0






Neodol 25-20






64-06




15




1.0





10.0






ceteareth-27






64-07




15




1.0





10.0






ceteareth-55






64-08




15




1.0





10.0






Genapol UD-110






64-09




15






10.0






ceteareth-27






64-10




15






10.0






ceteareth-55






64-11




15






10.0






Genapol UD-110






64-12




15






10.0






oleth-20






64-13




10






10.0






oleth-20






64-14




10




1.0





10.0






oleth-20






64-15




20






10.0






oleth-20






64-16




15




0.5





5.0






oleth-20






64-17




15




0.5





10.0






oleth-20














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Application of spray compositions were 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B, C and J were applied as comparative treatments. Results, average for all replicates of each treatment, are shown in Table 64b.















TABLE 64b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




0




0







250




8




20







350




27




40







450




62




50






Formulation C




150




27




50







250




75




70







350




92




80







450




97




92






Formulation J




150




23




30







250




72




50







350




94




63







450




95




80






64-01




150




22




30







250




60




40







350




83




57







450




90




67






64-02




150




12




33







250




45




50







350




73




63







450




83




83






64-03




150




27




43







250




68




50







350




80




63







450




87




87






64-04




150




68




47







250




95




73







350




99




78







450




95




90






64-05




150




50




50







250




77




77







350




90




83







450




98




83






64-06




150




78




67







250




93




82







350




97




87







450




99




97






64-07




150




87




57







250




96




73







350




99




85







450




99




97






64-08




150




42




30







250




73




53







350




82




85







450




95




89






64-09




150




67




40







250




95




73







350




99




95







450




99




98






64-10




150




85




60







250




96




68







350




96




91







450




100




88






64-11




150




13




10







250




67




50







350




78




60







450




88




73






64-12




150




72




43







250




97




68







350




98




83







450




99




93






64-13




150




73




57







250




88




70







350




98




87







450




99




96






64-14




150




80




50







250




96




70







350




99




85







450




98




88






64-15




150




70




43







250




96




53







350




97




82







450




99




89






64-16




150




62




53







250




88




72







350




99




81







450




99




91






64-17




150




72




58







250




95




68







350




100




89







450




100




93














The greatest herbicidal effectiveness in this test was exhibited by compositions containing a C


16-18


alkylether surfactant (oleth-20. ceteareth-27 or ceteareth-55).




Example 65




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 65a. All are oil-in-water emulsions and were prepared by process (vii).















TABLE 65a













% w/w
















Concentrate




Glyphosate




Butyl





Type of






composition




g a.e./1




stearate




Surfactant




surfactant


















61-01




163




1.00




10.0




Tween 80






65-02




163




1.00




10.0




Emerest 2661






65-03




326




1.00




10.0




Genapol UD-110






65-04




326




0.50




10.0




Genapol UD-110






65-05




326




0.25




10.0




Genapol UD-110






65-06




163




0.25




10.0




Genapol UD-110






65-07




163




1.00




10.0




Genapol UD-110






65-08




163




1.00




10.0




Neodol 1-9






65-09




163




1.00




10.0




Neodol 1-12






65-10




163




1.00




10.0




Neodol 25-20






65-11




163




1.00




10.0




Neodol 25-12






65-12




163




1.00




10.0




Neodox 25-11






65-13




163




1.00




10.0




laureth-23






65-14




163




1.00




10.0




ceteth-20






65-15




163




1.00




10.0




steareth-20






65-16




163




1.00




10.0




oleth-20














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 15 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 23 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 65b.















TABLE 65b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




0




0







250




25




22







350




60




40







450




65




52






Formulation C




150




43




52







250




72




83







350




87




98







450




97




95






Formulation J




150




50




43







250




75




91







350




86




96







450




95




97






65-01




150




50




30







250




75




75







350




85




87







450




90




92






65-02




150




35




47







250




58




77







350




75




85







450




80




96






65-03




150




33




32







250




57




53







350




75




78







450




84




94






65-04




150




20




25







250




55




68







350




78




91







450




82




97






65-05




150




37




12







250




58




42







350




81




70







450




86




73






65-06




150




50




8







250




65




40







350




81




65







450




92




85






65-07




150




50




30







250




63




48







350




84




68







450




98




84






65-08




150




43




35







250




52




65







350




73




85







450




84




85






65-09




150




55




40







250




68




58







350




79




65







450




97




73






65-10




150




69




40







250




81




68







350




94




92







450




99




96






65-11




150




58




50







250




84




60







350




90




83







450




94




93






65-12




150




50




40







250




57




67







350




65




84







450




75




98






65-13




150




57




53







250




78




73







350




89




97







450




98




97






65-14




150




68




67







250




85




73







350




97




98







450




100




97






65-15




150




72




50







250




88




89







350




89




98







450




99




97






65-16




150




65




53







250




87




72







350




97




85







450




100




95














Activity overall in this test was very high, and differences among compositions in herbicidal effectivess are difficult to discern clearly.




Example 66




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 66a. All are oil-in-water emulsions and were prepared by process (vii). The pH of all compositions was approximately 5.















TABLE 66a













% w/w
















Concentrate




Glyphosate




Butyl





Type of






composition




g a.e./1




stearate




Surfactant




surfactant


















61-01




163




1.00




10.0




Tween 80






65-02




163




1.00




10.0




Emerest 2661






65-03




163




1.00




10.0




Neodol 25-20






65-04




163




1.00




10.0




oleth-20






65-05




163




0.50




5.0




oleth-20






65-06




163




0.25




2.5




oleth-20






65-07




163




0.50




2.5




oleth-20






65-08




163




0.50




1.0




oleth-20






65-09




163




0.25




5.0




oleth-20






65-10




326




1.00




10.0




Neodol 1-12






65-11




326




0.50




10.0




Neodol 1-12






65-12




326




0.25




10.0




Neodol 1-12






65-13




326




1.00




5.0




Neodol 1-12






65-14




326




0.50




5.0




Neodol 1-12






65-15




326




0.25




5.0




Neodol 1-12






65-16




326




0.10




5.0




Neodol 1-12














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 15 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 20 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment. are shown in Table 66b.















TABLE 66b













Glyphosate rate




% Inhibition
















Concentrate composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




7




50








250




45




60








350




73




73








450




80




78







Formulation C




150




75




77








250




87




100








350




96




99








450




99




97







Formulation J




150




72




77








250




83




89








350




97




99








450




97




98







66-01




150




60




75








250




80




85








350




93




97








450




98




98







66-02




150




57




75








250




70




83








350




87




83








450




90




94







66-03




150




77




80








250




87




92








350




97




87








450




99




98







66-04




150




80




89








250




93




92








350




99




99








450




100




99







66-05




150




83




83








250




92




93








350




97




90








450




100




93







66-06




150




77




77








250




80




91








350




90




99








450




98




99







66-07




150




77




83








250




82




89








350




90




91








450




97




98







66-08




150




47




82








250




73




82








350




80




97








450




92




91







66-09




150




73




78








250




87




88








350




97




94








450




99




99







66-10




150




52




67








250




70




80








350




93




88








450




93




94







66-11




150




40




68








250




72




85








350




87




96








450




93




96







66-12




150




37




60








250




68




83








350




85




85








450




93




75







66-13




150




28




63








250




53




80








350




85




97








450




88




97







66-14




150




37




63








250




58




73








350




83




96








450




90




91







66-15




150




30




70








250




47




83








350




82




89








450




87




89







66-16




150




40




53








250




53




82








350




80




80








450




88




77















Composition 66-04, containing 1% butyl stearate and 10% oleth-20 (surfactant to glyphosate a.e. weight/weight ratio about 1:1.5), exhibited marginally greater herbicidal effectiveness than composition 66-03. containing 1% butyl stearate and 10% Neodol 25-20. At this very high surfactant to glyphosate ratio, however, both performed extremely well. Surprisingly, when the butyl stearate and oleth-20 concentrations were significantly lowered, this high level of performance was maintained to a remarkable degree. Even when butyl stearate was reduced to 0.25% and oleth-20 to 2.5% (surfactant to glyphosate a.e. ratio about 1:6), as in composition 66-06, herbicidal effectiveness was still similar to that obtained with commercial standard Formulations C and J.




Example 67




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 67a. Concentrate compositions 67-01 to 67-08 and 67-11 to 67-16 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 67-09 and 67-10 are aqueous solution concentrates and were prepared by process (viii). The pH of all compositions was approximately 5.















TABLE 67a













% w/w
















Concentrate




Glyphosate




Butyl





Type of






composition




a.e.




stearate




Surfactant




surfactant


















67-01




15.0




0.25




5.0




Emerest 2661






67-02




15.0




0.25




5.0




Tween 80






67-03




15.0




0.25




5.0




Neodol 25-20






67-04




15.0




0.25




5.0




laureth-23






67-05




15.0




0.25




5.0




ceteth-20






67-06




15.0




0.25




2.5




Tween 80






67-07




15.0




0.10




1.0




Tween 80






67-08




15.0




1.00




10.0




Tween 80






67-09




15.0





5.0




laureth-23






67-10




15.0





5.0




ceteth-20






67-11




15.0




1.00




10.0




Neodol 25-20






67-12




15.0




1.00




10.0




oleth-20






67-13




15.0




0.50




5.0




oleth-20






67-14




15.0




0.25




5.0




oleth-20






67-15




15.0




0.25




2.5




oleth-20






67-16




15.0




0.25




5.0




Genapol UD-110














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 12 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 67b.















TABLE 67b













Glyphosate rate




% Inhibition
















Concentrate composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




2




10








250




5




20








350




43




30








450




58




43







Formulation C




150




68




50








250




92




79








350




96




90








450




98




85







Formulation J




150




57




43








250




90




63








350




95




80








450




95




95







67-01




150




7




33








250




50




43








350




77




53








450




80




93







67-02




150




17




50








250




72




70








350




80




80








450




80




93







67-03




150




43




40








250




75




68








350




87




75








450




96




95







67-04




150




33




47








250




73




63








350




80




77








450




90




93







67-05




150




73




37








250




92




57








350




95




88








450




95




73







67-06




150




25




35








250




68




47








350




80




92








450




88




85







67-07




150




3




30








250




57




40








350




77




53








450




80




67







67-08




150




53




43








250




77




62








350




80




88








450




93




80







67-09




150




32




60








250




77




53








350




93




73








450




97




93







67-10




150




75




35








250




92




77








350




96




77








450




97




93







67-11




150




75




53








250




90




78








350




95




89








450




98




97







67-12




150




80




43








250




95




73








350




96




92








450




98




89







67-13




150




75




53








250




92




97








350




97




99








450




96




93







67-14




150




78




70








250




90




92








350




93




97








450




95




93







67-15




150




70




60








250




83




98








350




95




99








450




97




99







67-16




150




27




52








250




75




73








350




80




98








450




83




99















Extremely high herbicidal effectiveness was again observed with a composition (67-15) containing 15% glyphosate a.e. and just 2.5% oleth-20 together with 0.25% butyl stearate. A comparison of 15% glyphosate a.e. compositions containing 5% alkylether surfactant and 0.25% butyl stearate provided the following ranking of alkylethers in descending order of effectiveness: oleth-20 (67-14)>ceteth-20 (67-05)>Neodol 25-20 (67-03)=laureth-23 (67-04).




Example 68




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 68a. All are oil-in-water emulsions and were prepared by process (vii).















TABLE 68a













% w/w


















Concentrate




Glyphosate




Butyl





Type of







composition




g a.e./l




stearate




Surfactant




surfactant





















68-01




163




0.50




5.0




oleth-20







68-02




163




0.25




5.0




oleth-20







68-03




163




0.25




2.5




oleth-20







68-04




163




1.00




10.0




oleth-20







68-05




163




0.50




5.0




steareth-20







68-06




163




0.25




5.0




steareth-20







68-07




163




0.25




2.5




steareth-20







68-08




163




1.00




10.0




steareth-20















Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 68b.















TABLE 68b













Glyphosate rate




% Inhibition
















Concentrate composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




0




30








250




20




43








350




43




53








450




68




57







Formulation C




150




60




47








250




75




53








350




87




80








450




87




78







Formulation J




150




42




43








250




83




60








350




87




73








450




93




87







68-01




150




60




60








250




78




63








350




87




89








450




92




78







68-02




150




70




43








250




80




91








350




87




86








450




96




87







68-03




150




52




43








250




75




72








350




83




93








450




87




94







68-04




150




72




50








250




93




73








350




97




95








450




97




91







68-05




150




72




43








250




80




78








350




87




91








450




93




85







68-06




150




68




40








250




80




50








350




93




75








450




95




85







68-07




150




63




37








250




78




55








350




87




84








450




83




82







68-08




150




70




50








250




80




70








350




92




84








450




94




98















All compositions containing butyl stearate and either oleth-20 or steareth-20 showed a very high level of performance by comparison with commercial standard Formulations C and J.




Example 69




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 69a. All are oil-in-water emulsions and were prepared by process (vii).















TABLE 69a













% w/w


















Concentrate




Glyphosate




Butyl





Type of







composition




g a.e./l




stearate




Surfactant




surfactant





















69-01




163




0.50




5.0




oleth-20







69-02




163




0.25




5.0




oleth-20







69-03




163




0.25




2.5




oleth-20







69-04




163




1.00




10.0




oleth-20







69-05




163




0.50




5.0




steareth-20







69-06




163




0.25




5.0




steareth-20







69-07




163




0.25




2.5




steareth-20







69-08




163




1.00




10.0




steareth-20















Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 69b.















TABLE 69b













Glyphosate rate




% Inhibition
















Concentrate composition




g a.e./ha




ABUTH




ECHCF











Formulation B




150




 3




10








250




28




23








350




72




37








450




73




50







Formulation C




150




57




43








250




87




62








350




93




83








450




99




95







Formulation J




150




27




47








250




70




53








350




92




75








450




94




92







69-01




150




68




50








250




85




47








350




97




70








450




99




83







69-02




150




67




40








250




78




50








350




96




63








450




99




68







69-03




150




52




40








250




72




50








350




95




63








450




97




85







69-04




150




72




40








250




97




53








350




97




77








450




99




90







69-05




150




75




40








250




missing




53








350




88




53








450




96




78







69-06




150




98




40








250




93




50








350




97




68








450




97




82







69-07




150




73




40








250




92




50








350




98




63








450




98




80







69-08




150




77




43








250




93




57








350




97




77








450




98




88















All compositions containing butyl stearate and either oleth-20 or steareth-20 showed a very high level of performance by comparison with commercial standard Formulations C and J.




Example 70




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 70a. All contain colloidal particulates and were prepared by process (ix).




All compositions of this example showed acceptable storage stability. The compositions containing oleth-20 were not acceptably storage-stable in the absence of the colloidal particulate.















TABLE 70a













% w/w

















Concentrate




Glyphosate




Butyl






Type of






composition




g a.e./l




stearate




Oleth-20




Aerosil




Aerosil



















70-01




488





3.0




0.4




OX-50






70-02




488





3.0




0.8




OX-50






70-03




488





3.0




1.5




OX-50






70-04




488






0.4




OX-50






70-05




488






0.8




OX-50






70-06




488






1.5




OX-50






70-07




488





3.0




0.4




MOX-80






70-08




488





3.0




0.8




MOX-80






70-09




488





3.0




1.5




MOX-80






70-10




488






0.4




MOX-80






70-11




488






0.8




MOX-80






70-12




488






1.5




MOX-80






70-13




488





3.0




0.4




MOX-170






70-14




488





3.0




0.8




MOX-170






70-15




488





3.0




1.5




MOX-170






70-16




488






0.4




MOX-170






70-17




488






0.8




MOX-170






70-18




488






1.5




MOX-170






70-19




488




3.0




3.0




1.5




MOX-80














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 20 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 70b.















TABLE 70b













Glyphosate rate




% Inhibition
















Concentrate composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




0




27








250




17




37








350




47




57








450




60




60







Formulation J




150




57




50








250




82




87








350




95




99








450




98




99







70-01




150




37




60








250




73




70








350




96




97








450




96




99







70-02




150




43




50








250




73




63








350




93




96








450




98




99







70-03




150




53




60








250




83




87








350




87




97








450




98




98







70-04




150




45




40








250




57




60








350




78




95








450




94




100







70-05




150




47




50








250




60




82








350




92




96








450




95




99







70-06




150




38




53








250




68




96








350




82




99








450




83




95







70-07




150




50




57








250




87




88








350




91




99








450




98




98







70-08




150




53




50








250




88




85








350




96




97








450




97




100







70-09




150




40




30








250




37




47








350




57




80








450




77




94







70-10




150




47




50








250




70




95








350




75




99








450




77




98







70-11




150




27




60








250




72




85








350




82




98








450




75




99







70-12




150




37




57








250




73




86








350




80




99








450




85




100







70-13




150




45




53








250




85




94








350




95




100








450




98




99







70-14




150




50




50








250




78




83








350




94




98








450




98




99







70-15




150




53




67








250




75




88








350




93




97








450




96




99







70-16




150




42




50








250




47




96








350




70




98








450




90




99







70-17




150




27




83








250




57




98








350




87




99








450




87




100







70-18




150




33




60








250




47




94








350




83




99








450




93




99







70-19




150




45




47








250




80




73








350




96




94








450




99




98















Remarkably high levels of herbicidal effectiveness were obtained in this test with compositions containing oleth-20 at a weight/weight ratio to glyphosate a.e. of about 1:14, and stabilized with colloidal particulates. In some cases the colloidal particulate alone contributed a major part of the efficacy enhancement. Results with composition 70-09 are out of line with other data and an application problem is suspected.




Example 71




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 71 a. Concentrate compositions 71-01 to 71-04, 71-06, 71-08, 71-09, 71-11, 71-12, 71-14 and 71-16 are oil-in-water emulsion were prepared by process (vii). Concentrate compositions 71-05, 71-07, 71-10, 71-13, 71-15 and 71-17 are aqueous solution concentrates and were prepared by process (viii).















TABLE 71a













% w/w


















Concentrate




Glyphosate




Butyl





Type of







composition




g a.e./l




stearate




Surfactant




surfactant











71-01




163




0.25




2.5




Neodol 1-12







71-02




163




0.25




2.5




laureth-23







71-03




163




0.25




2.5




steareth-10







71-04




163




0.25




2.5




steareth-20







71-05




163





2.5




steareth-20







71-06




163




0.25




2.5




steareth-100







71-07




163





2.5




steareth-100







71-08




163




0.25




2.5




oleth-10







71-09




163




0.25




2.5




oleth-20







71-10




163





2.5




oleth-20







71-11




163




0.25




2.5




ceteth-10







71-12




163




0.25




2.5




ceteth-20







71-13




163





2.5




ceteth-20







71-14




326




0.50




5.0




ceteareth-27







71-15




326





5.0




ceteareth-27







71-16




163




0.25




2.5




ceteareth-55







71-17




163





2.5




ceteareth-55















Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 71b.















TABLE 71b













Glyphosate rate




% Inhibition
















Concentrate composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




0




33








250




20




43








350




63




63








450




75




70







Formulation C




150




53




55








250




80




87








350




94




97








450




98




99







Formulation J




150




40




57








250




80




90








350




96




99








450




98




99







71-01




150




52




40








250




65




73








350




77




70








450




77




70







71-02




150




37




70








250




75




80








350




83




97








450




95




99







71-03




150




47




53








250




77




86








350




83




97








450




93




100







71-04




150




80




60








250




93




83








350




96




85








450




99




99







71-05




150




80




43








250




93




79








350




96




94








450




98




96







71-06




150




77




53








250




85




83








350




94




99








450




97




99







71-07




150




63




50








250




80




88








350




85




96








450




96




99







71-08




150




27




45








250




75




83








350




77




99








450




96




98







71-09




150




75




57








250




80




82








350




97




95








450




99




98







71-10




150




70




40








250




85




83








350




97




98








450




99




99







71-11




150




53




37








250




75




63








350




88




93








450




92




98







71-12




150




70




40








250




78




75








350




90




91








450




98




98







71-13




150




72




40








250




92




80








350




97




90








450




99




97







71-14




150




78




53








250




89




88








350




97




95








450




99




100







71-15




150




80




60








250




95




97








350




98




100








450




99




99







71-16




150




60




63








250




87




78








350




96




94








450




98




99







71-17




150




73




60








250




85




57








350




93




80








450




99




85















In combination with butyl stearate, steareth-20 (composition 71-04) gave greater herbicidal effectiveness than steareth-10 (71-03) on ABUTH. Similarly, oleth-20 (71-09) was more efficacious than oleth-10 (71-08) and ceteth-20 (71-12) than ceteth-10 (71-11) In the absence of butyl stearate, ceteareth-55 (71-17) was noticeably weaker on ECHCF than ceteareth-27 (71-15) but inclusion of butyl stearate (71-16) tended to correct this weakness. Note that while compositions 71-14 and 71-15 contained twice as high a concentration of excipients as the other compositions of the test, the concentration of glyphosate was also twice as high, thus the concentrations as sprayed were the same.




Example 72




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 72a. Concentrate compositions 72-01 to 72-05, 72-07, 72-08, 72-10 and 72-12 to 72-16 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 72-06, 72-09 and 72-11 are aqueous solution concentrates and were prepared by process (viii).















TABLE 72a













% w/w
















Concentrate




Glyphosate




Butyl





Type of






composition




g a.e./l




stearate




Surfactant




surfactant









72-01




163




0.25




2.5




Neodol 1-12






72-02




163




0.25




2.5




laureth-23






72-03




163




0.25




2.5




steareth-10






72-04




163




0.25




2.5




steareth-20






72-05




163




0.25




2.5




Pluronic F-68






72-06




163





2.5




Pluronic F-68






72-07




326




1.00




5.0




Pluronic F-108






72-08




326




0.50




5.0




Pluronic F-108






72-09




326





5.0




Pluronic F-108






72-10




163




0.25




2.5




Pluronic F-127






72-11




163





2.5




Pluronic F-127






72-12




326




0.50




5.0




ceteareth-27






72-13




163




0.25




2.5




ceteareth-55






72-14




163




0.25




2.5




oleth-20






72-15




163




0.25




2.5




ceteth-20






72-16




163




0.25




2.5




steareth-100














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 72b.















TABLE 72b













Glyphosate rate




% Inhibition
















Concentrate composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




5




0








250




47




5








350




70




23








450




75




43







Formulation C




150




73




47








250




99




50








350




98




67








450




99




75







Formulation J




150




73




43








250




89




50








350




97




83








450




98




77







72-01




150




37




30








250




70




33








350




77




40








450




90




47







72-02




150




52




37








250




77




67








350




90




77








450




92




75







72-03




150




40




30








250




77




70








350




80




82








450




90




83







72-04




150




75




37








250




95




53








350




99




91








450




99




82







72-05




150




58




37








250




65




53








350




80




80








450




75




68







72-06




150




40




30








250




75




33








350




78




43








450




80




43







72-07




150




50




30








250




75




33








350




78




53








450




86




53







72-08




150




47




30








250




75




33








350




77




40








450




80




50







72-09




150




43




33








250




77




40








350




78




63








450




83




50







72-10




150




27




40








250




77




43








350




80




50








450




92




40







72-11




150




37




30








250




72




33








350




80




60








450




95




40







72-12




150




78




37








250




98




40








350




99




53








450




100




50







72-13




150




75




30








250




88




40








350




98




47








450




100




65







72-14




150




73




30








250




87




40








350




98




50








450




99




53







72-15




150




72




30








250




93




40








350




96




43








450




99




50







72-16




150




73




40








250




83




40








350




98




40








450




100




47















Composition 72-04 containing streath-20 outperformed its counterpart 72-03 containing steareth-10, though both gave greater herbicidal effectiveness, especially on ECHCF, than 72-02 containing laureth-23 or 72-01 containing Neodol 1-12.




Example 73




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 73a. Concentrate compositions 73-01 to 73-07 and 73-09 to 73-15 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 73-08 and 73-16 are aqueous solution concentrates and were prepared by process (viii).















TABLE 73a













% w/w

















Concentrate




Glyphosate





Surfact-




Type of




Type of






composition




g a.e./l




Oil




ant




oil




surfactant









73-01




163




0.5




5.0




methyl stearate




oleth-20






73-02




163




0.5




5.0




butyl stearate




oleth-20






73-03




163




0.5




5.0




methyl oleate




oleth-20






73-04




163




0.5




5.0




butyl oleate




oleth-20






73-05




163




0.5




5.0




methyl laurate




oleth-20






73-06




163




0.5




5.0




butyl laurate




oleth-20






73-07




163




0.5




5.0




Orchex 796




oleth-20






73-08




163





5.0




none




oleth-20






73-09




163




0.5




5.0




methyl stearate




Neodol 1-9






73-10




163




0.5




5.0




butyl stearate




Neodol 1-9






73-11




163




0.5




5.0




methyl oleate




Neodol 1-9






73-12




163




0.5




5.0




butyl oleate




Neodol 1-9






73-13




163




0.5




5.0




methyl laurate




Neodol 1-9






73-14




163




0.5




5.0




butyl laurate




Neodol 1-9






73-15




163




0.5




5.0




Orchex 796




Neodol 1-9






73-16




163





5.0




none




Neodol 1-9














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 19 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 73b.















TABLE 73b













Glyphosate rate




% Inhibition
















Concentrate composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




3




10








250




58




57








350




78




53








450




77




53







Formulation C




150




60




98








250




87




99








350




95




98








450




99




100







Formulation J




150




60




75








250




89




87








350




93




90








450




98




99







73-01




150




75




96








250




99




97








350




97




99








450




99




100







73-02




150




60




60








250




97




67








350




99




98








450




100




95







73-03




150




63




40








250




83




82








350




97




86








450




97




88







73-04




150




73




40








250




94




82








350




97




100








450




99




100







73-05




150




67




47








250




86




67








350




97




88








450




99




100







73-06




150




60




43








250




78




91








350




97




83








450




94




86







73-07




150




70




53








250




80




53








350




97




82








450




97




92







73-08




150




70




62








250




83




83








350




91




87








450




98




98







73-09




150




45




42








250




72




72








350




77




73








450




78




89







73-10




150




40




30








250




82




80








350




78




98








450




89




93







73-11




150




40




30








250




65




60








350




77




90








450




96




92







73-12




150




20




30








250




63




73








350




80




75








450




93




86







73-13




150




20




27








250




67




60








350




82




91








450




88




92







73-14




150




 7




30








250




72




81








350




87




78








450




80




85







73-15




150




20




23








250




65




60








350




77




81








450




87




88







73-16




150




12




30








250




57




53








350




68




85








450




85




85















Composition 73-08, containing as sole excipient substance oleth-20 at a 1:3 weight/weight ratio to glyphosate a.e., exhibited high herbicidal effectiveness, at least equal to commercial standard Formulations C and J on ABUTH but a little weaker on ECHCF. By comparison, composition 73-16, wherein the sole excipient substance was Neodol 1-9 at the same ratio to glyphosate, had much weaker activity. Addition of a small amount of fatty acid ester in most cases enhanced effectiveness, especially on ECHCF. In this study the most efficacious composition was 73-01, containing oleth-20 and methyl stearate. When added to Neodol 1-9, butyl stearate was more efficacious than methyl stearate, methyl oleate or butyl oleate. The mineral oil Orchex 796 did not substitute effectively for butyl stearate, either with oleth-20 or with Neodol 1-9.




Example 74




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 74a. Concentrate compositions 74-01, 74-03, 74-05 to 74-08, 74-10 and 74-14 to 74-17 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 74-02, 74-04, 74-09 and 74-11 to 74-13 are aqueous solution concentrates and were prepared by process (viii). Some compositions contained a coupling agent as indicated in Table 74a; the coupling agent was added with the surfactant.
















TABLE 74a













% w/w



















Conc.




Glyphosate




Butyl





Coupling




Type of




Type of






comp.




g a.e./l




stearate




Surfactant




agent




coupling agent




surfactant









74-01




326




1.0




5.0




2.5




Arcosolve DPM




oleth-20






74-02




326





5.0




2.5




Arcosolve DPM




oleth-20






74-03




163




0.5




2.5





none




oleth-20






74-04




163





2.5





none




oleth-20






74-05




326




1.0




5.0





none




ceteareth-27






74-06




326




1.0




5.0




2.5




PEG-400




ceteareth-27






74-07




326




1.0




5.0




2.5




Dowanol TPNB




ceteareth-27






74-08




326




1.0




5.0




2.5




Dowanol PNB




ceteareth-27






74-09




163





2.5





none




ceteareth-27






74-10




326




0.5




5.0





none




ceteareth-27






74-11




326





5.0




2.5




PEG-400




ceteareth-27






74-12




326





5.0




2.5




Dowanol TPNB




ceteareth-27






74-13




326





5.0




2.5




Dowanol PNB




ceteareth-27






74-14




163




0.5




2.5





none




Neodol 1-9






74-15




163




0.5




2.5





none




laureth-23






74-16




163




0.5




2.5





none




steareth-20






74-17




163




0.5




2.5





none




ceteareth-27














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 74b.















TABLE 74b













Glyphosate rate




% Inhibition
















Concentrate composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




0




5








250




38




20








350




63




30








450




70




70







Formulation C




150




70




75








250




92




94








350




99




99








450




99




98







Formulation J




150




65




50








250




88




92








350




97




99








450




98




97







74-01




150




58




83








250




77




88








350




93




96








450




93




99







74-02




150




40




76








250




75




100








350




92




100








450




92




100







74-03




150




48




75








250




83




96








350




92




100








450




99




100







74-04




150




40




82








250




78




99








350




87




99








450




98




100







74-05




150




68




92








250




87




99








350




95




99








450




99




99







74-06




150




55




60








250




83




99








350




97




99








450




98




98







74-07




150




63




57








250




80




96








350




95




97








450




99




98







74-08




150




73




75








250




90




90








350




95




97








450




100




97







74-09




150




73




68








250




87




73








350




92




90








450




97




95







74-10




150




70




63








250




87




80








350




98




94








450




99




96







74-11




150




73




60








250




90




77








350




99




93








450




100




95







74-12




150




72




67








250




83




75








350




90




82








450




99




94







74-13




150




73




70








250




80




83








350




99




94








450




100




92







74-14




150




5




20








250




55




63








350




77




93








450




78




99







74-15




150




43




57








250




78




88








350




88




98








450




90




98







74-16




150




65




57








250




83




82








350




88




98








450




95




97







74-17




150




72




50








250




80




93








350




88




90








450




95




97















The superiority of herbicidal effectiveness provided by C


16-18


alkylethers (oleth-20, ceteareth-27, steareth-20) over that provided by shorter chain alkylethers (Neodol 1-9, laureth-23) was very pronounced in this test.




Example 75




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 75a. Concentrate compositions 75-01 to 75-07 and 75-09 to 75-15 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 75-08 and 75-16 are aqueous solution concentrates and were prepared by process (viii).















TABLE 75a













% w/w

















Concentrate




Glyphosate





Surfact-




Type of




Type of






composition




g a.e./l




Oil




ant




oil




surfactant









75-01




163




0.5




5.0




methyl stearate




steareth-20






75-02




163




0.5




5.0




butyl stearate




steareth-20






75-03




163




0.5




5.0




methyl oleate




steareth-20






75-04




163




0.5




5.0




butyl oleate




steareth-20






75-05




163




0.5




5.0




methyl laurate




steareth-20






75-06




163




0.5




5.0




butyl laurate




steareth-20






75-07




163




0.5




5.0




Orchex 796




steareth-20






75-08




163





5.0




none




steareth-20






75-09




163




0.5




5.0




methyl stearate




ceteareth-27






75-10




163




0.5




5.0




butyl stearate




ceteareth-27






75-11




163




0.5




5.0




methyl oleate




ceteareth-27






75-12




163




0.5




5.0




butyl oleate




ceteareth-27






75-13




163




0.5




5.0




methyl laurate




ceteareth-27






75-14




163




0.5




5.0




butyl laurate




ceteareth-27






75-15




163




0.5




5.0




Orchex 796




ceteareth-27






75-16




163





5.0




none




ceteareth-27














Velvetleaf (


Abutilon theophrasti,


ABUTH) and Japanese millet (


Echinochloa crus


-


galli,


ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions w ere made 19 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 75b.















TABLE 75b













Glyphosate rate




% Inhibition
















Concentrate composition




g a.e./ha




ABUTH




ECHCF




















Formulation B




150




15




5








250




57




20








350




83




50








450




78




73







Formulation C




150




65




63








250




87




93








350




92




94








450




98




100







Formulation J




150




50




73








250




90




90








350




94




98








450




98




99







75-01




150




72




70








250




88




85








350




96




83








450




99




86







75-02




150




73




53








250




83




87








350




97




99








450




97




98







75-03




150




68




33








250




87




92








350




93




97








450




98




93







75-04




150




72




50








250




87




88








350




94




86








450




98




97







75-05




150




72




67








250




83




82








350




99




97








450




98




98







75-06




150




73




33








250




95




83








350




99




95








450




99




88







75-07




150




73




55








250




93




73








350




95




83








450




98




91







75-08




150




75




40








250




94




60








350




98




86








450




99




92







75-09




150




77




50








250




90




50








350




98




92








450




99




98







75-10




150




72




53








250




92




77








350




96




86








450




99




99







75-11




150




72




60








250




87




87








350




97




97








450




97




99







75-12




150




70




57








250




90




90








350




96




96








450




98




99







75-13




150




68




40








250




90




77








350




99




95








450




99




98







75-14




150




77




33








250




94




70








350




96




82








450




99




93







75-15




150




75




30








250




96




75








350




97




88








450




99




92







75-16




150




77




40








250




99




47








350




98




67








450




98




78















Steareth-20 and ceteareth-27, as sole excipient substances (compositions 75-08 and 75-16 respectively) provided excellent herbicidal effectiveness, but further enhancements, especially on ECHCF, were obtained by inclusion of a small amount of fatty acid ester in the composition.




Example 76




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 76a. Concentrate compositions. 76-13 and 76-14 are aqueous solution concentrates and were prepared by process (viii). Concentrate compositions 76-01 to 76-12 and 76-15 are aqueous solution concentrates containing colloidal particulates and were prepared by process (ix). Concentrate compositions 76-16 and 76-17 contained colloidal particulates but no surfactant.




Compositions 76-13 and 76-14 (both containing 162 g a.e./l glyphosate) showed acceptable storage stability. However, at glyphosate loadings >480 g a.e./l (as in compositions 76-01 to 76-12 and 76-15) storage-stable compositions containing 3% oleth-20 could not be made except with the addition of colloidal particulate as shown below.















TABLE 76a











Concentrate




Glyphosate




% w/w




Type of
















composition




g a.e./l




Oleth-20




Glycerin




Aerosil




Aerosil









76-01




492




3.00




2.0




0.8




380






76-02




492




3.00




5.0




1.5




380






76-03




492




3.00




2.0




0.8




380






76-04




492




3.00




5.0




1.5




380






76-05




492




3.00





0.8




OX-50






76-06




492




3.00





1.5




OX-50






76-07




492




3.00





0.8




380/











OX-50











blend






76-08




492




3.00





1.5




380











/OX-50











blend






76-09




492




3.00





0.8




380






76-10




492




3.00





1.5




380






76-11




492




3.00





0.8




380






76-12




492




3.00





1.5




380






76-13




162




1.13






none






76-14




162




1.13






none






76-15




492




3.00




2.0




1.5




380






76-16




488






0.8




380






76-17




488






1.5




380














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 76b.
















TABLE 76b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




18




40







250




57




53







350




72




63







450




83




85






Formulation J




150




70




65







250




85




95







350




98




98







450




100




99






76-01




150




62




67







250




72




93







350




99




96







450




99




97






76-02




150




57




50







250




70




91







350




92




97







450




99




99






76-03




150




48




40







250




68




67







350




97




97







450




98




98






76-04




150




55




50







250




82




83







350




95




90







450




99




94






76-05




150




65




43







250




87




87







350




100




94







450




96




95






76-06




150




55




53







250




75




82







350




95




95







450




100




96






76-07




150




45




83







250




78




82







350




90




93







450




95




99






76-08




150




55




47







250




75




88







350




93




99







450




99




97






76-09




150




47




47







250




65




82







350




78




99







450




97




97






76-10




150




47




40







250




72




96







350




77




80







450




85




97






76-11




150




37




53







250




73




82







350




80




83







450




90




92






76-12




150




35




57







250




70




82







350




80




97







450




90




99






76-13




150




50




40







250




68




75







350




95




92







450




99




95






76-14




150




40




33







250




70




82







350




93




89







450




98




93






76-15




150




23




33







250




67




73







350




83




91







450




94




92






76-16




150




13




40







250




45




50







350




62




72







450




77




77






76-17




150




7




33







250




50




50







350




60




70







450




75




73














Several high-loaded (492 g a.e./l) glyphosate compositions containing oleth-20 at just 3% exhibited surprisingly high herbicidal effectiveness, approaching or equalling that of commercial standard Formulation J, which is loaded at only about 360 g a.e./l and has a much higher surfactant to glyphosate ratio.




Example 77




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 77a. Concentrate composition 77-08 to 77-14 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 77-15 to 77-17 are aqueous solution concentrates and were prepared by process (viii). Concentrate compositions 77-01 to 77-07 contain colloidal particulates and were prepared by process (ix).




Compositions 77-08 to 77-17 (all containing 163 g a.e./l glyphosate) showed acceptable storage stability. However, at a glyphosate loading of 400 g a.e./l (as in compositions 77-01 to 77-07) storage-stable compositions containing 0.5-1% butyl stearate and 5-10% alkylether surfactant could not be made except with the addition of colloidal particulate as shown below.















TABLE 77a













% w/w

















Concentrate




Glyphosate




Butyl





Aerosil




Type of






composition




g a.e./l




stearate




Surfactant




90




surfactant



















77-01




400




1.0




10.0




1.0




ceteareth-27






77-02




400




1.0




10.0




1.0




steareth-20






77-03




400




0.5




5.0




1.0




ceteareth-27






77-04




400




0.5




5.0




1.0




steareth-20






77-05




400




1.0




5.0




1.0




ceteareth-27






77-06




400




1.0




5.0




1.0




steareth-20






77-07




400




1.0




5.0




1.0




steareth-30






77-08




163




0.5




5.0





oleth-20






77-09




163




0.5




5.0





steareth-20






77-10




163




0.5




5.0





ceteth-20






77-11




163




0.5




5.0





laureth-23






77-12




163




0.5




5.0





ceteareth-27






77-13




163




0.5




5.0





Neodol











25-12






77-14




163




0.5




5.0





Neodol











25-20






77-15




163





5.0





steareth-20






77-16




163





5.0





ceteth-20






77-17




163





5.0





laureth-23














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 19 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 77b.
















TABLE 77b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




0




40







250




20




60







350




68




82







450




83




96






Formulation C




150




68




93







250




93




99







350




100




100







450




100




100






Formulation J




150




43




89







250




93




100







350




100




100







450




100




100






77-01




150




78




97







250




96




100







350




98




100







450




100




100






77-02




150




91




98







250




100




100







350




100




100







450




100




100






77-03




150




90




97







250




99




99







350




100




100







450




100




100






77-04




150




77




98







250




100




100







350




100




100







450




100




100






77-05




150




82




93







250




100




99







350




100




100







450




100




100






77-06




150




83




85







250




100




99







350




100




100







450




100




100






77-07




150




83




87







250




100




100







350




100




100







450




100




100






77-08




150




90




92







250




100




100







350




100




100







450




100




100






77-09




150




90




85







250




100




98







350




100




100







450




100




100






77-10




150




80




85







250




100




92







350




100




100







450




100




100






77-11




150




83




88







250




96




99







350




100




98







450




100




100






77-12




150




93




85







250




100




99







350




100




100







450




100




100






77-13




150




72




73







250




92




97







350




100




99







450




100




100






77-14




150




72




80







250




99




99







350




100




100







450




100




100






77-15




150




100




93







250




100




99







350




100




100







450




100




100






77-16




150




100




98







250




100




100







350




100




100







450




100




100






77-17




150




83




83







250




100




99







350




100




99







450




100




99














Outstanding herbicidal effectiveness was provided by compositions containing C


16-18


alkylether surfactants (ceteareth-27, steareth-20, steareth-30, oleth-20, ceteth-20). High-loaded (400 g a.e./l) glyphosate compositions containing a C


16-18


alkylether surfactant, butyl stearate and a colloidal particulate (Aerosil 90) to stabilize the compositions performed especially impressively in this test.




Example 78




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 78a. Concentrate composition 78-01 to 78-09, 78-11 to 78-14, 78-16 and 78-17 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 78-10 and 78-15 are aqueous solution concentrates and were prepared by process (viii).















TABLE 78a













% w/w


















Conc.




Glyphosate





Oleth-




Other





Other






comp.




g a.e./l




Oil




20




surfactant




Type of oil




surfactant









78-01




163




0.25




2.5





methyl laurate







78-02




163




0.25




2.5





methyl myristate






78-03




163




0.25




2.5





methyl palmitoleate






78-04




163




0.25




2.5





methyl palmitate






78-05




163




0.25




2.5





methyl linoleate






78-06




163




0.25




2.5





methyl oleate






78-07




163




0.25




2.5





methyl stearate






78-08




163




0.25




2.5





ethyl stearate






78-09




163




0.25




2.5





butyl stearate






78-10




163





2.5





none






78-11




163




0.25





2.5




methyl palmitoleate




MON 0818






78-12




163




0.25





2.5




methyl palmitate




MON 0818






78-13




163




0.25





2.5




methyl oleate




MON 0818






78-14




163




0.25





2.5




methyl stearate




MON 0818






78-15




163






2.5




none




MON 0818






78-16




163




0.25





2.5




butyl stearate




laureth-23






78-17




163




0.25





2.5




butyl stearate




Neodol 1-9














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 20 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 78b.
















TABLE 78b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




2




35







200




52




67







300




77




83







400




78




87






Formulation C




100




25




77







200




72




99







300




87




100







400




99




100






Formulation J




100




13




73







200




70




97







300




90




100







400




97




100






78-01




100




22




55







200




65




86







300




78




98







400




89




98






78-02




100




20




63







200




67




91







300




83




99







400




97




100






78-03




100




30




75







200




63




98







300




83




99







400




94




100






78-04




100




23




63







200




60




98







300




90




99







400




95




100






78-05




100




27




57







200




62




91







300




83




96







400




93




98






78-06




100




23




50







200




63




89







300




83




99







400




96




99






78-07




100




25




53







200




65




94







300




83




99







400




92




99






78-08




100




13




47







200




53




88







300




89




97







400




95




99






78-09




100




27




53







200




60




85







300




83




97







400




97




98






78-10




100




13




53







200




62




94







300




83




97







400




88




99






78-11




100




23




60







200




50




90







300




85




98







400




95




99






78-12




100




17




55







200




35




94







300




78




98







400




94




99






78-13




100




8




50







200




43




90







300




73




98







400




90




99






78-14




100




30




63







200




45




92







300




80




98







400




94




98






78-15




100




20




63







200




70




96







300




82




99







400




94




98






78-16




100




18




62







200




62




83







300




80




97







400




97




97






78-17




100




17




52







200




58




85







300




75




90







400




95




98














No great or consistent enhancement of herbicidal effectiveness of glyphosate composition containing oleth-20 was obtained by adding a small amount of any of a variety of fatty acid esters in this study with (compare 78-10 with 78-01 to 78-09).




Example 79




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 79a. Concentrate composition 79-01 to 79-09, 79-11 to 79-14, 79-16 and 79-17 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 79-10 and 79-15 are aqueous solution concentrates and were prepared by process (viii).















TABLE 79a













% w/w


















Concentrate




Glyphosate





Oleth-




Other





Other






composition




g a.e./l




Oil




20




surfactant




Type of oil




surfactant









79-01




163




0.25




2.5





isopropyl myristate







79-02




163




0.25




2.5





ethyl myristate







79-03




163




0.25




2.5





methyl palmitate






79-04




163




0.25




2.5





ethyl palmitate






79-05




163




0.25




2.5





ethyl linoleate






79-06




163




0.25




2.5





ethyl oleate






79-07




163




0.25




2.5





methyl stearate






79-08




163




0.25




2.5





ethyl stearate






79-09




163




0.25




2.5





butyl stearate






79-10




163





2.5





none






79-11




163




0.25





2.5




methyl palmitate




MON 0818






79-12




163




0.25





2.5




methyl stearate




MON 0818






79-13




163




0.25





2.5




ethyl stearate




MON 0818






79-14




163




0.25





2.5




ethyl oleate




MON 0818






79-15




163






2.5




none




MON 0818






79-16




163




0.25





2.5




butyl stearate




laureth-23






79-17




163




0.25





2.5




butyl stearate




Neodol 1-9














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 79b.
















TABLE 79b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




12




33







200




45




43







300




73




63







400




80




63






Formulation C




100




43




57







200




75




88







300




95




99







400




100




99






Formulation J




100




53




60







200




77




75







300




96




95







400




99




98






79-01




100




35




40







200




73




72







300




83




91







400




99




97






79-02




100




38




30







200




70




43







300




87




82







400




96




80






79-03




100




25




27







200




68




50







300




90




73







400




96




82






79-04




100




27




27







200




75




50







300




80




73







400




96




80






79-05




100




33




27







200




68




43







300




83




70







400




97




91






79-06




100




33




28







200




72




53







300




83




60







400




99




70






79-07




100




37




25







200




72




40







300




83




50







400




97




65






79-08




100




32




25







200




73




43







300




87




60







400




98




67






79-09




100




35




25







200




75




43







300




95




57







400




98




63






79-10




100




35




27







200




73




40







300




83




76







400




97




73






79-11




100




35




33







200




67




67







300




80




86







400




92




70






79-12




100




25




30







200




67




70







300




83




76







400




88




80






79-13




100




27




33







200




70




66







300




78




63







400




93




60






79-14




100




33




30







200




67




47







300




80




70







400




92




77






79-15




100




20




30







200




68




40







300




83




75







400




90




72






79-16




100




30




25







200




62




43







300




73




73







400




77




70






79-17




100




30




23







200




58




40







300




75




60







400




80




73














In this study, isopropyl myristate (composition 79-01) was the most effective of the fatty acid esters tested as additives to oleth-20 (79-10) in glyphosate compositions.




Example 80




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 80a. Concentrate composition 80-01 to 80-13 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 80-14 to 80-17 are aqueous solution concentrates and were prepared by process (viii).















TABLE 80a











Concen-









trate




Gly-




% w/w
















compo-




phosate





Sur-





Type of






sition




g a.e./l




Oil




factant




Type of oil




surfactant









80-01




163




0.25




2.5




butyl stearate




laureth-23






80-02




163




0.25




2.5




butyl stearate




steareth-20






80-03




163




0.25




2.5




butyl stearate




ceteareth-20






80-04




163




0.25




2.5




butyl stearate




ceteareth-15






80-05




163




0.25




2.5




butyl stearate




Neodol 45-13






80-06




163




0.25




2.5




methyl stearate




steareth-20






80-07




163




0.25




2.5




methyl stearate




ceteareth-20






80-08




163




0.25




2.5




methyl stearate




ceteareth-15






80-09




163




0.25




2.5




methyl stearate




Neodol 45-13






80-10




163




0.25




2.5




methyl palmitate




steareth-20






80-11




163




0.25




2.5




methyl palmitate




ceteareth-20






80-12




163




0.25




2.5




methyl palmitate




ceteareth-15






80-13




163




0.25




2.5




methyl palmitate




Neodol 45-13






80-14




163





2.5




none




steareth-20






80-15




163





2.5




none




ceteareth-20






80-16




163





2.5




none




ceteareth-15






80-17




163





2.5




none




Neodol 45-13














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 24 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 80b.
















TABLE 80b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




10




37







200




30




40







300




43




57







400




23




33






Formulation C




100




50




67







200




75




96







300




85




99







400




94




100






Formulation J




100




40




75







200




73




94







300




93




98







400




95




99






80-01




100




63




77







200




67




94







300




77




99







400




88




96






80-02




100




63




75







200




83




88







300




93




98







400




95




99






80-03




100




67




75







200




82




95







300




95




99







400




98




99






80-04




100




60




75







200




82




97







300




96




99







400




98




100






80-05




100




63




73







200




75




89







300




80




98







400




87




97






80-06




100




58




63







200




78




93







300




93




99







400




98




100






80-07




100




60




67







200




78




93







300




93




99







400




100




99






80-08




100




missing




missing







200




missing




missing







300




78




95







400




98




99






80-09




100




23




30







200




65




83







300




80




98







400




93




99






80-10




100




65




67







200




83




95







300




97




99







400




99




99






80-11




100




72




73







200




90




98







300




96




97







400




99




99






80-12




100




68




63







200




90




92







300




98




99







400




97




99






80-13




100




43




73







200




72




87







300




83




98







400




93




96






80-14




100




62




77







200




78




99







300




95




99







400




98




100






80-15




100




52




60







200




78




93







300




94




98







400




97




99






80-16




100




38




68







200




68




99







300




87




97







400




94




99






80-17




100




55




75







200




68




91







300




83




96







400




87




98














Herbicidal effectiveness exceeding that of commercial standard composition J, at least on ABUTH, was recorded with several compositions, including 80-02 (steareth-20 plus butyl stearate), 80-03 (ceteareth-20 plus butyl stearate), 80-04 (ceteareth-15 plus butyl stearate), 80-10 (steareth-20 plus methyl palmitate), 80-1 1 (ceteareth-20 plus methyl palmitate) and 80-12 (ceteareth-15 plus methyl palmitate). Compositions lacking fatty acid ester performed slightly less well overall than those containing butyl stearate or methyl palmitate.




Example 81




Spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 81a. Compositions were prepared by simple mixing of ingredients. Soybean lecithin (45% phospholipid, Avanti), where included, was first prepared with sonication in water to make a homogeneous composition. Four different concentrations of glyphosate (not shown in Table 81 a) were prepared, calculated to provide, when applied in a spray volume of 93 l/ha, the glyphosate rates shown in Table 81b.















TABLE 81a













% w/w



















Spray






Butyl




Methyl




Oleth-




Lecithin




Methyl oleate






comp.




Lecithin




FC-754




stearate




oleate




20




supplied as




supplied as









81-01




0.05




0.050







soybean lecithin







81-02




0.05





0.050






soybean lecithin






81-03




0.05








soybean lecithin






81-04





0.050






81-05






0.050






81-06




0.05








LI-700






81-07






0.005





0.05






81-08







0.01




0.05






81-09








0.05






81-10






0.005






81-11







0.01






pure






81-12







0.01






methylated seed oil














Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and Prickly sida (


Sida spinosa


, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 14 days after planting ECHCF and 21 days after planting SIDSP. Evaluation of herbicidal inhibition was done 14 days after application.




Formulations B and C were applied as comparative treatments, representing technical glyphosate IPA salt and a commercial formulation of glyphosate IPA salt respectively. Results, averaged for all replicates of each treatment, are shown in Table 81b.















TABLE 81b













Glyphosate rate




% Inhibition















Composition applied




g a.e./ha




ABUTH




ECHCF




SIDSP


















Formulation B




50




0




0




0






(technical)




100




38




35




35







200




87




50




90







300




95




88




94






Formulation C




50




0




2




0






(commercial)




100




32




55




25







200




85




97




93







300




96




99




96






81-01




50




78




53




88







100




90




60




95







200




99




96




99







300




99




97




98






81-02




50




25




15




43







100




72




30




82







200




94




62




93







300




95




77




94






81-03




50




20




8




32







100




52




22




78







200




87




55




91







300




95




65




93






81-04




50




62




37




85







100




82




68




92







200




97




96




95







300




98




95




97






81-05




50




15




10




25







100




47




27




23







200




85




62




87







300




90




63




92






81-06




50




0




2




0







100




20




15




20







200




85




60




82







300




90




65




90






81-07




50




67




27




82







100




87




55




93







200




94




92




96







300




97




99




97






81-08




50




62




30




75







100




78




63




91







200




93




96




96







300




94




98




98






81-09




50




65




45




77







100




80




73




95







200




93




98




97







300




95




99




99






81-10




50




10




25




5







100




23




35




37







200




90




50




93







300




92




73




94






81-11




50




10




25




0







100




52




33




43







200




88




72




93







300




94




78




94






81-12




50




0




15




0







100




43




35




33







200




91




70




90







300




94




82




93














Results of this test using glyphosate as the exogenous chemical are summarized as follows:




At the low concentration of 0.05% used here. soybean lecithin containing 45% phospholipid (81-03) was a much more effective excipient than the lecithin-based adjuvant LI-700 (81-06) widely used in the art.




Butyl stearate alone at 0.05% (81-05) did not greatly enhance effectiveness.




The combination of lecithin and butyl stearate (81-02) gave surprisingly strong enhancement of effectiveness, suggesting a synergistic interaction between these two excipient substances.




Fluorad FC-754, either alone (81-04) or in combination with lecithin (81-01) gave extremely high effectiveness, superior to that obtained with the commercial standard.




Oleth-20 at the low concentration of 0.05% (81-09) gave extremely high effectiveness, superior to that obtained with the commercial standard. Addition of 0.005% butyl stearate (81-07) or 0.01% methyl oleate (81-08) did not provide further enhancement.




Example 82




Spray compositions were prepared containing paraquat dichloride and excipient ingredients. Compositions 82-01 to 82-12 were exactly like compositions 81-01 to 81-12 except that a different active ingredient was used and a range of active ingredient concentrations was selected appropriate to the active ingredient being applied.




Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and prickly sida (


Sida spinosa


, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 8 days after planting ECHCF and 21 days after planting SIDSP. Evaluation of herbicidal inhibition was done 12 days after application.




Standards included technical paraquat dichloride and Gramoxone, a commercial formulation of paraquat from Zeneca. Results, averaged for all replicates of each treatment, are shown in Table 82.















TABLE 82













Paraquat rate




% Inhibition















Spray composition




g a.i./ha




ABUTH




ECHCF




SIDSP


















Paraquat dichloride




25




50




83




55






(technical)




50




57




78




60







100




73




84




69







200




85




95




99






Gramoxone




25




40




72




40






(commercial)




50




60




70




52







100




72




58




55







200




72




89




63






82-01




25




75




93




67







50




82




97




91







100




95




98




97







200




100




99




99






82-02




25




67




80




48







50




68




87




65







100




88




97




93







200




96




99




98






82-03




25




55




65




42







50




62




87




65







100




83




96




93







200




95




99




97






82-04




25




53




82




45







50




63




94




53







100




88




99




86







200




92




99




98






82-05




25




58




67




50







50




60




62




45







100




70




73




62







200




85




90




88






82-06




25




53




77




43







50




60




92




40







100




80




93




55







200




96




99




78






82-07




25




65




80




45







50




82




92




70







100




96




96




89







200




100




98




99






82-08




25




67




80




37







50




82




90




71







100




97




98




65







200




99




99




93






82-09




25




72




90




50







50




80




97




57







100




91




99




94







200




97




100




97






82-10




25




67




87




45







50




68




75




57







100




78




93




63







200




82




97




82






82-11




25




65




80




45







50




73




77




62







100




90




95




62







200




94




98




78






82-12




25




67




78




37







50




75




90




55







100




77




97




90







200




85




99




92














Results of this test using paraquat as the exogenous chemical are summarized as follows:




At the low concentration of 0.05% used here, soybean lecithin containing 45% phospholipid (82-03) was a much more effective excipient on SIDSP than the lecithin-based adjuvant LI-700 (82-06) widely used in the art.




Butyl stearate alone at 0.05% (82-05) did not enhance effectiveness.




The combination of lecithin and butyl stearate (82-02) gave surprisingly strong enhancement of effectiveness, suggesting a synergistic interaction between these two excipient substances.




Fluorad FC-754 (82-04) gave extremely high effectiveness, superior to that obtained with the commercial standard. In the presence of lecithin (82-01), effectiveness was further increased dramatically, suggesting a synergistic interaction between these two excipient substances.




Oleth-20 at the low concentration of 0.05% (82-09) gave extremely high effectiveness, superior to that obtained with the commercial standard. Addition of 0.005% butyl stearate (82-07) or 0.01 % methyl oleate (82-08) did not provide further enhancement.




Example 83




Spray compositions were prepared containing acifluorfen sodium salt and excipient ingredients. Compositions 83-01 to 83-12 were exactly like compositions 81-01 to 81-12 respectively except that a different active ingredient was used and a range of active ingredient concentrations was selected appropriate to the active ingredient being applied.




Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and prickly sida (


Sida spinosa


, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 15 days after planting ABUTH, 9 days after planting ECHCF and 22 days after planting SIDSP. Evaluation of herbicidal inhibition was done 10 days after application.




Standards included technical acifluorfen sodium and Blazer, a commercial formulation of acifluorfen from Rohm & Haas. Results, averaged for all replicates of each treatment, are shown in Table 83.















TABLE 83













Acifluorfen rate




% Inhibition















Spray composition




g a.i./ha




ABUTH




ECHCF




SIDSP


















Acifluorfen




25




20




2




15






(technical)




50




32




7




17







100




52




18




35







200




62




35




40






Blazer




25




30




30




5






(commercial)




50




53




53




12







100




55




55




7







200




65




65




32






83-01




25




60




7




20







50




63




20




20







100




65




43




33







200




80




70




48






83-02




25




25




7




5







50




42




12




25







100




60




30




22







200




68




68




50






83-03




25




22




5




10







50




55




7




33







100




62




25




27







200




65




55




48






83-04




25




57




7




13







50




67




10




32







100




67




35




32







200




70




70




45






83-05




25




30




3




15







50




47




27




27







100




55




42




37







200




65




60




38






83-06




25




28




0




3







50




50




0




10







100




55




30




25







200




67




58




47






83-07




25




35




20




17







50




55




35




27







100




58




63




32







200




67




67




55






83-08




25




40




20




8







50




57




30




28







100




60




60




30







200




70




77




48






83-09




25




47




20




22







50




55




35




35







100




62




65




38







200




68




82




50






83-10




25




28




0




5







50




48




0




10







100




53




5




25







200




62




35




40






83-11




25




35




0




5







50




43




0




30







100




50




0




35







200




65




43




47






83-12




25




40




5




5







50




55




18




35







100




60




47




38







200




70




62




48














Results of this test using acifluorfen as the exogenous chemical are summarized as follows:




At the low concentration of 0.05% used here, soybean lecithin containing 45% phospholipid (83-03) gave effectiveness similar to that obtained with the lecithin-based adjuvant LI-700 (83-06) widely used in the art.




Butyl stearate at 0.05% alone (83-05) and in combination with lecithin (83-02) enhanced effectiveness, particularly on ECHCF.




Fluorad FC-754, either alone (83-04) or in combination with lecithin (83-01) gave effectiveness on ABUTH and SIDSP superior to that obtained with the commercial standard.




Oleth-20 at the low concentration of 0.05% (83-09) gave effectiveness superior to that obtained with the commercial standard. Addition of 0.005% butyl stearate (83-07) or 0.01% methyl oleate (83-08) did not provide further enhancement.




Example 84




Spray compositions were prepared containing asulam and excipient ingredients. Compositions 84-01 to 84-12 were exactly like compositions 81-01 to 81-12 respectively except that a different active ingredient was used and a range of active ingredient concentrations was selected appropriate to the active ingredient being applied.




Velvetleaf (


Abutilon theophrasti


, ABUTH). Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and prickly sida (


Sida spinosa


, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 11 days after planting ECHCF and 21 days after planting SIDSP. Evaluation of herbicidal inhibition was done 14 days after application.




Standards included technical asulam and Asulox. a commercial formulation of asulam from Rhône-Poulenc. Results. averaged for all replicates of each treatment, are shown in Table 84.















TABLE 84













Asulam rate




% Inhibition















Spray composition




g a.i./ha




ABUTH




ECHCF




SIDSP


















Asulam




200




0




12




0






(technical)




400




17




27




5







800




48




32




20







1400




42




50




37






Asulox




200




3




5




0






(commercial)




400




27




30




20







800




52




45




25







1400




50




60




40






84-01




200




5




8




13







400




23




45




22







800




50




50




30







1400




60




65




48






84-02




200




0




20




17







400




33




40




20







800




47




48




33







1400




53




68




55






84-03




200




3




20




3







400




28




52




7







800




50




50




23







1400




50




58




43






84-04




200




3




40




7







400




35




45




18







800




52




50




25







1400




58




60




42






84-05




200




0




10




3







400




23




30




18







800




33




50




32







1400




45




57




38






84-06




200




2




30




10







400




8




47




17







800




50




55




28







1400




52




63




40






84-07




200




0




43




3







400




22




48




17







800




40




55




28







1400




52




60




33






84-08




200




7




47




22







400




20




48




22







800




53




55




30







1400




57




60




33






84-09




200




0




45




7







400




25




50




7







800




53




60




32







1400




55




63




37






84-10




200




22




37




10







400




27




45




10







800




50




43




23







1400




52




52




27






84-11




200




25




33




5







400




15




37




13







800




48




42




25







1400




42




52




28






84-12




200




3




25




17







400




13




42




18







800




50




45




30







1400




52




50




33














Results of this test using asulam as the exogenous chemical are summarized as follows:




At the low concentration of 0.05% used here, soybean lecithin containing 45% phospholipid (84-03) gave similar enhancement to that obtained with the lecithin-based adjuvant LI-700 (84-06) widely used in the art. Butyl stearate alone at 0.05% (84-05) enhanced effectiveness on ECHCF.




The combination of lecithin and butyl stearate (84-02) gave greater enhancement of effectiveness than either excipient substance alone.




Fluorad FC-754, either alone (84-04) or in combination with lecithin (84-01) gave effectiveness equal to that obtained with the commercial standard.




Oleth-20 at the low concentration of 0.05% (84-09) gave, at low exogenous chemical rates, effectiveness on ECHCF superior to that obtained with the commercial standard. Addition of 0.005% butyl stearate (84-07) or 0.01 % methyl oleate (84-08) did not provide further enhancement.




Example 85




Spray compositions were prepared containing dicamba sodium salt and excipient ingredients. Compositions 85-01 to 85-12 were exactly like compositions 81-01 to 81-12 respectively except that a different active ingredient was used and a range of active ingredient concentrations was selected appropriate to the active ingredient being applied.




Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli,


ECHCF) and prickly sida (


Sida spinosa


, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 8 days after planting ECHCF and 21 days after planting SIDSP. Evaluation of herbicidal inhibition was done 17 days after application.




Standards included technical dicamba sodium and Banvel, a commercial formulation of dicamba from Sandoz. Results, averaged for all replicates of each treatment, are shown in Table 85.















TABLE 85













Dicamba rate




% Inhibition















Spray composition




g a.i./ha




ABUTH




ECHCF




SIDSP


















Dicamba




25




47




0




30






(technical)




50




63




0




40







100




82




0




50







200




93




5




58






Banvel




25




47




0






(commercial)




50




68




0




40







100




91




0




53







200




93




3




63






85-01




25




42




0




38







50




67




0




48







100




92




0




67







200




93




3




73






85-02




25




43




0




43







50




58




0




50







100




85




0




62







200




89




8




72






85-03




25




50




0




32







50




65




0




45







100




90




0




60







200




94




13




68






85-04




25




43




0




35







50




65




0




42







100




94




0




53







200




94




13




67






85-05




25




50




0




35







50




68




0




40







100




88




0




53







200




92




15




60






85-06




25




40




0




40







50




65




0




45







100




88




0




52







200




92




8




70






85-07




25




45




0




42







50




57




0




45







100




88




0




62







200




88




20




68






85-08




25




40




0




38







50




62




0




45







100




97




18




62







200




93




17




73






85-09




25




33




0




35







50




60




0




45







100




93




0




63







200




96




15




73






85-10




25




35




0




30







50




57




0




43







100




90




0




50







200




90




3




70






85-11




25




45




0




30







50




53




0




42







100




89




0




55







200




92




0




73






85-12




25




38




0




37







50




60




0




45







100




96




0




52







200




93




0




70














Results of this test using dicamba as the exogenous chemical are summarized as follows:




At the low concentration of 0.05% used here, soybean lecithin containing 45% phospholipid (85-03) gave similar enhancement of effectiveness to that obtained with the lecithin-based adjuvant LI-700 (85-06) widely used in the art.




Butyl stearate alone at 0.05% (85-05) provided slight enhancement of effectiveness.




The combination of lecithin and butyl stearate (85-02) gave greater enhancement of effectiveness on SIDSP than either of these two excipient substances alone.




Fluorad FC-754 (85-04) provided effectiveness similar to that obtained with the commercial standard. Further enhancement on SIDSP was obtained with the combination of Fluorad FC-754 and lecithin (85-01).




Oleth-20 at the low concentration of 0.05% (85-09) gave effectiveness on SIDSP superior to that obtained with the commercial standard. Addition of 0.005% butyl stearate (85-07) or 0.01% methyl oleate (85-08) did not provide significant further enhancement.




Example 86




Spray compositions were prepared containing metsulfuron-methyl and excipient ingredients. Compositions


86-


-01 to 86-12 were exactly like compositions 81-01 to 81-12 respectively except that a different active ingredient was used and a range of active ingredient concentrations was selected appropriate to the active ingredient being applied. Velvetleaf (


Abutilon theophrasti


, ABUTH). Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and prickly sida (


Sida spinosa


, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 8 days after planting ECHCF and 21 days after planting SIDSP. Evaluation of herbicidal inhibition was done 14 days after application.




Standards included technical metsulfuron-methyl and Ally, a commercial formulation of metsulfuron from Du Pont. Results, averaged for all replicates of each treatment, are shown in Table 86.















TABLE 86













Metsulfuron rate




% Inhibition















Spray composition




g a.i./ha




ABUTH




ECHCF




SIDSP


















Metsulfuron




0.5




72




0




5






(technical)




1




90




0




23







5




96




0




50







10




97




30




55






Ally




0.5




75




0




5






(commercial)




1




85




0




22







5




95




0




42







10




97




25




53






86-01




0.5




95




0




47







1




96




20




53







5




97




25




62







10




98




45




62






86-02




0.5




87




0




40







1




90




10




55







5




95




10




58







10




96




40




63






86-03




0.5




87




0




27







1




90




0




40







5




96




10




57







10




97




33




63






86-04




0.5




90




0




33







1




95




10




50







5




98




17




62







10




99




28




58






86-05




0.5




85




0




27







1




90




0




33







5




95




0




47







10




95




13




60






86-06




0.5




77




0




30







1




89




10




47







5




96




17




62







10




98




33




60






86-07




0.5




94




0




55







1




97




10




60







5




98




43




60







10




97




55




65






86-08




0.5




93




0




55







1




96




5




58







5




97




42




60







10




97




50




60






86-09




0.5




93




0




55







1




97




10




62







5




98




55




62







10




98




65




63






86-10




0.5




85




0




28







1




82




0




30







5




95




10




52







10




96




17




57






86-11




0.5




73




0




25







1




88




20




28







5




94




25




53







10




96




32




57






86-12




0.5




75




0




32







1




85




20




37







5




94




23




55







10




96




25




57














Results of this test using metsulfuron as the exogenous chemical are summarized as follows:




At the low concentration of 0.05% used here, soybean lecithin containing 45% phospholipid (86-03) was a slightly more effective excipient than the lecithin-based adjuvant LI-700 (86-06) widely used in the art in improving perfromance on ABUTH at the lowest exogenous chemical rate tested.




Butyl stearate alone at 0.05% (86-05) enhanced effectiveness to a level superior to that obtained with the commercial standard.




The combination of lecithin and butyl stearate (86-02) gave greater enhancement of effectiveness than was obtained with either of these two excipient substances alone.




Fluorad FC-754, either alone (86-04) or in combination with lecithin (86-01) gave high effectiveness, superior to that obtained with the commercial standard.




Oleth-20 at the low concentration of 0.05% (86-09) gave high effectiveness, superior to that obtained with the commercial standard. Addition of 0.005% butyl stearate (86-07) or 0.01 % methyl oleate (86-08) did not provide further enhancement.




Example 87




Spray compositions were prepared containing imazethapyr and excipient ingredients. Compositions 87-01 to 87-12 were exactly like compositions 81-01 to 81-12 respectively except that a different active ingredient was used and a range of active ingredient concentrations was selected appropriate to the active ingredient being applied.




Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and prickly sida (


Sida spinosa


, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 14 days after planting ECHCF and 21 days after planting SIDSP. Evaluation of herbicidal inhibition was done 14 days after application.




Standards included technical imazethapyr and Pursuit, a commercial formulation of imazethapyr from American Cvanamid. Results, averaged for all replicates of each treatment, are shown in Table 87.














TABLE 87












Imazethapyr rate




% Inhibition















Spray composition




g a.i./ha




ABUTH




ECHCF




SIDSP


















Imazethapyr




5




78




5




20






(technical)




10




83




20




30







25




93




35




40







50




94




53




50






Pursuit




5




70




5




25






(commercial)




10




73




33




30







25




90




50




42







50




93




62




57






87-01




5




70




45




35







10




75




62




52







25




92




63




57







50




93




72




62






87-02




5




73




57




32







10




75




67




43







25




90




70




52







50




92




72




57






87-03




5




70




42




27







10




78




42




35







25




90




53




45







50




92




62




52






87-04




5




73




55




33







10




77




68




45







25




93




68




47







50




94




68




60






87-05




5




73




47




32







10




73




45




40







25




90




62




47







50




91




68




52






87-06




5




78




72




30







10




83




70




35







25




93




77




62







50




94




78




58






87-07




5




82




75




38







10




90




90




52







25




93




93




53







50




97




97




62






87-08




5




75




77




38







10




90




92




50







25




95




93




57







50




97




99




63






87-09




5




78




80




40







10




83




89




63







25




93




93




62







50




96




93




60






87-10




5




85




50




37







10




77




50




45







25




91




63




48







50




93




75




57






87-11




5




75




38




43







10




80




38




37







25




92




62




45







50




93




73




53






87-12




5




75




55




38







10




83




60




43







25




92




67




53







50




93




77




55














Results of this test using imazethapyr as the exogenous chemical are summarized as follows:




At the low concentration of 0.05% used here, soybean lecithin containing 45% phospholipid (87-03) was a less effective excipient than the lecithin-based adjuvant LI-700 (87-06).




Butyl stearate alone at 0.05% (87-05) significantly enhanced effectiveness on ECHCF and slightly on SIDSP.




The combination of lecithin and butyl stearate (87-02) gave enhancement of effectiveness on ECHCF greater than that obtained with either of these two excipient substances alone.




Fluorad FC-754 (87-04) gave effectiveness on ECHCF superior to that obtained with the commercial standard. The combination of Fluorad FC-754 and lecithin (87-01) provided slight further enhancement of effectiveness on SIDSP.




Oleth-20 at the low concentration of 0.05% (87-09) gave extremely high effectiveness, greatly superior to that obtained with the commercial standard, especially on ECHCF. Addition of 0.005% butyl stearate (87-07) further enhanced performance of low exogenous chemical rates on ABUTH more effectively than addition of 0.01% methyl oleate (87-08).




Example 88




Spray compositions were prepared containing fluazifop-p-butyl salt and excipient ingredients. Compositions 88-01 to 88-12 were exactly like compositions 81-01 to 81-12 respectively except that a different active ingredient was used and a range of active ingredient concentrations was selected appropriate to the active ingredient being applied.




Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and broadleaf signalgrass (Brachiaria platyphylla, BRAPP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 15 days after planting ABUTH, 15 days after planting ECHCF and 16 days after planting BRAPP. Evaluation of herbicidal inhibition was done 10 days after application.




Standards included technical fluazifop-p-butyl and Fusilade 5, a commercial formulation of fluazifop-p-butyl from Zeneca. Results, averaged for all replicates of each 88.














TABLE 88












Fluazifop-p rate




% Inhibition















Spray composition




g a.i./ha




ABUTH




ECHCF




BRAPP


















Fluazifop-p-butyl




2




0




0




20






(technical)




5




0




3




35







15




5




45




65







30




5




57




78






Fusilade 5




2




0




0




27






(commercial)




5




0




27




33







15




5




52




78







30




7




75




85






88-01




2




0




0




20







5




2




27




30







15




5




58




78







30




10




87




83






88-02




2




0




7




25







5




0




35




30







15




2




58




75







30




8




78




75






88-03




2




0




0




18







5




0




8




27







15




0




45




75







30




0




55




75






88-04




2




0




20




32







5




2




42




25







15




2




55




72







30




5




80




78






88-05




2




0




13




32







5




2




42




32







15




2




55




72







30




7




58




73






88-06




2




2




17




23







5




0




20




25







15




0




75




75







30




0




73




77






88-07




2




0




50




40







5




0




52




60







15




0




67




80







30




0




92




85






88-08




2




0




43




35







5




0




55




37







15




7




88




82







30




3




96




85






88-09




2




0




47




18







5




0




50




35







15




0




80




80







30




3




93




85






88-10




2




0




23




10







5




0




37




42







15




5




55




75







30




10




58




80






88-11




2




0




7




10







5




0




30




28







15




0




50




62







30




12




53




68






88-12




2




0




5




20







5




0




7




35







15




5




48




68







30




12




60




77














Results of this test using fluazifop-p-butyl as the exogenous chemical are summarized as follows:




At the low concentration of 0.05% used here, soybean lecithin containing 45% phospholipid (88-03) was a less effective excipient on ECHCF than the lecithin-based adjuvant LI-700 (88-06).




Butyl stearate alone at 0.05% (88-05) and in combination with lecithin (88-02) enhanced effectiveness, especially on ECHCF.




Fluorad FC-754, either alone (88-04) or in combination with lecithin (88-01) gave effectiveness equal or superior to that obtained with the commercial standard.




Oleth-20 at the low concentration of 0.05% (88-09) gave extremely high effectiveness on ECHCF, superior to that obtained with the commercial standard. Addition of 0.005% butyl stearate (88-07) or 0.01 % methyl oleate (88-08) did not provide significant further enhancement.




Example 89




Spray compositions were prepared containing alachlor and excipient ingredients. Compositions 89-01 to 89-12 were exactly like compositions 81-01 to 81-12 respectively except that a different active ingredient was used and a range of active ingredient concentrations was selected appropriate to the active ingredient being applied.




Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and prickly sida (


Sida spinosa


, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 8 days after planting ECHCF and 14 days after planting SIDSP. Evaluation of herbicidal inhibition was done 9 days after application.




Standards included technical alachlor and Lasso, a commercial formulation of alachlor from Monsanto Company. Results, averaged for all replicates of each treatment, are shown in Table 89.














TABLE 89












Alachlor rate




% Inhibition















Spray composition




g a.i./ha




ABUTH




ECHCF




SIDSP


















Alachlor




500




0




0




0






(technical)




1000




0




0




0







2000




0




0




0







4000




0




0




0






Lasso




500




0




0




0






(commercial)




1000




0




5




13







2000




0




30




17







4000




15




43




65






89-01




500




0




0




0







1000




0




0




0







2000




0




0




0







4000




10




0




7






89-02




500




0




0




0







1000




0




0




0







2000




0




22




7







4000




12




47




12






89-03




500




0




0




0







1000




0




0




0







2000




0




0




0







4000




10




0




0






89-04




500




0




0




0







1000




0




0




0







2000




0




0




0







4000




5




0




15






89-05




500




0




0




0







1000




0




0




0







2000




0




0




0







4000




3




0




0






89-06




500




0




0




0







1000




0




0




0







2000




0




13




7







4000




0




37




12






89-07




500




0




0




0







1000




0




8




0







2000




0




28




15







4000




12




50




20






89-08




500




0




0




0







1000




0




8




0







2000




0




8




0







4000




5




20




5






89-09




500




0




0




0







1000




0




0




0







2000




0




3




0







4000




12




42




32






89-10




500




0




0




0







1000




0




0




0







2000




0




0




0







4000




0




0




0






89-11




500




0




0




0







1000




0




0




0







2000




0




0




0







4000




0




0




0






89-12




500




0




0




0







1000




0




0




0







2000




0




0




0







4000




0




0




0














None of the compositions tested enhanced post-emergence foliar-applied herbicidal effectiveness of alachlor in this test. Alachlor is not known as a foliar-applied herbicide.




Example 90




Spray compositions were prepared containing glufosinate ammonium salt and excipient ingredients. Compositions 90-01 to 90-12 were exactly like compositions 81-01 to 81-12 respectively except that a different active ingredient was used and a range of active ingredient concentrations was selected appropriate to the active ingredient being applied.




Velvetleaf (


Abutilon theophrasti


, ABUTH), Japanese millet (


Echinochloa crus


-


galli


, ECHCF) and prickly sida (


Sida spinosa


, SIDSP) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 14 days after planting ABUTH, 10 days after planting ECHCF and 17 days after planting SIDSP. Evaluation of herbicidal inhibition was done 11 days after application.




Standards included technical glufosinate ammonium and Liberty, a commercial formulation of glufosinate from AgrEvo. Results, averaged for all replicates of each treatment, are shown in Table 90.














TABLE 90












Glufosinate rate




% Inhibition















Spray composition




g a.i./ha




ABUTH




ECHCF




SIDSP


















Glufosinate




50




0




0




5






(technical)




100




47




0




10







300




90




23




96







600




98




43




94






Liberty




50




77




70




20






(commercial)




100




88




96




93







300




98




100




97







600




99




100




99






90-01




50




77




33




70







100




95




58




93







300




98




95




97







600




99




99




98






90-02




50




33




30




50







100




63




32




93







300




96




52




90







600




98




96




97






90-03




50




15




30




38







100




50




33




87







300




92




40




94







600




98




70




98






90-04




50




92




47




50







100




90




53




85







300




98




98




96







600




98




99




98






90-05




50




35




20




20







100




37




30




20







300




97




45




78







600




91




53




92






90-06




50




10




0




20







100




20




3




20







300




89




47




82







600




91




94




89






90-07




50




50




35




70







100




73




52




80







300




95




87




98







600




98




98




97






90-08




50




48




30




88







100




83




50




93







300




98




97




96







600




98




99




96






90-09




50




58




35




92







100




91




62




93







300




98




96




97







600




98




99




96






90-10




50




30




30




0







100




43




35




10







300




96




43




92







600




95




70




91






90-11




50




33




35




0







100




53




35




7







300




96




43




89







600




97




88




93






90-12




50




37




5




5







100




37




20




10







300




95




40




88







600




97




85




93














Results of this test using glufosinate as the exogenous chemical are summarized as follows:




At the low concentration of 0.05% used here, soybean lecithin containing 45% phospholipid (90-03) was a much more effective excipient than the lecithin-based adjuvant LI-700 (90-06) widely used in the art.




Butyl stearate alone at 0.05% (90-05) enhanced effectiveness on ECHCF.




The combination of lecithin and butyl stearate (90-02) gave greater enhancement of effectiveness than either of these two excipient substances alone.




Fluorad FC-754, either alone (90-04) or in combination with lecithin (90-01) gave extremely high effectiveness, similar to that obtained with the commercial standard.




Oleth-20 at the low concentration of 0.05% (90-09) gave extremely high effectiveness, superior on SIDSP to that obtained with the commercial standard. Addition of 0.005% butyl stearate (90-07) or 0.01 % methyl oleate (90-08) did not provide further enhancement.




Example 91




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 91a. Concentrate compositions 91-01 to 91-12 are aqueous solution concentrates containing colloidal particulates and were prepared by process (ix). Concentrate compositions 91-13 to 91-18 contained colloidal particulates but no surfactant.




The colloidal particulates of this example were in general too large to confer good storage stability to the compositions tested.
















TABLE 91a












Gly-









Concentrate




phosate




% w/w




Type of




Type of
















composition




g a.e./l




Surfactant




Silica




surfactant




silica



















91-01




488




3.0




0.8




steareth-20




Sident 9






91-02




488




3.0




0.8




steareth-20




Sipemat 22






91-03




488




3.0




0.8




steareth-20




Sipernat 22S






91-04




488




3.0




0.8




oleth-20




Sident 9






91-05




488




3.0




0.8




oleth-20




Sipernat 22






91-06




488




3.0




0.8




oleth-20




Sipernat 22S






91-07




488




3.0




1.5




steareth-20




Sident 9






91-08




488




3.0




1.5




steareth-20




Sipernat 22






91-09




488




3.0




1.5




steareth-20




Sipemat 22S






91-10




488




3.0




1.5




oleth-20




Sident 9






91-11




488




3.0




1.5




oleth-20




Sipernat 22






91-12




488




3.0




1.5




oleth-20




Sipernat 22S






91-13




488





0.8




none




Sident 9






91-14




488





1.5




none




Sipernat 22






91-15




488





0.8




none




Sipernat 22S






91-16




488





1.5




none




Sident 9






91-17




488





0.8




none




Sipernat 22






91-18




488





1.5




none




Sipernat 22S














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 21 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was don 14 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 91b.














TABLE 91b












Glyphosate rate




% Inhibition














Concentrate compostion




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




3




37







200




10




57







300




43




87







400




57




88






Formulation J




100




33




80







200




72




98







300




96




99







400




97




99






91-01




100




47




89







200




78




97







300




87




99







400




98




99






91-02




100




37




83







200




70




99







300




90




99







400




95




100






91-03




100




40




89







200




70




99







300




90




100







400




95




100






91-04




100




37




94







200




58




98







300




87




99







400




95




100






91-05




100




30




60







200




73




95







300




85




99







400




97




99






91-06




100




33




67







200




70




97







300




78




99







400




92




100






91-07




100




32




81







200




60




99







300




83




98







400




88




100






91-08




100




40




63







200




65




93







300




90




99







400




90




100






91-09




100




43




70







200




55




98







300




88




99







400




94




100






91-10




100




33




91







200




70




99







300




83




99







400




94




99






91-11




100




20




63







200




70




97







300




92




100







400




94




100






91-12




100




48




67







200




70




93







300




88




98







400




94




100






91-13




100




20




50







200




60




83







300




83




97







400




94




99






91-14




100




43




43







200




67




88







300




83




97







400




91




99






91-15




100




30




50







200




67




73







300




77




96







400




97




96






91-16




100




43




43







200




75




79







300




87




94







400




87




91






91-17




100




40




27







200




68




53







300




87




92







400




93




98






91-18




100




47




10







200




75




37







300




83




63







400




92




88














Many of the high-load (488 g a.e./l) glyphosate formulations of this Example exhibited herbicidal effectiveness equal to or greater than that obtained with commercial standard Formulation J, in spite of containing only 3% alkylether surfactant.




Example 92




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 92a. Concentrate compositions 92-01 to 92-12 and 92-14 to 92-16 are oil-in-water emulsions and were prepared by process (vii). Concentrate composition 92-13 is an aqueous solution concentrate and was prepared by process (viii).
















TABLE 92a











Concentrate




Glyphosate




% w/w




Type of




Type of
















composition




g a.e./l




Oil




Surfactant




oil




surfactant









92-01




163




0.5




5.0




butyl stearate




steareth-30






92-02




163




0.5




5.0




methyl




steareth-30










stearate






92-03




163




0.5




5.0




butyl stearate




Neodol











45-13






92-04




163




0.5




5.0




methyl




Neodol










stearate




45-13






92-05




163




0.5




5.0




butyl stearate




ceteareth-15






92-06




163




0.5




5.0




methyl




ceteareth-15










stearate






92-07




163




0.5




5.0




butyl stearate




laureth-23






92-08




163




0.5




5.0




butyl stearate




oleth-20






92-09




163




0.5




5.0




butyl stearate




steareth-20






92-10




163




0.5




5.0




butyl stearate




ceteareth-27






92-11




163




0.3




5.0




butyl stearate




ceteareth-27






92-12




163




0.3




2.5




butyl stearate




ceteareth-27






92-13




163





5.0




none




ceteareth-27






92-14




163




0.5




5.0




methyl




ceteareth-27










stearate






92-15




163




0.5




5.0




methyl




steareth-20










stearate






92-16




163




0.5




5.0




methyl




oleth-20










stearate














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given. above. Applications of spray compositions were made 20 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B, C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment. are shown in Table 92b.














TABLE 92b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




45




57







200




35




53







300




50




57







400




38




33






Formulation C




100




70




98







200




90




99







300




97




100







400




100




100






Formulation J




100




72




88







200




93




99







300




97




99







400




98




99






92-01




100




83




97







200




97




100







300




99




100







400




100




100






92-02




100




80




99







200




96




100







300




99




100







400




99




100






92-03




100




73




98







200




92




100







300




98




99







400




99




100






92-04




100




73




98







200




87




99







300




97




99







400




99




100






92-05




100




80




98







200




87




100







300




98




100







400




100




100






92-06




100




78




97







200




95




98







300




98




100







400




99




100






92-07




100




78




98







200




88




100







300




96




100







400




98




100






92-08




100




75




98







200




93




99







300




97




99







400




100




99






92-09




100




83




93







200




95




100







300




98




100







400




100




100






92-10




100




80




97







200




95




98







300




98




99







400




100




100






92-11




100




80




97







200




93




99







300




98




100







400




100




99






92-12




100




77




93







200




88




100







300




99




100







400




99




100






92-13




100




80




73







200




95




95







300




99




100







400




100




100






92-14




100




77




94







200




92




99







300




98




100







400




100




99






92-15




100




78




92







200




94




99







300




98




100







400




99




100






92-16




100




77




93







200




90




98







300




98




99







400




99




100














Extremely high herbicidal effectiveness was provided by ceteareth-27 (composition 92-13); this was further enhanced by addition of a small amount of butyl stearate (92-10, 92-11) or methyl stearate (92-14). Compositions performing better than commercial standard Formulations C and J, at least on ABUTH, included those containing steareth-30, steareth-20 or ceteareth-27; in this test oleth-20 was not quite as effective as these saturated alkylethers.




Example 93




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 93a. All are oil-in-water emulsions and were prepared by process (vii). Lecithin (45% phospholipid, Avanti) was first dispersed in water using sonication.














TABLE 93a











Con-








centrate




Gly-




% w/w

















com-




phosate





Butyl




Ethomeen




Ceteareth-




Ceteareth-






position




g a.e./l




Lecithin




stearate




T/25




20




27









93-01




220




0.75




0.75




1.5








93-02




220




0.75




0.75




1.5







93-03




220




0.75




0.75




3.0







93-04




220




0.75




1.50




1.5







93-05




220




0.75




1.50




3.0







93-06




220




3.75




3.75




3.0







93-07




220




1.50




1.50




3.0







93-08




220




1.50




1.50




1.5







93-09




220




3.75




3.75




1.5




1.5






93-10




220




1.50




1.50




I.5




1.5






93-11




220




3.75




7.50




1.5




1.5






93-12




220




3.75




1.50




1.5




1.5






93-13




220




0.75




3.75




1.5





1.5






93-14




220




0.75




7.50




1.5





1.5






93-15




220




0.75




3.75




3.0





3.0






93-16




220




0.75




7.50




3.0





3.0






93-17




220





7.50




3.0






93-18




220




0.75




7.50






3.0














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 23 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 93b.














TABLE 93b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




12




62







200




5




55







300




23




63







400




43




78






Formulation J




100




27




82







200




62




98







300




88




95







400




96




99






93-01




100




13




79







200




68




95







300




82




99







400




95




91






93-02




100




27




82







200




60




97







300




81




95







400




87




99






93-03




100




37




77







200




62




96







300




78




98







400




89




90






93-04




100




37




84







200




57




95







300




84




99







400




89




100






93-05




100




33




77







200




65




100







300




78




97







400




88




97






93-06




100




43




78







200




62




95







300




87




97







400




95




96






93-07




100




48




78







200




80




91







300




90




99







400




76




93






93-08




100




48




83







200




67




89







300




86




96







400




93




97






93-09




100




62




84







200




82




98







300




85




99







400




91




97






93-10




100




63




80







200




75




96







300




85




99







400




99




99






93-11




100




42




75







200




78




98







300




92




99







400




93




100






93-12




100




52




80







200




73




93







300




86




99







400




97




97






93-13




100




55




83







200




75




97







300




97




99







400




92




99






93-14




100




52




87







200




73




95







300




91




97







400




87




98






93-15




100




57




83







200




92




96







300




98




100







400




100




98






93-16




100




79




88







200




87




97







300




99




99







400




97




94






93-17




100




58




83







200




47




94







300




88




98







400




91




93






93-18




100




58




87







200




75




91







300




83




99







400




91




98














Outstanding herbicidal effectiveness was provided by composition 93-18, containing lecithin, ceteareth-27 and butyl stearate. Addition of 3% Ethomeen T/25 (93-16) further enhanced effectiveness. Slightly reduced effectiveness at the lowest glyphosate rate was observed on ABUTH when the butyl stearate concentration was cut in half (93-15).




Example 94




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 94a. Concentrate compositions 94-01 to 94-04, 94-06, 94-08, 94-10 and 94-18 are oil-in-water emulsions and were prepared by process (vii). Concentrate compositions 94-05. 94-07 and 94-09 are aqueous solution concentrates and were prepared by process (viii). Concentrate compositions 94-11 to 94-17 contain colloidal particulates and were prepared by process (ix).




The compositions of this example all showed acceptable storage stability. The compositions shown as containing colloidal particulate were not storage-stable unless the colloidal particulate was included as shown.















TABLE 94a












Gly-




% w/w

















Concentrate




phosate




Butyl





Aerosil




Type of






composition




g a.e./l




stearate




Surfactant




380




surfactant



















94-01




163




0.5




5.0





steareth-20






94-02




163




0.5




5.0





ceteareth-27






94-03




163




0.5




5.0





oleth-20






94-04




163




0.5




5.0





ceteth-20






94-05




163





5.0





ceteth-20






94-06




163




0.5




5.0





Neodol 45-13






94-07




163





5.0





Neodol 45-13






94-08




163




0.5




5.0





ceteareth-15






94-09




163





5.0





ceteareth-15






94-10




163




0.5




5.0





steareth-30






94-11




360




1.0




10.0




1.25




ceteth-20






94-12




360




1.0




10.0




1.25




Neodol 45-13






94-13




360




1.0




10.0




1.25




ceteareth-15






94-14




360




1.0




10.0




1.25




steareth-30






94-15




360




1.0




10.0




1.25




steareth-20






94-16




360




1.0




10.0




1.25




oleth-20






94-17




360




1.0




10.0




1.25




ceteareth-27






94-18




163




0.5




5.0





laureth-23














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 22 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 94b.














TABLE 94b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




0




30







200




2




60







300




17




75







400




50




73






Formulation J




100




20




63







200




42




98







300




75




100







400




83




98






94-01




100




27




57







200




67




98







300




80




99







400




87




98






94-02




100




27




63







200




53




87







300




77




99







400




87




99






94-03




100




12




50







200




53




99







300




65




100







400




83




99






94-04




100




20




63







200




50




98







300




73




98







400




87




98






94-05




100




18




70







200




57




93







300




80




99







400




83




99






94-06




100




17




63







200




35




95







300




60




100







400




75




100






94-07




100




3




43







200




43




95







300




62




100







400




68




96






94-08




100




20




43







200




43




88







300




75




99







400




80




97






94-09




100




37




57







200




55




93







300




83




100







400




83




99






94-10




100




37




50







200




60




96







300




83




99







400




88




99






94-11




100




8




37







200




37




93







300




68




99







400




70




97






94-12




100




13




43







200




40




91







300




67




100







400




77




96






94-13




100




25




40







200




40




80







300




62




97







400




78




98






94-14




100




23




33







200




37




86







300




75




99







400




78




94






94-15




100




23




30







200




43




78







300




53




93







400




78




98






94-16




100




23




37







200




37




95







300




63




97







400




78




95






94-18




100




18




50







200




45




88







300




75




69







400




73




93






94-19




100




missing




missing







200




missing




missing







300




missing




missing







400




mlssing




missing














Compositions exhibiting herbicidal effectiveness greater than that provided by commercial standard Formulation J included 94-01 (steareth-20 plus butyl stearate), 94-09 (ceteareth-15) and 94-10 (steareth-20 plus butyl stearate).




Example 95




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 95a. All are oil-in-water emulsions and were prepared by process (vii).















TABLE 95a













% w/w
















Concentrate




Glyphosate




Butyl





Type of






composition




g a.e./l




stearate




Surfactant




surfactant









95-01




163




1.00




10.0




laureth-23






95-02




163




0.50




5.0




laureth-23






95-03




163




0.25




2.5




laureth-23






95-04




163




1.00




10.0




Neodol 1-9






95-05




163




0.50




5.0




Neodol 1-9






95-06




163




O.25




2.5




Neodol 1-9






95-07




163




1.00




10.0




steareth-10






95-08




163




0.50




5.0




steareth-10






95-09




163




0.25




2.5




steareth-10






95-10




163




0.50




5.0




steareth-20






95-11




163




0.25




2.5




steareth-20






95-12




163




0.25




1.0




steareth-20






95-13




163




0.50




5.0




oleth-20






95-14




163




0.25




2.5




oleth-20






95-15




163




0.25




1.0




oleth-20






95-16




163




0.50




5.0




ceteareth-27






95-17




163




0.25




2.5




ceteareth-27






95-18




163




0.25




1.0




ceteareth-27














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 21 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 20 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 95b.














TABLE 95b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




0




42







200




0




43







300




23




50







400




0




28






Formulation J




100




0




73







200




57




85







300




68




93







400




87




94






95-01




100




18




75







200




58




92







300




85




90







400




94




95






95-02




100




3




77







200




47




90







300




65




89







400




87




95






95-03




100




13




80







200




53




88







300




72




98







400




82




99






95-04




100




0




0







200




53




88







300




67




95







400




83




95






95-05




100




2




60







200




50




83







300




70




93







400




85




92






95-06




100




0




52







200




55




83







300




62




96







400




77




98






95-07




100




8




70







200




68




95







300




91




99







400




95




100






95-08




100




10




65







200




67




99







300




78




99







400




93




100






95-09




100




5




80







200




52




98







300




75




100







400




86




98






95-10




100




0




65







200




62




84







300




58




94







400




75




100






95-11




100




5




83







200




50




99







300




63




97







400




87




99






95-12




100




10




76







200




60




96







300




72




100







400




100




100






95-13




100




20




85







200




67




100







300




91




100







400




96




98






95-14




100




23




68







200




62




89







300




80




100







400




99




99






95-15




100




5




57







200




55




93







300




89




95







400




90




98






95-16




100




30




68







200




68




94







300




83




98







400




100




100






95-17




100




43




68







200




62




99







300




78




100







400




100




99






95-18




100




25




52







200




53




84







300




85




94







400




98




95














Compositions having a 1:3 or lower weight/weight ratio of surfactant to glyphosate a.e., yet outperforming commercial standard Formulation J at least on ABUTH in this test, included those containing just 1% alkylether surfactant (ratio about 1:15) together with 0.25% butyl stearate, where the alkylether surfactant was steareth-20 (95-12), oleth-20 (95-15) or ceteareth-27 (95-18).




Example 96




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 96a. All are aqueous solution concentrates containing colloidal particulates and were prepared by process (ix).




The compositions of this example all showed acceptable storage stability. The compositions shown as containing colloidal particulate were not storage-stable unless the colloidal particulate was included as shown.

















TABLE 96a











Conc.




Glyphosate




% w/w




Type of




Type of




Other


















comp.




g a.e./l




Surfactant




Aerosil




Other




surfactant




Aeorsil




component









96-01




488




3.0




1.5





steareth-20




MOX-80/380 (1:2)







96-02




488




4.5




1.5





steareth-20




380






96-03




488




4.5




1.5





steareth-20




MOX-80/380 (1:2)






96-04




488




4.5




1.5





steareth-20




MOX-80/MOX-170 (1:2)






96-05




488




6.0




1.5




4.12




steareth-20




380




glycerin






96-06




488




3.0




1.5





steareth-20




380






96-07




488




3.0




1.5




7.12




oleth-20




380




propylene glycol






96-08




488




3.0




1.5





oleth-20




MOX-80/380 (1:2)






96-09




488




4.5




1.5





oleth-20




380






96-10




488




4.5




1.5





oleth-20




MOX-80/380 (1:2)














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 21 days after planting ABUTH and ECHCF. and evaluation of herbicidal inhibition was done 20 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 96b.














TABLE 96b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




0




25







200




35




27







300




48




28







400




47




48






Formulation J




100




50




75







200




80




90







300




97




96







400




99




98






96-01




100




53




33







200




83




52







300




98




72







400




98




79






96-02




100




43




27







200




80




57







300




87




73







400




96




78






96-03




100




48




30







200




81




70







300




98




78







400




63




57






96-04




100




45




32







200




87




75







300




97




73







400




98




83






96-05




100




38




27







200




37




23







300




45




32







400




35




18






96-06




100




42




40







200




78




52







300




91




72







400




96




80






96-07




100




37




43







200




48




32







300




73




58







400




55




28






96-08




100




43




37







200




68




57







300




84




62







400




89




82






96-09




100




37




32







200




83




67







300




94




82







400




63




48






96-10




100




32




40







200




75




68







300




90




88







400




65




63














Several high-load (488 g a.e./l) glyphosate compositions exhibited herbicidal effectiveness on ABUTH equal to commercial standard Formulation J, but none was equal to Formulation J on ECHCF in this test.




Example 97




Dry granular concentrate compositions were prepared containing glyphosate ammonium salt and excipient ingredients as shown in Table 97a. The preparation procedure was as follows. Ammonium glyphosate powder was added to a blender. Excipient ingredients were slowly added, together with sufficient water to wet the powder and form a stiff dough. The blender was operated for sufficient time to thoroughly mix all ingredients. The dough was then transferred to extrusion apparatus and was extruded to form granules, which were finally dried in a fluid bed dryer.















TABLE 97a













% w/w



















Conc.




Glyphosate





Butyl





Colloidal





Type of colloidal






comp.




a.e.




Lecithin




stearate




Surfactant




particulate




Type of surfactant




particulate









97-01




68.7






21.0





steareth-20







97-02




66.0





2.2




22.0





steareth-20






97-03




66.1






24.0





oleth-20






97-04




66.0





2.2




22.0





oleth-20






97-05




67.9




10.0




2.0




10.0





MON 0818






97-06




59.2




10.0





20.0 + 2.0





FC-754 + MON 0818






97-07




68.0






21.0




0.8




Flomo 1407




Aerosil 90






97-08




68.0






21.0




0.8




Flomo 1407




Aluminum oxide C






97-09




66.1






24.0





ceteth-20






97-10




66.0





2.2




22.0





ceteth-20






97-11




71.2






16.1




2.0




ceteth-20




Aerosil 380






97-12




71.1






16.3




1.0




ceteth-20




Aerosil blend (*)






97-13




71.2






16.1




2.0




steareth-20




Aerosil 380






97-14




71.2






16.1




1.0




steareth-20




Aerosil blend (*)






97-15




68.0






20.0




1.9




oleth-20




Aerosil-380






97-16




70.8






16.6




1.0




oleth-20




Aerosil blend (*)











(*) Aerosil MOX-80 + Aerosil MOX-170 (1:1)













Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 21 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 20 days after application.




Formulations J and K were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 97b.















TABLE 97b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation J




100




52




80







200




90




96







300




96




100







400




97




99






Formulation K




100




33




70







200




67




93







300




83




99







400




93




100






97-01




100




47




60







200




87




98







300




97




98







400




100




98






97-02




100




47




63







200




80




94







300




90




99







400




98




100






97-03




100




62




62







200




83




93







300




97




96







400




97




100






97-04




100




47




57







200




78




94







300




87




100







400




98




100






97-05




100




25




53







200




60




88







300




80




97







400




83




98






97-06




100




35




37







200




65




62







300




83




83







400




90




95






97-07




100




63




55







200




72




97







300




83




100







400




94




100






97-08




100




30




65







200




72




94







300




87




100







400




92




99






97-09




100




37




63







200




77




83







300




88




99







400




97




99






97-10




100




40




55







200




83




93







300




94




96







400




98




99






97-11




100




42




55







200




78




94







300




88




92







400




94




99






97-12




100




38




58







200




78




97







300




92




97







400




95




100






97-13




100




25




50







200




80




88







300




96




95







400




98




98






97-14




100




50




53







200




88




92







300




98




99







400




99




99






97-15




100




33




57







200




75




91







300




94




97







400




98




99






97-16




100




33




55







200




77




90







300




88




99







400




96




100














Several dry granular compositions of this Example outperformed commercial standard composition K, at least on ABUTH. They included 97-01 to 97-04 and 97-10 to 97-16, all containing an alkylether surfactant ( steareth-20, oleth-20 or ceteth-20).




Example 98




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 98a. All are oil-in-water emulsions and were prepared by process (vii). Soybean lecithin (45% phospholipid, Avanti) was first dispersed in water either by ultrasonication or by use of a microfluidizer as indicated in the column of Table 98a headed “Process”.















TABLE 98a













% w/w




















Conc.




Glyphosate





Butyl




Ethomeen




MON




Ceteareth-




Ceteareth-




Process






comp.




g a.e./l




Lecithin




stearate




T/25




0818




20




27




(*)






















98-01




220




0.75




3.75




3.0






3.0




B






98-02




220




0.75




0.75




3.0






3.0




B






98-03




220




0.75




3.75




3.0





3.0





B






98-04




220




0.75




0.75




3.0





3.0





B






98-05




220




6.00




1.50




3.0





3.0





B






98-06




220




6.00




1.50




3.0






3.0




B






98-07




220




4.00




1.00




3.0





3.0





B






98-08




220




4.00




1.00




3.0






3.0




B






98-09




220




0.75




3.75




3.0






3.0




A






98-10




220




0.75




0.75




3.0






3.0




A






98-11




220




0.75




3.75




6.0







B






98-12




220




0.75




3.75






6.0





B






98-13




345




6.00




1.50




4.5




4.5






B






98-14




345




6.00




1.50




6.0






3.0




B






98-15




345




6.00




1.50




6.0




6.0






B






98-16




345




0.50




7.50




12.0







B






98-17




345




6.00




1.50




4.5




4.5





3.0




B











(*) Process










A Ultrasonicated










B Microfluidized, 3 cycles













Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 19 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 98b. Table 98b















TABLE 98b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




150




45




82







250




55




71







350




80




72







450




88




77






Formulation J




150




55




83







250




89




88







350




97




93







450




99




93







550




99




87






98-01




150




92




83







250




96




96







350




99




96







450




100




86






98-02




150




85




93







250




97




78







350




97




90







450




99




90






98-03




150




87




85







250




98




92







350




99




95







450




100




95






98-04




150




87




89







250




97




92







350




99




94







450




99




91






98-05




150




87




77







250




98




89







350




99




93







450




99




84






98-06




150




12




18







250




96




73







350




99




85







450




99




84






98-07




150




82




89







250




88




96







350




96




98







450




97




97






98-08




150




88




94







250




95




90







350




99




98







450




99




98






98-09




150




94




94







250




95




100







350




97




99







450




99




98






98-10




150




94




94







250




98




99







350




99




97







450




99




96






98-11




150




83




81







250




94




88







350




98




93







450




99




99






98-12




150




68




79







250




95




96







350




98




100







450




99




98






98-13




150




86




98







250




95




98







350




99




100







450




100




98






98-14




150




85




98







250




98




98







350




99




98







450




100




98






98-15




150




86




95







250




97




97







350




99




95







450




100




96






98-16




150




93




94







250




98




98







350




99




98







450




100




97






98-17




150




95




96







250




98




100







350




100




100







450




100




98














Many compositions containing lecithin and butyl stearate outperformed commercial standard Formulation J in this test.




Example 99




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 99a. Concentrate compositions 99-04 and 99-05 are aqueous solution concentrates and were prepared by process (viii). Concentrate compositions 99-06 to 99-13 are aqueous solution concentrates containing colloidal particulates and were prepared by process (ix). Concentrate compositions 99-01 to 99-03 contain colloidal particulate but no surfactant.




The compositions of this example containing colloidal particulate all showed acceptable storage stability. Of those containing steareth-20 but no colloidal particulate, composition 99-04 was acceptable storage-stable but composition 99-05 was not.















TABLE 99a











Con-









cen-









trate




Gly-




% w/w
















com-




phosate




Steareth-




Oleth-




Aero-




Type of






position




g a.e./l




20




20




sil




Aerosil









99-01




484






1.5




MOX-80






99-02




484






1.5




380






99-03




484






1.5




MOX-80/MOX-170(1:1)






99-04




484




1.5






none






99-05




484




3.0






none






99-06




484




3.0





1.5




MOX-170






99-07




484




3.0





1.5




380






99-08




484




3.0





1.5




MOX-80/380(1:1)






99-09




484




3.0





1.5




MOX-80/MOX-170(1:1)






99-10




484





3.0




1.5




MOX-80






99-11




484





3.0




1.5




MOX-170






99-12




484





3.0




1.5




380






99-13




484





3.0




1.5




MOX-80/380(1:1)














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 20 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 19 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 99b.















TABLE 99b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




3




38







200




28




63







300




37




75







400




55




78






Formulation J




100




23




73







200




43




92







300




67




96







400




92




97






99-01




100




23




60







200




40




77







300




65




91







400




75




92






99-02




100




18




50







200




25




53







300




33




75







400




67




82






99-03




100




27




57







200




35




72







300




50




86







400




70




93






99-04




100




42




67







200




48




78







300




78




82







400




80




85






99-05




100




28




43







200




45




77







300




70




92







400




80




95






99-06




100




42




57







200




70




75







300




89




87







400




94




94






99-07




100




43




68







200




62




90







300




88




92







400




97




92






99-08




100




53




57







200




72




87







300




88




94







400




92




97






99-09




100




27




60







200




62




75







300




75




92







400




83




90






99-10




100




47




43







200




73




73







300




82




88







400




97




93






99-11




100




48




57







200




63




75







300




80




91







400




89




98






99-12




100




30




40







200




42




63







300




68




75







400




73




83






99-13




100




37




40







200




57




75







300




73




80







400




78




94














Remarkably strong herbicidal effectiveness was provided by composition 99-05, in spite of its very low surfactant (steareth-20) to glyphosate a.e. ratio of about 1:13. Activity, at least on ABUTH, was further improved to a significant degree by inclusion in the composition of colloidal particulates such as Aerosil MOX-170 (99-06), Aerosil 380 (99-07), a blend of Aerosil MOX-80 and Aerosil 380 (99-08), and a blend of Aerosil MOX-80 and Aerosil MOX-170 (99-09).




Example 100




Aqueous and dry granular concentrate compositions were prepared as shown in Table 100a. Dry granular concentrate compositions 100-01 to 100-1 1 contain glyphosate ammonium salt, and were prepared by the process described in Example 97.




Aqueous concentrate compositions 100-12 to 100-16 contain glyphosate IPA salt and were prepared by process (v), using soybean lecithin (45% phospholipid, Avanti).
















TABLE 100a













% w/w





Type of



















Conc.




Glyphosate




Glyphosate





Butyl





Colloidal




Type of




colloidal






comp.




g a.e./l




a.e.




Lecithin




stearate




Surfactant




particulate




surfactant




particulate






















100-01





68.7






21.0





steareth-20







100-02





66.1






24.0





oleth-20






100-03





67.9




10.0




2.0




10.0





MON 0818






100-04





59.2




10.0





20.0 + 2.0





FC-754 + MON 0818






100-05





66.1






24.0





ceteth-20






100-06





71.2






16.1




2.0




steareth-20




Aerosil 380






100-07





71.2






16.1




2.0




steareth-20




Aerosil blend






100-08





68.0






20.0




1.9




oleth-20




Aerosil 380






100-09





63.5






25.0




2.0




steareth-20




Aerosil blend






100-10





67.9






20.0




2.0




steareth-20




Aerosil blend






100-11





72.2






15.0




2.0




steareth-20




Aerosil blend






100-12




370





4.7





4.7





steareth-20






100-13




350





4.9





4.9





ceteareth-27






100-14




348





5.0





5.0





ceteareth-15






100-15




348





5.0





5.0





oleth-20






100-16




351





4.4





5.0





steareth-30











Aerosil blend: Aerosil MOX-80 + Aerosil MOX-170 (1:1)













Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 20 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations J and K were applied as comparative treatments. Results, averaged for all replicates of each treatment. are shown in Table 100b.















TABLE 100b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation J




100




0




20







200




28




57







300




58




96







400




73




99






Formulation K




100




22




13







200




42




83







300




48




91







400




58




95






100-01




100




28




30







200




48




80







300




80




97







400




85




99






100-02




100




43




52







200




68




80







300




72




88







400




86




94






100-03




100




23




37







200




50




83







300




75




88







400




85




96






100-04




100




50




45







200




73




80







300




85




92







400




95




94






100-05




100




18




45







200




65




83







300




87




95







400




94




86






100-06




100




47




50







200




62




68







300




82




94







400




91




87






100-07




100




50




47







200




60




78







300




87




87







400




93




93






100-08




100




30




55







200




55




77







300




82




85







400




88




97






100-09




100




45




50







200




57




78







300




83




83







400




84




89






100-10




100




42




50







200




57




80







300




73




91







400




91




90






100-11




100




28




48







200




50




75







300




70




87







400




82




89






100-12




100




20




40







200




63




80







300




67




96







400




80




88






100-13




100




27




35







200




50




85







300




77




90







400




84




86






100-14




100




27




25







200




40




70







300




68




94







400




89




91






100-15




100




17




20







200




47




82







300




58




89







400




91




95






100-16




100




22




20







200




41




80







300




84




89







400




99




98














All compositions of the invention in this study exhibited greater herbicidal effectiveness on both ABUTH and ECHCF, in some cases by a very substantial margin, than commercial standard Formulation K.




Example 101




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 101a. All contain colloidal particulates and were prepared by process (ix).




The compositions of this example all showed acceptable storage stability. The compositions shown as containing colloidal particulate were not storage-stable unless the colloidal particulate was included as shown.
















TABLE 101a












Gly-




% w/w



















Conc.




phosate





Sur-




Aerosil




Type of




Type of






comp.




g a.e./l




Oil




factant




380




oil




surfactant









101-01




360




1.0




10.0




1.25




butyl stearate




oleth-20






101-02




360




1.0




10.0




1.25




stearylamine




oleth-20






101-03




360




1.0




10.0




1.25




stearyl alcohol




oleth-20






101-04




360




1.0




10.0




1.25




docosane




oleth-20






101-05




360





10.0




1.25




none




oleth-20






101-06




360




1.0




10.0




1.25




butyl stearate




steareth-30






101-07




360




1.0




10.0




1.25




stearylamine




steareth-30






101-08




360




1.0




10.0




1.25




stearyl alcohol




steareth-30






101-09




360




1.0




10.0




1.25




docosane




steareth-30






101-10




360





10.0




1.25




none




steareth-30






101-11




360





5.0 +




1.25




none




oleth-20 +









5.0






steareth-20






101-12




360





5.0 +




1.25




none




oleth-20 +









5.0






steareth-30






101-13




360





5.0 +




1.25




none




oleth-20 +









5.0






ceteareth-27






101-14




360





5.0 +




1.25




none




oleth-20 +









5.0






ceteareth-15






101-15




360





5.0 +




1.25




none




steareth-30 +









5.0






steareth-20






101-16




360





5.0 +




1.25




none




steareth-30 +









5.0






ceteareth-27






101-17




360





5.0 +




1.25




none




steareth-30 +









5.0






ceteareth-15






101-18




360





10.0




1.25




none




laureth-23














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 19 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 101b.















TABLE 101b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




0




60







200




15




73







300




33




88







400




57




91






Formulation J




100




5




70







200




37




92







300




80




99







400




77




96






101-01




100




13




88







200




32




85







300




48




98







400




90




93






101-02




100




10




70







200




45




98







300




72




99







400




80




98






101-03




100




3




77







200




25




94







300




47




98







400




75




99






101-04




100




7




67







200




23




94







300




40




99







400




7




47






101-05




100




7




76







200




25




88







300




45




96







400




75




97






101-06




100




12




96







200




30




97







300




45




98







400




15




60






101-07




100




8




83







200




12




97







300




35




94







400




50




98






101-08




100




15




72







200




30




88







300




40




99







400




0




33






101-09




100




5




73







200




15




94







300




47




99







400




5




53






101-10




100




7




79







200




15




95







300




45




98







400




62




99






101-11




100




5




84







200




13




98







300




30




98







400




55




100






101-12




100




3




95







200




17




99







300




28




99







400




67




100






101-13




100




5




90







200




17




99







300




30




100







400




60




98






101-14




100




3




98







200




25




97







300




38




100







400




57




100






101-15




100




5




97







200




25




97







300




40




100







400




40




99






101-16




100




10




97







200




15




98







300




52




100







400




0




47






101-17




100




7




97







200




25




94







300




40




98







400




33




97






101-18




100




7




96







200




25




99







300




55




100







400




73




100














Percent inhibition data for the 400 g a.e./ha glyphosate rate in this test are unreliable and should be ignored. Neither oleth-20 (composition 101-05) nor steareth-20 (101-10) provided herbicidal effectiveness equal to Formulation J in this study, and no great or consistent further enhancement was obtained by adding butyl stearate.




Example 102




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 102a. Concentrate compositions 102-01 to 102-03 are oil-in-water emulsions and were prepared by process (vii). Compositions 102-04 to 102-18 all contain colloidal particulates and were prepared by process (ix). Different mixing methods were employed in the final stage of preparation of these compositions, as indicated in the column of Table 102a headed “Process”.




The compositions of this example all showed acceptable storage stability. The compositions shown as containing colloidal particulate were not storage-stable unless the colloidal particulate was included as shown.
















TABLE 102a











Con-










centrate




Gly-




% w/w

















com-




phosate




Butyl




Sur-




Aerosil




Type of




Process






position




g a.e./l




stearate




factant




380




surfactant




(*)




















102-01




163




0.5




5.0





oleth-20







102-02




163




0.5




5.0





steareth-20






102-03




163




0.5




5.0





ceteareth-27






102-04




360




1.0




10.0




1.25




ceteareth-15




A






102-05




360




1.0




10.0




1.25




ceteth-20




A






102-06




360




1.0




10.0




1.25




steareth-20




A






102-07




360




1.0




10.0




I.25




oleth-20




A






102-08




360




1.0




10.0




1.25




ceteareth-27




A






102-09




360




1.0




10.0




1.25




steareth-30




A






102-10




360





10.0




1.25




steareth-30




A






102-11




360




1.0




10.0




1.25




oleth-20




A






102-12




360




1.0




10.0




1.25




oleth-20




B






102-13




360




1.0




10.0




1.25




oleth-20




C






102-14




360




1.0




10.0




1.25




oleth-20




D






102-15




360




1.0




10.0




1.25




oleth-20




E






102-16




360




1.0




10.0




1.25




oleth-20




F






102-17




360




1.0




10.0




1.25




oleth-20




G






102-18




360




1.0




10.0




1.25




oleth-20




A











(*) Process:










A Silverson mixer, medium screen, 3 minutes at 7000 rpm










B Silverson mixer, coarse screen, 3 minutes at 7000 rpm










C Fann mixer, 50% output, 5 minutes










D Turrax mixer, 3 minutes at 8000 rpm










E Overhead stirrer, low speed










F Overhead stirrer, high speed










G Hand shaking, 3 minutes













Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 19 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 102b.















TABLE 102b












Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




20




40







200




45




50







300




65




72







400




78




85






Formulation J




100




43




53







200




80




80







300




96




82







400




99




94






102-01




100




45




57







200




80




72







300




89




78







400




98




83






102-02




100




53




57







200




80




78







300




89




77







400




93




83






102-03




100




45




60







200




83




75







300




97




73







400




97




85






102-04




100




45




45







200




80




80







300




83




83







400




95




95






102-05




100




42




42







200




77




77







300




93




93







400




98




98






102-06




100




30




30







200




42




42







300




27




30







400




3




20






102-07




100




40




40







200




77




75







300




90




93







400




97




86






102-08




100




43




50







200




80




80







300




92




93







400




96




98






102-09




100




0




2







200




82




75







300




83




96







400




90




88






102-10




100




57




60







200




80




70







300




88




88







400




95




93






102-11




100




35




47







200




72




75







300




80




75







400




85




77






102-12




100




47




47







200




72




77







300




80




90







400




86




78






102-13




100




55




50







200




75




83







300




78




92







400




91




92






102-14




100




52




50







200




75




78







300




83




88







400




99




92






102-15




100




47




47







200




70




73







300




87




87







400




75




63






102-16




100




43




40







200




78




75







300




88




88







400




87




91






102-17




100




43




43







200




67




88







300




80




75







400




92




83






102-18




100




27




40







200




63




57







300




82




73







400




87




70














Results obtained with composition 102-06 are out of line with other data in this Example and an error in formulation or application is suspected. Some differences in herbicidal effectiveness were evident when a composition containing 360 g a.e./l glyphosate, 1% butyl stearate, 10% oleth-20 and 1.25% Aerosil 380 was processed in different ways (102-11 to 102-17). However, as compositions 102-07 and 102-11 were identically processed yet differed in effectiveness. no firm conclusions can be drawn from this test.




Example 103




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 103a. Concentrate compositions 103-01 to 103-09 are aqueous solution concentrates and were prepared by process (viii). Concentrate compositions 103-10 to 103-18 are aqueous solution concentrates containing colloidal particulates and were prepared by process (ix).




Compositions of this example containing 3% or 6% surfactant were not acceptably storage-stable except in the presence of colloidal particulate as shown.















TABLE 103a













% w/w


















Composition




Glyphosate




Steareth-




Oleth-




Velvetex





Type of






no.




g a.e./l




20




20




AB-45




Aerosil




Aerosil









103-01




488




1.0







none






103-02




488




3.0







none






103-03




488




6.0







none






103-04




488





1.0






none






103-05




488





3.0






none






103-06




488





6.0






none






103-07




488






1.0





none






103-08




488






3.0





none






103-09




488






4.6





none






103-10




488




1.0






1.5




MOX-80/MOX-170 (1:1)






103-11




488




3.0






1.5




MOX-80/MOX-170 (1:1)






103-12




488




6.0






1.5




MOX-80/MOX-170 (1:1)






103-13




488





1.0





1.5




MOX-80/MOX-170 (1:1)






103-14




488





3.0





1.5




MOX-80/MOX-170 (1:1)






103-15




488





6.0





1.5




MOX-80/MOX-170 (1:1)






103-16




488






1.0




1.5




MOX-80/MOX-170 (1:1)






103-17




488






3.0




1.5




MOX-80/MOX-170 (1:1)






103-18




488






4.6




1.5




MOX-80/MOX-170 (1:1)














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 103b.















TABLE 103b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




10




40







200




38




67







300




70




80







400




86




92






Formulation J




100




43




58







200




65




82







300




91




94







400




100




95






103-01




100




23




60







200




40




65







300




73




87







400




80




92






103-02




100




38




67







200




77




82







300




95




83







400




99




93






103-03




100




33




67







200




78




73







300




90




94







400




100




96






103-04




100




23




63







200




48




81







300




68




87







400




72




88






103-05




100




30




63







200




63




80







300




78




89







400




95




93






103-06




100




25




85







200




68




93







300




77




93







400




99




95






103-07




100




13




60







200




42




80







300




57




95







400




92




96






103-08




100




20




73







200




43




92







300




83




93







400




72




96






103-09




100




30




73







200




50




94







300




65




96







400




75




98






103-10




100




10




65







200




53




88







300




72




94







400




83




95






103-11




100




15




50







200




57




77







300




82




95







400




92




97






103-12




100




30




70







200




68




98







300




78




97







400




96




98






103-13




100




15




77







200




43




93







300




68




95







400




77




99






103-14




100




10




73







200




40




93







300




68




98







400




78




98






103-15




100




missing




missing







200




missing




missing







300




missing




missing







400




missing




missing






103-16




100




0




60







200




30




93







300




40




99







400




50




99






103-17




100




2




83







200




43




99







300




67




100







400




67




100






103-18




100




5




95







200




37




100







300




60




100







400




78




100














In high-load (488 g a.e./l) glyphosate compositions, steareth-20 at 3% or 6% provided greater herbicidal effectiveness in this test than the same concentrations of oleth-20. Even at just 3%, steareth-20 (composition 103-02) gave effectiveness equal to commercial standard Formulation J. Addition of a blend of colloidal particulates to stabilize the composition (103-11) slightly reduced effectiveness in this study.




Example 104




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 104a. Concentrate compositions 104-01 to 104-04 are aqueous solution concentrates and were prepared by process (viii). Concentrate compositions 104-08 to 104-18 are aqueous solution concentrates containing colloidal particulates and were prepared by process (ix). Concentrate compositions 104-05 to 104-07 contain colloidal particulate but no surfactant.




All compositions of this example except 104-01 to 104-03 were acceptably storage-stable.















TABLE 104a













% w/w


















Concentrate




Glyphosate




Steareth-




Steareth-




MON





Type of






composition




g a.e./l




20




100




0818




Aerosil




Aerosil









104-01




488




3.0










104-02




488




4.5









104-03




488




6.0









104-04




488






3.0







104-05




488







1.5




380






104-06




488







1.5




MOX-80/MOX-170 (1:1)






104-07




488







3.0




MOX-80/380 (1:1)






104-08




488





1.5








104-09




488




3.0





3.0




1.5




380






104-10




488




4.5





3.0




1.5




380






104-11




488




6.0





3.0




1.5




380






104-12




488




3.0





3.0




1.5




MOX-80/MOX-170 (1:1)






104-13




488




4.5





3.0




1.5




MOX-80/MOX-170 (1:1)






104-14




488




6.0





3.0




1.5




MOX-80/MOX-170 (1:1)






104-15




488




3.0





3.0




1.5




MOX-80/380 (1:1)






104-16




488




4.5





3.0




1.5




MOX-80/380 (1:1)






104-17




488




6.0





3.0




1.5




MOX-80/380 (1:1)






104-18




488





4.5




3.0




1.5




MOX-80/MOX-170 (1:1)














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 21 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment. are shown in Table 104b.














TABLE 104b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




2




23







200




18




50







300




42




67







400




63




80






Formulation J




100




20




47







200




40




86







300




83




98







400




93




98






104-01




100




10




75







200




62




83







300




80




96







400




93




99






104-02




100




40




60







200




77




92







300




87




97







400




93




99






104-03




100




23




40







200




38




63







300




78




91







400




97




91






104-04




100




20




38







200




23




77







300




43




94







400




73




94






104-05




100




7




30







200




25




37







300




42




60







400




67




63






104-06




100




7




30







200




20




53







300




52




67







400




83




67






104-07




100




5




35







200




20




63







300




57




80







400




43




85






104-08




100




22




83







200




47




99







300




86




98







400




78




100






104-09




100




12




45







200




25




77







300




40




83







400




37




95






104-10




100




13




53







200




73




99







300




85




98







400




99




99






104-11




100




25




50







200




60




88







300




93




99







400




99




99






104-12




100




25




45







200




57




88







300




85




97







400




100




94






104-13




100




30




52







200




68




87







300




93




99







400




100




92






104-14




100




40




45







200




73




88







300




81




98







400




100




99






104-15




100




8




57







200




33




96







300




81




99







400




95




99






104-16




100




10




62







200




48




83







300




99




98







400




100




100






104-17




100




27




58







200




65




92







300




75




98







400




93




99






104-18




100




5




40







200




33




87







300




55




98







400




75




98














Among stabilized high-load (488 g a.e./l) glyphosate compositions providing herbicidal effectiveness superior to commercial standard Formulation J, at least on ABUTH, were 104-10 and 104-11 (respectively 4.5% and 6% steareth-20+3% MON 0818+1.5% Aerosil 380), 104-13 (4.5% steareth-20+3% MON 0818+1.5% Aerosil MOX-80/MOX-170 blend) and 104-16 (4.5% steareth-20+3% MON 0818+1.5% Aerosil MOX-80/380 blend). The relatively poor performance of composition 104-04 and the good performance of composition 104-02 shows that the excellent results obtained with the stabilized compositions listed above are primarily attributable to the steareth-20 component.




Example 105




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 105a. Concentrate compositions 105-01 to 105-09 are aqueous solution concentrates and were prepared by process (viii). Concentrate compositions 105-10 to 105-18 are aqueous solution concentrates containing colloidal particulates and were prepared by process (ix).




Compositions of this example containing 3% or 6% surfactant were not acceptably storage-stable except in the presence of colloidal particulate as shown.















TABLE 105a













% w/w


















Concentrate




Glyphosate




Steareth-




Oleth-




Velvetex





Type of






composition




g a.e./l




20




20




AB-45




Aerosil




Aerosil









105-01




488




1.5







none






105-02




488




3.0







none






105-03




488




6.0







none






105-04




488





1.5






none






105-05




488





3.0






none






1O5-06




488





6.0






none






105-07




488






1.5




none






105-08




488






3.0





none






105-09




488






4.5





none






105-10




488




1.5






1.5




MOX-80/380 (1:1)






105-11




488




3.0






1.5




MOX-80/380 (1:1)






105-12




488




6.0






1.5




MOX-80/380 (1:1)






105-13




488





1.5





1.5




MOX-80/380 (1:1)






105-14




488





3.0





1.5




MOX-80/380 (1:1)






105-15




488





6.0





1.5




MOX-80/380 (1:1)






105-16




488






1.5




1.5




MOX-80/380 (1:1)






105-17




488






3.0




1.5




MOX-80/380 (1:1)






105-18




488






4.5




1.5




MOX-80/380 (1:1)














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 15 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 22 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 105b.














TABLE 105b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




0




10







200




3




27







300




13




30







400




33




40






Formulation J




100




2




53







200




30




97







300




70




99







400




80




99






105-01




100




5




67







200




30




89







300




58




98







400




80




100






105-02




100




20




60







200




45




90







300




78




99







400




80




100






105-03




100




20




57







200




47




93







300




78




96







400




83




98






105-04




100




3




57







200




30




83







300




63




99







400




82




98






105-05




100




5




53







200




27




83







300




47




98







400




77




100






105-06




100




5




40







200




23




70







300




47




92







400




77




99






105-07




100




3




53







200




30




85







300




60




94







400




72




97






105-08




100




3




50







200




22




88







300




53




97







400




80




100






105-09




100




0




40







200




20




83







300




40




99







400




67




99






105-10




100




0




40







200




27




60







300




47




83







400




78




94






105-11




100




5




47







200




25




77







300




57




96







400




87




97






105-12




100




15




43







200




52




88







300




87




98







400




87




98






105-13




100




0




40







200




17




70







300




35




83







400




53




88






105-14




100




0




33







200




18




67







300




28




90







400




62




98






105-15




100




2




33







200




25




70







300




53




85







400




72




97






105-16




100




0




30







200




17




50







300




27




67







400




72




87






105-17




100




0




0







200




7




63







300




32




88







400




47




90






105-18




100




0




5







200




12




60







300




25




83







400




45




97














Compositions containing steareth-20 generally performed better than counterparts containing oleth-20 in this study, both in the presence and in the absence of colloidal particulates.




Example 106




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 106a. All contain colloidal particulates and were prepared by process (ix).




The compositions of this example all showed acceptable storage stability. The compositions shown as containing colloidal particulate were not storage-stable unless the colloidal particulate was included as shown.















TABLE 106a













% w/w



















Gly-











Concentrate




phosate






Aerosil




Type of




Type of






composition




a.e.




Oil




Surfactant




380




oil




surfactant









106-01




31




1.0




10.0




1.25




Butyl




steareth-20











stearate






106-02




31




1.0




10.0




1.25




Butyl




oleth-20











stearate






106-03




31




1.0




10.0




1.25




Butyl




steareth-30











stearate






106-04




31





10.0




1.25




none




steareth-30














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Treatments were applied at four different hours of the day. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 22 days after application.




Formulation J was applied as a comparative treatment. Results, averaged for all replicates of each treatment, are shown in Table 106b.















TABLE 106b











Concentrate




Hour when




Glyphosate rate




% Inhibition















composition




applied




g a.e./ha




ABUTH




ECHCF


















Formulation J




1000




100




5




33








200




42




75








300




67




83








400




77




93






106-01




1000




100




7




33








200




40




70








300




50




82








400




78




91






106-02




1000




100




18




33








200




37




73








300




48




91








400




80




92






106-03




1000




100




30




33








200




40




75








300




82




85








400




83




80






106-04




1000




100




30




30








200




43




78








300




78




92








400




93




95






Formulation J




1200




100




5




38








200




35




87








300




53




96








400




88




99






106-01




1200




100




10




30








200




47




91








300




70




89








400




78




97






106-02




1200




100




5




37








200




40




75








300




48




87








400




70




94






106-03




1200




100




20




37








200




50




82








300




78




98








400




83




97






106-04




1200




100




33




33








200




45




93








300




75




98








400




95




100






Formulation J




1400




100




15




40








200




30




90








300




55




100








400




80




100






106-01




1400




100




17




40








200




45




70








300




75




97








400




80




98






106-02




1400




100




17




47








200




35




83








300




67




97








400




63




97






106-03




1400




100




30




40








200




63




80








300




77




97








400




78




100






106-04




1400




100




23




40








200




45




87








300




73




100








400




78




100






Formulation J




1600




100




10




37








200




32




83








300




52




97








400




75




98






106-01




1600




100




27




43








200




40




89








300




77




99








400




95




99






106-02




1600




100




20




53








200




40




95








300




53




98








400




80




98






106-03




1600




100




27




60








200




60




93








300




78




97








400




96




100






106-04




1600




100




15




37








200




43




83








300




67




97








400




78




96














Composition 106-03 illustrates the consistency of high-level performance obtainable with, in this case, steareth-30 at an approximately 1:3 weight/weight ratio to glyphosate a.e., together with a small amount of butyl stearate and Aerosil 380. An average of percent inhibition of ABUTH across all four glyphosate rates shows the following comparison of 106-03 with Formulation J, applied at four different hours of the day:

















Hour




Formulation J




Composition 106-03











1000




48




59






1200




45




58






1400




48




62






1600




42




65














Example 107




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 107a. Concentrate compositions 107-01 to 107-07 are aqueous solution concentrates and were prepared by process (viii). Concentrate compositions 107-08 to 107-18 are aqueous solution concentrates containing colloidal particulates and were prepared by process (ix).




Compositions 107-01 to 107-06 were not acceptably storage-stable. All other compositions showed acceptable storage stability.














TABLE 107a













% w/w
















Concentrate




Glyphosate




Steareth-




Steareth-




Agrimul




Aerosil






composition




g a.e./l




30




20




PG-2069




380









107-01




488




3.00









107-02




488




4.50









107-03




488




6.00









107-04




488





3.00








107-05




488





4.50








107-06




488





6.00








107-07




488






2.0







107-08




488




3.00






1.5






107-09




488




4.50






1.5






107-10




488




6.00






1.5






107-11




488





3.00





1.5






107-12




488





4.50





1.5






107-13




488





6.00





1.5






107-14




488




1.50




1.50





1.5






107-15




488




2.25




2.25





1.5






107-16




488




3.00




3.00





1.5






107-17




488




2.25




2.25




2.0




1.5






107-18




488




3.00




3.00




2.0




1.5














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 23 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 107b.














TABLE 107b












Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




2




20







200




22




33







300




35




67







400




68




73






Formulation J




100




32




63







200




78




90







300




83




93







400




92




97






107-01




100




38




57







200




50




63







300




62




80







400




75




89






107-02




100




20




57







200




63




70







300




75




88







400




80




96






107-03




100




47




53







200




72




80







300




87




96







400




100




99






107-04




100




33




30







200




48




60







300




75




73







400




90




83






107-05




100




10




30







200




43




50







300




68




82







400




83




92






107-06




100




22




40







200




43




50







300




75




83







400




83




87






107-07




100




10




37







200




40




63







300




78




86







400




95




96






107-08




100




23




43







200




68




63







300




92




88







400




98




93






107-09




100




47




57







200




78




70







300




95




92







400




100




96






107-10




100




37




57







200




85




68







300




92




85







400




100




93






107-11




100




28




43







200




63




73







300




85




83







400




95




96






107-12




100




40




53







200




75




88







300




90




92







400




100




97






107-13




100




40




53







200




75




75







300




99




92







400




100




98






107-14




100




30




43







200




68




72







300




83




82







400




96




97






107-15




100




38




47







200




77




72







300




94




92







400




100




96






107-16




100




33




43







200




75




67







300




92




88







400




100




94






107-17




100




25




43







200




68




82







300




78




96







400




99




96






107-18




100




13




37







200




72




70







300




87




80







400




99




85














Several stabilized high-load (488 g a.e./l) glyphosate compositions of this Example provided herbicidal effectiveness equal or superior, at least on ABUTH, to that obtained with commercial standard Formulation J.




Example 108




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 108a. Concentrate compositions 108-12 to 108-14 are aqueous solution concentrates and were prepared by process (viii).




Concentrate compositions 108-01 to 108-11 and 108-15 to 108-17 are aqueous solution concentrates containing colloidal particulates and were prepared by process (ix).















TABLE 108a













% w/w


















Conc.




Glyphosate




Steareth-




Ethomeen




Propylene





Type of






comp.




g a.e./l




20




T/25




glycol




Aerosil




Aerosil









108-01




488




3.0






0.8




380






108-02




488




6.0






1.5




MOX-80/MOX-170 (1:1)






108-03




488




4.5






1.5




380






108-04




488




4.5




2.25




0.5




1.5




MOX-80/380 (1:2)






108-05




488




4.5





0.5




1.5




MOX-80/380 (1:2)






108-06




488




6.0





0.5




1.5




MOX-80/380 (1:2)






108-07




488




3.0




1.50




0.5




1.5




MOX-80/380 (1:2)






108-08




488




6.0




3.00




0.5




1.5




MOX-80/380 (1:2)






108-09




488




3.0




1.50




0.5




1.5




380






108-10




488




4.5




2.25




0.5




1.5




380






108-11




488




6.0




3.00




0.5




1.5




380






108-12




488





1.50




0.5





none






108-13




488





2.25




0.5





none






108-14




488





3.00




0.5





none






108-15




488





1.50




0.5




1.5




MOX-80/380 (1:2)






108-16




488





2.25




0.5




1.5




MOX-80/380 (1:2)






108-17




488





3.00




0.5




1.5




MOX-80/380 (1:2)














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 20 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 108b.















TABLE 108b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF

















Formulation B




100




0




3







200




10




12







300




43




22







400




47




27






Formulation J




100




13




15







200




25




22







300




58




53







400




68




82






108-01




100




30




20







200




60




53







300




73




88







400




87




96






108-02




100




40




23







200




63




55







300




88




87







400




93




93






108-03




100




42




20







200




72




55







300




82




83







400




90




88






108-04




100




60




32







200




70




57







300




90




88







400




90




93






108-05




100




47




32







200




67




57







300




88




85







400




94




88






108-06




100




33




37







200




68




67







300




82




80







400




90




88






108-07




100




35




37







200




67




70







300




87




85







400




97




93






108-08




100




32




35







200




67




77







300




85




92







400




97




95






108-09




100




27




33







200




57




67







300




88




83







400




93




95






108-10




100




13




33







200




62




58







300




80




80







400




92




92






108-11




100




13




20







200




60




57







300




88




63







400




93




82






108-12




100




10




27







200




53




53







300




70




67







400




88




85






108-13




100




3




28







200




50




57







300




67




70







400




90




82






108-14




100




3




28







200




55




57







300




70




83







400




87




87






108-15




100




10




20







200




58




43







300




70




72







400




83




85






108-16




100




12




22







200




55




57







300




73




77







400




92




90






108-17




100




7




20







200




53




55







300




70




75







400




85




88














Several stabilized high-load (488 g a.e./l) glyphosate compositions of this Example provided herbicidal effectiveness equal or superior, on both ABUTH and ECHCF, to that obtained with commercial standard Formulation J.




Example 109




Glyphosate-containing spray compositions were prepared by tank-mixing Formulation B with excipients as shown in Table 109.




Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 22 days after application. Results, averaged for all replicates of each treatment, are shown in Table 109.
















TABLE 109












Glypho-










sate





Ratio







Glyphosate




rate





add./




% Inhibition
















composition




g a.e./ha




Additive




a.e.




ABUTH




ECHCF



















Formulation B




150




none





18




25







250






73




58







350






80




82






Formulation J




150




none





47




90







250






77




93







350






95




94






Formulation B




150




steareth-10




1:0.3




53




88







250






83




94







350






98




98






Formulation B




150




steareth-10




1:1




48




73







250






67




97







350






93




99






Formulation B




150




steareth-10




1:1.5




52




60







250






65




95







350






86




99






Formulation B




150




steareth-10




1:3




48




73







250






65




83







350






80




98






Formulation B




150




steareth-10




1:6




50




81







250






60




87







350






85




97






Formulation B




150




steareth-20




1:0.3




76




92







250






100




93







350






100




99






Formulation B




150




steareth-20




1:11




65




75







250






94




96







350






99




99






Formulation B




150




steareth-20




1:1.5




52




95







250






84




92







350






98




98






Formulation B




150




steareth-20




1:3




53




82







250






82




100







350






98




93






Formulation B




150




steareth-20




1:6




47




62







250






68




93







350






92




97






Formulation B




150




steareth-30




1:0.3




63




88







250






97




100







350






100




100






Formulation B




150




steareth-30




1:1




53




72







250






88




96







350






97




97






Formulation B




150




steareth-30




1:1.5




50




79







250






81




89







350






96




100






Formulation B




150




steareth-30




1:3




50




67







250






78




88







350






97




91






Formulation B




150




steareth-30




1:6




47




58







250






75




99







350






89




99






Formulation B




150




ceteareth-30




1:0.3




55




86







250






89




91







350






99




100






Formulation B




150




ceteareth-30




1:1




50




86







250






85




95







350






97




100






Formulation B




150




ceteareth-30




1:1.5




43




75







250






80




100







350






88




98






Formulation B




150




ceteareth-30




1:3




33




73







250






60




92







350






94




100






Formulation B




150




ceteareth-30




1:6




37




73







250






53




89







350






88




100






Formulation B




150




Ethomeen T/25




1:0.3




67




90







250






92




99







350






100




100






Formulation B




150




Ethomeen T/25




1:1




58




94







250






83




96







350






93




98






Formulation B




150




Ethomeen T/25




1:1.5




50




73







250






86




100







350






99




100






Formulation B




150




Ethomeen T/25




1:3




45




83







250






89




95







350






100




100






Formulation B




150




Ethomeen T/25




1:6




35




82







250






73




98







350






88




98














Steareth-20, steareth-30 and ceteareth-30 were more effective additives for Formulation B than steareth-10 in this study.




Example 110




Aqueous spray compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 110a. Process (iii) was followed for spray compositions 110-01 to 110-22 and 110-26 to 110-72, using soybean lecithin (45% phospholipid, Avanti). Process (i) was followed for spray compositions 110-23 to 110-25.














TABLE 110a













% w/w
















Spray





Butyl








compositions




Lecithin




stearate




MON 0818











110-01




0.10




0.10








110-02




0.10




0.08








110-03




0.10




0.05








110-04




0.10




0.03








110-05




0.10




0.01








110-06




0.08




0.10








110-07




0.05




0.10








110-08




0.03




0.10








110-09




0.01




0.10








110-10




0.08




0.01








110-11




0.05




0.01








110-12




0.03




0.01








110-13




0.01




0.01








110-14




0.01




0.03








110-15




0.01




0.05








110-16




0.01




0.08








110-17




0.03




0.03








110-18




0.05




0.05








110-19




0.08




0.08








110-20




0.08




0.03








110-21




0.03




0.08








110-22




0.05









110-23





0.05








110-24






0.09







110-25






0.03







110-26




0.09




0.02




0.09







110-27




0.09




0.02




0.05







110-28




0.01




0.01




0.01







110-29




0.01




0.01




0.03







110-30




0.01




0.01




0.05







110-31




0.01




0.01




0.08







110-32




0.01




0.01




0.10







110-33




0.01




0.05




0.01







110-34




0.01




0.05




0.03







110-35




0.01




0.05




0.05







110-36




0.01




0.05




0.08







110-37




0.01




0.05




0.10







110-38




0.01




0.10




0.01







110-39




0.01




0.10




0.03







110-40




0.01




0.10




0.05







110-41




0.01




0.10




0.08







110-42




0.01




0.10




0.10







110-43




0.05




0.01




0.01







110-44




0.05




0.01




0.03







110-45




0.05




0.01




0.05







110-46




0.05




0.01




0.08







110-47




0.05




0.01




0.10







110-48




0.05




0.05




0.01







110-49




0.05




0.05




0.03







110-50




0.05




0.05




0.05







110-51




0.05




0.05




0.08







110-52




0.05




0.05




0.10







110-53




0.05




0.10




0.01







110-54




0.05




0.10




0.03







110-55




0.05




0.10




0.05







110-56




0.05




0.10




0.08







110-57




0.05




0.10




0.10







110-58




0.10




0.01




0.01







110-59




0.10




0.01




0.03







110-60




0.10




0.01




0.05







110-61




0.10




0.01




0.08







110-62




0.10




0.01




0.10







110-63




0.10




0.05




0.01







110-64




0.10




0.05




0.03







110-65




0.10




0.05




0.05







110-66




0.10




0.05




0.08







110-67




0.10




0.05




0.10







110-68




0.10




0.10




0.01







110-69




0.10




0.10




0.03







110-70




0.10




0.10




0.05







110-71




0.10




0.10




0.08







110-72




0.10




0.10




0.10















Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




Formulations C and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 110b.















TABLE 110b













Glyphosate rate




% Inhibition
















Spray composition




g a.e./ha




ABUTH




ECHCF











Formulation C




280




71




73







Formulation J




280




65




77







110-01




280




60




49







110-02




280




46




47







110-03




280




34




48







110-04




280




33




35







110-05




280




50




33







110-06




280




49




52







110-07




280




39




42







110-08




280




48




38







110-09




280




51




42







110-10




280




37




30







110-11




280




48




30







110-12




280




56




34







110-13




280




41




45







110-14




280




52




56







110-15




280




38




40







110-16




280




53




33







110-17




280




45




40







110-18




280




52




38







110-19




280




37




34







110-20




280




36




28







110-21




280




40




38







110-22




280




44




47







110-23




280




60




42







110-24




280




92




76







110-25




280




87




69







110-26




280




89




88







110-27




280




79




80







110-28




280




74




73







110-29




280




91




76







110-30




280




94




92







110-31




280




87




81







110-32




280




93




77







110-33




280




88




73







110-34




280




92




85







110-35




280




90




82







110-36




280




92




77







110-37




280




87




77







110-38




280




88




77







110-39




280




84




74







110-40




280




87




68







110-41




280




93




76







110-42




280




94




78







110-43




280




80




59







110-44




280




69




54







110-45




280




88




74







110-46




280




94




79







110-47




280




95




79







110-48




280




71




63







110-49




280




81




72







110-50




280




81




79







110-51




280




79




85







110-52




280




98




69







110-53




280




69




70







110-54




280




74




69







110-55




280




84




78







110-56




280




86




68







110-57




280




98




82







110-58




280




71




69







110-59




280




95




79







110-60




280




92




70







110-61




280




93




70







110-62




280




98




80







110-63




280




81




74







110-64




280




84




73







110-65




280




89




70







110-66




280




91




65







110-67




280




94




81







110-68




280




87




81







110-69




280




72




79







110-70




280




87




76







110-71




280




94




71







110-72




280




97




73















Compositions outperforming commercial standard Formulations C and J on both ABUTH and ECHCF in this test included 110-26, 110-27, 110-30, 110-34, 110-35, 110-51 and 110-57, all containing lecithin, butyl stearate and MON 0818.




Example 111




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 111a. Concentrate compositions 111-01 to 111-06 were prepared by process (x), using soybean lecithin (45% phospholipid, Avanti). Composition 111-07 was prepared by process (viii).














TABLE 111a













% w/w















Concentrate




Glyphosate





Butyl




Ethomeen






composition




g a.e./l




Lecithin




stearate




T/25


















111-01




200




6.0




2




6.0






111-02




200





3




6.0






111-03




200





1.5




9.0






111-04




200





3




9.0






111-05




200




6.0




1.5




9.0






111-06




200




6.0




1.5




3.0






111-07




200






9.0














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 16 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 15 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 111b.















TABLE 111b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF









Formulation B




150




29




22







250




41




29







350




53




32







450




68




35






Formulation J




150




43




32







250




76




43







350




86




47







450




94




66






111-01




150




67




33







250




85




40







350




96




71







450




97




59






111-02




150




65




36







250




81




52







350




97




68







450




98




62






111-03




150




67




40







250




85




77







350




94




77







450




97




63






111-04




150




69




38







250




86




58







350




93




84







450




98




62






111-05




150




73




40







250




83




53







350




93




75







450




96




61






111-06




150




45




30







250




71




38







350




91




45







450




89




39






111-07




150




59




39







250




83




44







350




95




63







450




95




70














Data for the 450 g a.e./ha glyphosate rate in this study are unreliable. Application error is suspected. The high levels of Ethomeen T/25 included in compositions of this Example tends to obscure the effects of lecithin and butyl stearate, but composition 111-05, for example, showed outstanding effectiveness.




Example 112




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 112a. Process (vii) was followed for concentrate composition 112-08 and process (x) for concentrate compositions 112-01 to 112-07 and 112-09, using soybean lecithin (45% phospholipid, Avanti).














TABLE 112a













% w/w















Concentrate




Glyphosate





Butyl







composition




g a.e./l




Lecithin




stearate




MON 0818









112-01




220




4.0





6.0






112-02




220




4.0




0.5




6.0






112-03




220




4.0




1.0




6.0






112-04




220




4.0




2.0




6.0






112-05




220




2.0




0.5




2.0






112-06




220




2.0




0.5




4.0






112-07




220




2.0




0.5




6.0






112-08




220





0.5




6.0






112-09




220




6.0




1.5




6.0














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 17 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B and C were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 112b.















TABLE 112b













Glyphosate rate




% Inhibition














Concentrate composition




g a.e./ha




ABUTH




ECHCF









Formulation B




150




40




59







250




68




61







350




90




91







450




93




94






Formulation C




150




74




78







250




93




90







350




97




96







450




100




94






112-01




150




79




85







250




93




98







350




96




97







450




97




95






112-02




150




71




87







250




93




96







350




96




94







450




98




94






112-03




150




87




99







250




94




100







350




99




97







450




97




94






112-04




150




89




100







250




94




99







350




97




98







450




98




95






112-05




150




73




100







250




90




100







350




95




98







450




96




94






112-06




150




80




99







250




94




96







350




95




100







450




99




98






112-07




150




88




83







250




94




92







350




96




92







450




100




90






112-08




150




81




91







250




92




96







350




97




89







450




99




92






112-09




150




90




96







250




93




93







350




95




95







450




94




98














Herbicidal effectiveness overall was very very high under the conditions of this study but a tendency can be discerned in compositions 112-01 to 112-04 for performance to improve as butyl stearate concentration was increased from zero to 2%.




Example 113




Aqueous spray compositions were prepared containing various tetraalkylammonium salts of glyphosate and excipient ingredients as shown in Table 113a. Process (iii) was followed for spray compositions 113-02 to 113-04, 113-06 to 113-08, 113-10 to 113-12 and 113-14 to 113-16, using soybean lecithin (45% phospholipid, Avanti). Compositions 113-01, 113-05, 113-09 and 113-13 are simple solutions of the tetraalkylammonium salts of glyphosate in water.














TABLE 113a









Spray




% w/w




Glyphosate






composition




Lecithin




salt











113-01





(Me)


4


N






113-02




0.10




(Me)


4


N






113-03




0.05




(Me)


4


N






113-04




0.02




(Me)


4


N






113-05





(Et)


4


N






113-06




0.10




(Et)


4


N






113-07




0.05




(Et)


4


N






113-08




0.02




(Et)


4


N






113-09





(Pr)


4


N






113-10




0.10




(Pr)


4


N






113-11




0.05




(Pr)


4


N






113-12




0.02




(Pr)


4


N






113-13





(BU)


4


N






113-14




0.10




(BU)


4


N






113-15




0.05




(BU)


4


N






113-16




0.02




(BU)


4


N














Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and 20 days after planting ECHCF, and evaluation of herbicidal inhibition was done 16 days after application.




Formulations B, C and J were applied as comparative treatments. In addition, Formulations B and C were tank-mixed with a pre-dispersed lecithin composition prepared from soybean lecithin (45% phospholipid, Avanti). Results, averaged for all replicates of each treatment, are shown in Table 113b.
















TABLE 113b













Glyphosate rate




% Inhibition

















Spray composition




g a.e./ha




ABUTH




ECHCF











Formulation B




200




23




34








400




43




38








600




69




54








800




75




41







Formulation B +




200




 7




15







lecithin 0.1% w/v




400




31




36








600




58




37







Formulation B +




200




10




17







lecithin 0.05% w/v




400




34




40








600




61




47







Formulation B +




200




11




17







lecithin 0.025% w/v




400




27




39








600




63




39







Formulation C




200




38




62








400




90




91








600




96




100 








800




100 




99







Formulation C +




200




36




55







lecithin 0.1% w/v




400




81




93








600




100 




95







Formulation C +




200




35




53







lecithin 0.05% w/v




400




79




90








600




91




99







Formulation C +




200




32




55







lecithin 0.025% w/v




400




77




88








600




96




100 







Formulation J




200




40




34








400




83




78








600




87




96








800




100 




95







113-01




200




27




34








400




74




52








600




84




46







113-02




200




39




37








400




73




64








600




89




68







113-03




200




24




35








400




73




59








600




88




75







113-04




200




29




43








400




71




59








600




82




90







113-05




200




51




43








400




79




48








600




98




49







113-06




200




58




47








400




84




81








600




86




97







113-07




200




69




41








400




83




84








600




90




94







113-08




200




55




48








400




79




79








600




93




92







113-09




200




73




60








400




96




58








600




98




73







113-10




200




69




75








400




94




94








600




99




91







113-11




200




72




62








400




94




98








600




100 




99







113-12




200




76




65








400




97




79








600




100 




100 







113-13




200




85




64








400




97




58








600




99




65







113-14




200




83




87








400




99




84








600




99




98







113-15




200




87




66








400




94




96








600




100 




100 







113-16




200




91




87








400




97




91








600




100 




94















Addition of lecithin to composition B (glyphosate IPA salt) did not provide significant enhancement of herbicidal effectiveness. However, when lecithin was added to tetraalkylammonium salts of glyphosate. significant improvements were obtained. In some cases adding a very low amount of lecithin (0.2%) gave better results than adding a larger amount (0.1 %). Outstanding effectiveness. for example, was obtained with composition 113-16, containing the tetrabutylammonium salt of glyphosate and 0.02% lecithin.




Example 114




Aqueous concentrate compositions were prepared containing glyphosate IPA salt and excipient ingredients as shown in Table 114a. Process (v) was followed for all concentrate compositions, using soybean lecithin (45% phospholipid, Avanti).

















TABLE 114a













Concentrate




Glyphosate




% w/w

















composition




g a.e./l




Lecithin




Benzalkonium Cl











114-01




363




8.1




5.4







114-02




363




8.1




4.1







114-03




363




8.1




3.0







114-04




363




8.1




2.1







114-05




372




8.3




2.5







114-06




363




6.8




4.0







114-07




362




6.8




2.9







114-08




355




3.5




10.0







114-09




354




3.0




13.3







114-10




352




2.5




16.7







114-11




352




2.0




20.0







114-12




295




5.0




10.0







114-13




295




4.5




13.3







114-14




294




4.0




16.7







114-15




294




3.5




20.0







114-16




292




3.0




23.3















Velvetleaf (


Abutilon theophrasti


, ABUTH) and Japanese millet (


Echinochloa crus


-


galli


, ECHCF) plants were grown and treated by the standard procedures given above. Applications of spray compositions were made 18 days after planting ABUTH and ECHCF, and evaluation of herbicidal inhibition was done 18 days after application.




Formulations B and J were applied as comparative treatments. Results, averaged for all replicates of each treatment, are shown in Table 114b.
















TABLE 114b













Glyphosate rate




% Inhibition















Concentrate composition




g a.e./ha




ABUTH




ECHCF









Formulation B




150




52




27







250




72




40







350




87




60







450




88




77






Formulation J




150




82




90







250




92




99







350




99




99







450




100 




100 






114-01




150




78




97







250




87




99







350




98




99







450




99




100 






114-02




150




68




83







250




73




99







350




96




99







450




98




99






114-03




150




65




53







250




77




92







350




93




99







450




98




100 






114-04




150




62




76







250




83




88







350




96




98







450




95




99






114-05




150




68




57







250




90




88







350




95




98







450




98




99






114-06




150




72




57







250




83




98







350




93




98







450




98




100 






114-07




150




77




69







250




85




85







350




97




98







450




98




99






114-08




150




80




85







250




93




99







350




99




100 







450




100 




100 






114-09




150




88




88







250




95




99







350




100 




99







450




100 




100 






114-10




150




99




97







250




97




100 







350




100 




100 







450




99




99






114-11




150




98




92







250




98




97







350




99




99







450




100 




100 






114-12




150




83




92







250




95




99







350




98




99







450




99




99






114-13




150




91




95







250




94




97







350




99




100 







450




99




100 






114-14




150




93




96







250




90




97







350




98




99







450




99




98






114-15




150




90




97







250




99




97







350




100 




100 







450




99




99






114-16




150




92




94







250




98




100 







350




99




100 







450




100 




99














Overall herbicidal effectiveness in this study was extremely high and enhancements over commercial standard Formulation J are therefore difficult to discern. However. particularly outstanding performance was obtained with compositions 114-10, 114-11 and 114-13 to 114-16 containing lecithin and benzalkonium chloride.




The preceding description of specific embodiments of the present invention is not intended to be a complete list of every possible embodiment of the invention. Persons skilled in this field will recognize that modifications can be made to the specific embodiments described here that would be within the scope of the present invention.



Claims
  • 1. A method of applying glyphosate or a herbicidal derivative thereof to a plant, comprising the steps of(a) contacting foliage of the plant with a biologically effective amount of glyphosate or a herbicidal derivative thereof, and (b) contacting the same foliage with an aqueous composition comprising an excipient substance that is amphiphilic, said aqueous composition being selected such that, upon evaporation of water from said aqueous composition, anisotropic aggregates are formed in or on a wax layer; wherein the weight/weight ratio of said excipient substance to the glyphosate or a herbicidal derivative thereof is between about 1:3 and about 1:100; and wherein step (b) occurs simultaneously with or within about 96 hours before or after step (a).
  • 2. The method of claim 1 wherein said excipient substance is an alkylether surfactant or mixture of such surfactants having the formulaR12—O—(CH2CH2O)n(CH(CH3)CH2O)m—R13 wherein R12 is an alkyl or alkenyl group having about 16 to about 22 carbon atoms, n is an average number of about 10 to about 100, m is an average number of 0 to about 5 and R13 is hydrogen or C1-4 alkyl.
  • 3. The method of claim 2 wherein, in the formula for the excipient substance, m is 0 and R13 is hydrogen.
  • 4. The method of claim 3 wherein, in the formula for the excipient substance, n is about 20 to about 40.
  • 5. The method of claim 1 wherein step (b) occurs simultaneously with step (a).
  • 6. The method of claim 5 wherein the glyphosate or a herbicidal derivative thereof is contained within said aqueous composition.
  • 7. The method of claim 5 wherein said glyphosate is contained within said aqueous composition.
  • 8. The method of claim 1 wherein the glyphosate or a herbicidal derivative thereof is a salt of glyphosate.
  • 9. The method of claim 8 wherein the salt of glyphosate is selected from the group consisting of sodium, potassium, ammonium, mono-, di-, tri- and tetra-C1-4-alkylammonium, mono-, di- and tri-C1-4-alkanolammonium, mono-, di- and tri-C1-4-alkylsulfonium and sulfoxonium salts.
  • 10. The method of claim 8 wherein the salt of glyphosate is the ammonium, monoisopropylammonium or trimethylsulfonium salt.
  • 11. An aqueous concentrate comprising(a) glyphosate or a herbicidal derivative thereof, and (b) an excipient substance that is amphiphilic; wherein the weight/weight ratio of said excipient substance to the glyphosate or herbicidal derivative thereof is between about 1:3 and about 1:100, and wherein, upon dilution of the concentrate with water to form a dilute composition, application of the dilute composition to foliage of a plant, and evaporation of water from the dilute composition, anisotropic aggregates are formed in or on a wax layer.
  • 12. The concentrate of claim 11, wherein said excipient substance is an alkylether surfactant or mixture of such surfactants having the formulaR12—O—(CH2CH2O)n(CH(CH3)CH2O)m—R13 wherein R12 is an alkyl or alkenyl group having about 16 to about 22 carbon atoms, n is an average number of about 10 to about 100, m is an average number of 0 to about 5 and R13 is hydrogen or C1-4 alkyl.
  • 13. The concentrate of claim 12 wherein, in the formula for the excipient substance, m is 0 and R13 is hydrogen.
  • 14. The concentrate of claim 12 wherein, in the formula for the excipient substance, n is from about 20 to about 40.
  • 15. The concentrate of claim 11 wherein the glyphosate or herbicidal derivative thereof is a salt of glyphosate.
  • 16. The concentrate of claim 15 wherein the salt of glyphosate is selected from the group consisting of sodium, potassium, ammonium, mono-, di-, tri- and tetra-C1-4-alkylammonium, mono-, di- and tri-C1-4-alkanolammonium, mono-, di- and tri-C1-4-alkylsulfonium and sulfoxonium salts.
  • 17. The concentrate of claim 15 wherein the salt of glyphosate is the ammonium, monoisopropylammonium or trimethylsulfonium salt.
  • 18. A plant treatment method comprising contacting foliage of a plant with a biologically effective amount of the concentrate of claim 11, or an application mixture formed by diluting said concentrate.
  • 19. The concentrate of claim 11 wherein said glyphosate is an alkanolamine glyphosate, ammonium glyphosate, potassium glyphosate, or a mixture thereof.
  • 20. The concentrate of claim 11 wherein said glyphosate comprises 15 to 90 percent by weight of the concentrate.
  • 21. The concentrate of claim 20 wherein said glyphosate comprises 30 to 90 percent by weight of the concentrate.
  • 22. The concentrate of claim 20 wherein said glyphosate comprises 15 to 60 percent by weight of the concentrate.
  • 23. The concentrate of claim 11 wherein the concentration of said glyphosate is at least 30% a.e.
  • 24. The concentrate of claim 11 wherein the concentration of said glyphosate is at least 326 grams glyphosate a.e. per liter.
  • 25. The concentrate of claim 24 wherein the concentration of said glyphosate is from 326 to 492 grams glyphosate a.e. per liter.
  • 26. The concentrate of claim 24 wherein the concentration of said glyphosate is at least 348 grams glyphosate a.e. per liter.
  • 27. The concentrate of claim 26 wherein the concentration of said glyphosate is from 348 to 488 grams glyphosate a.e. per liter.
  • 28. The concentrate of claim 26 wherein the concentration of said glyphosate is at least 360 grams glyphosate a.e. per liter.
  • 29. The concentrate of claim 28 wherein the concentration of said glyphosate is at least 400 grams glyphosate a.e. per liter.
  • 30. The concentrate of claim 11 wherein the anisotropic aggregates comprising said amphiphilic excipient are formed on or in the foliage of said plant irrespective of the presence or absence of another amphiphilic substance.
  • 31. The concentrate of claim 11 wherein at least 50% by weight of the amphiphilic excipient is present in said concentrate in the form of complex aggregates that are not simple micelles.
  • 32. The concentrate of claim 31 wherein said aggregates have an average diameter of at least about 20 nm.
  • 33. The concentrate of claim 11 comprising vesicles or liposomes comprising said amphiphilic excipient.
  • 34. The concentrate of claim 11 wherein said amphiphilic excipient comprises an amphiphilic substance comprising a compound having a hydrophilic headgroup and a hydrophobic tail, said amphiphilic compound having a critical packing diameter greater than about ⅓ where the critical packing diameter (“P”) is a dimensionless number determined by the algorithm:P=V/lA where V is the volume of the hydrophobic tail of the amphiphilic molecule, l is the effective length of the hydrophobic tail, and A is the area occupied by the hydrophilic headgroup of the molecule.
  • 35. The concentrate of claim 11 wherein, upon application of said dilute composition to the foliage of the plant, said anisotropic aggregates create or enlarge hydrophilic channels through the epicuticular wax of the plant cuticle, said channels being capable of accommodating the mass transfer of glyphosate into the plant.
  • 36. The concentrate of claim 11 wherein said amphiphilic excipient comprises a cationic headgroup which is effective to enhance initial adhesion of said dilute composition to the surface of foliage to which the dilute composition is applied, and is effective to attract water molecules and thereby enlarge said hydrophilic channels to provide an improved pathway of entry for glyphosate into said foliage.
  • 37. An aqueous concentrate comprising(a) potassium glyphosate, and (b) an excipient substance that is amphiphilic; wherein the weight/weight ratio of said excipient substance to the glyphosate or herbicidal derivative thereof is between about 1:3 and about 1:100, and wherein, upon dilution of the concentrate with water to form a dilute composition, application of the dilute composition to foliage of a plant, and evaporation of water from the dilute composition, anisotropic aggregates are formed in or on a wax layer.
  • 38. The concentrate of claim 37 wherein said glyphosate comprises 15 to 90 percent by weight of the concentrate.
  • 39. The concentrate of claim 38 wherein said glyphosate comprises 30 to 90 percent by weight of the concentrate.
  • 40. The concentrate of claim 39 wherein said glyphosate comprises 15 to 60 percent by weight of the concentrate.
  • 41. The concentrate of claim 37 wherein the concentration of said glyphosate is at least 30% a.e.
  • 42. The concentrate of claim 37 wherein the concentration of said glyphosate is at least 326 grams glyphosate a.e. per liter.
  • 43. The concentrate of claim 42 wherein the concentration of said glyphosate is from 326 to 492 grams glyphosate a.e. per liter.
  • 44. The concentrate of claim 42 wherein the concentration of said glyphosate is at least 348 grams glyphosate a.e. per liter.
  • 45. The concentrate of claim 44 wherein the concentration of said glyphosate is from 348 to 488 grams glyphosate a.e. per liter.
  • 46. The concentrate of claim 44 wherein the concentration of said glyphosate is at least 360 grams glyphosate a.e. per liter.
  • 47. The concentrate of claim 46 wherein the concentration of said glyphosate is at least 400 grams glyphosate a.e. per liter.
  • 48. The concentrate of claim 37 wherein the anisotropic aggregates comprising said amphiphilic excipient are formed on or in the foliage of said plant irrespective of the presence or absence of another amphiphilic substance.
  • 49. The concentrate of claim 37 wherein at least 50% by weight of the amphiphilic excipient is present in said concentrate in the form of complex aggregates that are not simple micelles.
  • 50. The concentrate of claim 49 wherein said aggregates have an average diameter of at least about 20 nm.
  • 51. The concentrate of claim 37 comprising vesicles or liposomes comprising said amphiphilic excipient.
  • 52. The concentrate of claim 37 wherein said amphiphilic excipient comprises an amphiphilic substance comprising a compound having a hydrophilic headgroup and a hydrophobic tail, said amphiphilic compound having a critical packing diameter greater than about ⅓ where the critical packing diameter (“P”) is a dimensionless number determined by the algorithm:P=V/lA where V is the volume of the hydrophobic tail of the amphiphilic molecule, l is the effective length of the hydrophobic tail, and A is the area occupied by the hydrophilic headgroup of the molecule.
  • 53. The concentrate of claim 37 wherein, upon application of said dilute composition to the foliage of the plant, said anisotropic aggregates create or enlarge hydrophilic channels through the epicuticular wax of the plant cuticle, said channels being capable of accommodating the mass transfer of glyphosate into the plant.
  • 54. The concentrate of claim 37 wherein said amphiphilic excipient comprises a cationic headgroup which is effective to enhance initial adhesion of said dilute composition to the surface of foliage to which the dilute composition is applied, and is effective to attract water molecules and thereby enlarge said hydrophilic channels to provide an improved pathway of entry for glyphosate into said foliage.
  • 55. An aqueous concentrate comprising(a) glyphosate or a herbicidal derivative thereof, and (b) an excipient substance that is amphiphilic; wherein the weight/weight ratio of said excipient substance to the glyphosate or herbicidal derivative thereof is between about 1:3 and about 1:100, and wherein, upon dilution of the concentrate with water to form a dilute composition, application of the dilute composition to foliage of a plant, and evaporation of water from the dilute composition, liquid crystals are formed in or on a wax layer.
  • 56. The concentrate of claim 55 wherein said glyphosate is an alkanolamine glyphosate, ammonium glyphosate, potassium glyphosate, or a mixture thereof.
  • 57. The concentrate of claim 55 wherein said glyphosate comprises 15 to 90 percent by weight of the concentrate.
  • 58. The concentrate of claim 57 wherein said glyphosate comprises 30 to 90 percent by weight of the concentrate.
  • 59. The concentrate of claim 57 wherein said glyphosate comprises 15 to 60 percent by weight of the concentrate.
  • 60. The concentrate of claim 55 wherein the concentration of said glyphosate is at least 30% a.e.
  • 61. The concentrate of claim 55 wherein the concentration of said glyphosate is at least 326 grams glyphosate a.e. per liter.
  • 62. The concentrate of claim 61 wherein the concentration of said glyphosate is from 326 to 492 grams glyphosate a.e. per liter.
  • 63. The concentrate of claim 61 wherein the concentration of said glyphosate is at least 348 grams glyphosate a.e. per liter.
  • 64. The concentrate of claim 63 wherein the concentration of said glyphosate is from 348 to 488 grams glyphosate a.e. per liter.
  • 65. The concentrate of claim 63 wherein the concentration of said glyphosate is at least 360 grams glyphosate a.e. per liter.
  • 66. The concentrate of claim 65 wherein the concentration of said glyphosate is at least 400 grams glyphosate a.e. per liter.
  • 67. The concentrate of claim 55 wherein said liquid crystals comprising said excipient substance form transcuticular hydrophilic channels through the cuticle of said plant.
  • 68. The concentrate of claim 67 wherein the liquid crystals which form said transcuticular hydrophilic channels are present in the form of a multilamellar structure.
  • 69. The concentrate of claim 68 wherein the liquid crystals which form said transcuticular hydrophilic channels are present in the form of a lyotropic mesophase.
  • 70. The concentrate of claim 69 wherein the lyotropic mesophase is in the form of a hexagonal phase.
  • 71. The concentrate of claim 69 wherein the lyotropic mesophase is in the form of a lamellar phase.
  • 72. The concentrate of claim 69 wherein the lyotropic mesophase is in the form of a reversed hexagonal phase.
  • 73. The concentrate of claim 55 wherein the liquid crystals comprising said amphiphilic excipient are formed on or in the foliage of said plant irrespective of the presence or absence of another amphiphilic substance.
  • 74. The concentrate of claim 55 wherein said liquid crystals comprise a stratified array of amphiphilic excipient molecules, hydrophilic moieties of amphiphilic excipient molecules in one stratum of said array being oriented toward hydrophilic moieties of amphiphilic excipient molecules in a second stratum of said array.
  • 75. The concentrate of claim 74 wherein an aqueous liquid may migrate within said liquid crystal in a hydrophilic region within which said hydrophilic moieties of said one stratum and said second stratum are disposed.
  • 76. The concentrate of claim 74 wherein hydrophobic moieties of said amphiphilic excipient molecules of said one stratum are in contact with a hydrophobic surface on said foliage or within a cuticle of said plant.
  • 77. The concentrate of claim 75 wherein said hydrophilic region comprises a channel for penetration of glyphosate into cuticles of said plant.
  • 78. The concentrate of claim 75 wherein said hydrophilic region comprises a channel for translocation of glyphosate within said plant.
  • 79. The concentrate of claim 74 wherein each of said strata of said array comprises a lamella of amphiphilic excipient molecules, the hydrophilic moieties of amphiphilic excipient molecules in the lamella of said one stratum of said array being oriented toward the hydrophilic moieties of amphiphilic excipient molecules in the lamella of said second stratum of said array.
  • 80. The concentrate of claim 74 wherein each of said one and said second strata of said array comprises a cylindrical configuration of amphiphilic excipient molecules, the hydrophilic moieties of amphiphilic excipient molecules in the cylindrical configuration of said one stratum of said array being oriented toward the hydrophilic moieties of amphiphilic excipient molecules in the cylindrical configuration of said second stratum of said array.
  • 81. The concentrate of claim 55 wherein said liquid crystals comprise a bilayer structure.
  • 82. The concentrate of claim 55 which is substantially devoid of liquid crystals comprising said amphiphilic excipient but having a composition such that, upon application to a plant of the formulation, liquid crystals comprising said amphiphilic excipient are formed in an aqueous layer on the surface of foliage of the plant.
  • 83. The concentrate of claims 55 having a composition such that, upon application to a plant of the dilute composition, a phase separation occurs resulting in the presence in said foliage of a phase comprising said liquid crystals.
  • 84. The concentrate of claim 55 wherein at least 50% by weight of the amphiphilic excipient is present in said concentrate in the form of complex aggregates that are not simple micelles.
  • 85. The concentrate of claim 55 comprising vesicles or liposomes comprising said amphiphilic excipient.
  • 86. The concentrate of claim 55 wherein said amphiphilic excipient comprises an amphiphilic substance comprising a compound having a hydrophilic headgroup and a hydrophobic tail, said amphiphilic compound having a critical packing diameter greater than about ⅓ where the critical packing diameter (“P”) is a dimensionless number determined by the algorithm:P=V/lA where V is the volume of the hydrophobic tail of the amphiphilic molecule, l is the effective length of the hydrophobic tail, and A is the area occupied by the hydrophilic headgroup of the molecule.
  • 87. The concentrate of claim 55 wherein said amphiphilic excipient comprises a cationic headgroup which is effective to enhance initial adhesion of said dilute composition to the surface of foliage to which the dilute composition is applied, and is effective to attract water molecules and thereby enlarge said hydrophilic channels to provide an improved pathway of entry for glyphosate into said foliage.
  • 88. An aqueous concentrate comprising(a) potassium glyphosate, and (b) an excipient substance that is amphiphilic; wherein the weight/weight ratio of said excipient substance to the glyphosate or herbicidal derivative thereof is between about 1:3 and about 1:100, and wherein, upon dilution of the concentrate with water to form a dilute composition, application of the dilute composition to foliage of a plant, and evaporation of water from the dilute composition, liquid crystals are formed in or on a wax layer.
  • 89. The concentrate of claim 88 wherein said glyphosate comprises 15 to 90 percent by weight of the concentrate.
  • 90. The concentrate of claim 89 wherein said glyphosate comprises 30 to 90 percent by weight of the concentrate.
  • 91. The concentrate of claim 89 wherein said glyphosate comprises 15 to 60 percent by weight of the concentrate.
  • 92. The concentrate of claim 88 wherein the concentration of said glyphosate is at least 30% a.e.
  • 93. The concentrate of claim 88 wherein the concentration of said glyphosate is at least 326 grams glyphosate a.e. per liter.
  • 94. The concentrate of claim 93 wherein the concentration of said glyphosate is from 326 to 492 grams glyphosate a.e. per liter.
  • 95. The concentrate of claim 93 wherein the concentration of said glyphosate is at least 348 grams glyphosate a.e. per liter.
  • 96. The concentrate of claim 95 wherein the concentration of said glyphosate is from 348 to 488 grams glyphosate a.e. per liter.
  • 97. The concentrate of claim 95 wherein the concentration of said glyphosate is at least 360 grams glyphosate a.e. per liter.
  • 98. The concentrate of claim 97 wherein the concentration of said glyphosate is at least 400 grams glyphosate a.e. per liter.
  • 99. The concentrate of claim 88 wherein said liquid crystals comprising said excipient substance form transcuticular hydrophilic channels through the cuticle of said plant.
  • 100. The concentrate of claim 99 wherein the liquid crystals which form said transcuticular hydrophilic channels are present in the form of a multilamellar structure.
  • 101. The concentrate of claim 100 wherein the liquid crystals which form said transcuticular hydrophilic channels are present in the form of a lyotropic mesophase.
  • 102. The concentrate of claim 101 wherein the lyotropic mesophase is in the form of a hexagonal phase.
  • 103. The concentrate of claim 101 wherein the lyotropic mesophase is in the form of a lamellar phase.
  • 104. The concentrate of claim 101 wherein the lyotropic mesophase is in the form of a reversed hexagonal phase.
  • 105. The concentrate of claim 88 wherein the liquid crystals comprising said amphiphilic excipient are formed on or in the foliage of said plant irrespective of the presence or absence of another amphiphilic substance.
  • 106. The concentrate of claim 88 wherein said liquid crystals comprise a stratified array of amphiphilic excipient molecules, hydrophilic moieties of amphiphilic excipient molecules in one stratum of said array being oriented toward hydrophilic moieties of amphiphilic excipient molecules in a second stratum of said array.
  • 107. The concentrate of claim 106 wherein an aqueous liquid may migrate within said liquid crystal in a hydrophilic region within which said hydrophilic moieties of said one stratum and said second stratum are disposed.
  • 108. The concentrate of claim 106 wherein hydrophobic moieties of said amphiphilic excipient molecules of said one stratum are in contact with a hydrophobic surface on said foliage or within a cuticle of said plant.
  • 109. The concentrate of claim 107 wherein said hydrophilic region comprises a channel for penetration of glyphosate into cuticles of said plant.
  • 110. The concentrate of claim 107 wherein said hydrophilic region comprises a channel for translocation of glyphosate within said plant.
  • 111. The concentrate of claim 106 wherein each of said strata of said array comprises a lamella of amphiphilic excipient molecules, the hydrophilic moieties of amphiphilic excipient molecules in the lamella of said one stratum of said array being oriented toward the hydrophilic moieties of amphiphilic excipient molecules in the lamella of said second stratum of said array.
  • 112. The concentrate of claim 106 wherein each of said one and said second strata of said array comprises a cylindrical configuration of amphiphilic excipient molecules, the hydrophilic moieties of amphiphilic excipient molecules in the cylindrical configuration of said one stratum of said array being oriented toward the hydrophilic moieties of amphiphilic excipient molecules in the cylindrical configuration of said second stratum of said array.
  • 113. The concentrate of claim 88 wherein said liquid crystals comprise a bilayer structure.
  • 114. The concentrate of claim 88 which is substantially devoid of liquid crystals comprising said amphiphilic excipient but having a composition such that, upon application to a plant of the formulation, liquid crystals comprising said amphiphilic excipient are formed in an aqueous layer on the surface of foliage of the plant.
  • 115. The concentrate of claims 88 having a composition such that, upon application to a plant of the dilute composition, a phase separation occurs resulting in the presence in said foliage of a phase comprising said liquid crystals.
  • 116. The concentrate of claim 88 wherein at least 50% by weight of the amphiphilic excipient is present in said concentrate in the form of complex aggregates that are not simple micelles.
  • 117. A liquid concentrate comprising an aqueous mixture containing glyphosate or a herbicidal derivative thereof other than monoisopropylamine glyphosate in a concentration of at least 326 grams glyphosate a.e. per liter, and an amphiphilic excipient substance selected from the group consisting of:(i) a liposome-forming compound having a hydrophobic moiety comprising two saturated or unsaturated hydrocarbyl groups each having about 7 to about 21 carbon atoms; (ii) a liposome-forming material that comprises an amphiphilic compound having two hydrophobic moieties, each of which is a saturated alkyl or acyl chain having from about 8 to about 22 carbon atoms; (iii) a quaternary ammonium compound having a hydrophobic moiety which is a saturated alkyl or haloalkyl group having about 6 to about 22 carbon atoms; (iv) an alkylether having the formula (VI): R12O(CH2CH2O)n(CH(CH3)CH2O)mR13  (VI)  wherein R12 is an alkyl or alkenyl group having about 16 to about 22 carbon atoms, n is an average number of about 10 to about 100, m is an average number of 0 to about 5 and R13 is hydrogen or C1-4 alkyl; and (v) a fatty alcohol ethoxylate; wherein the weight/weight ratio of said amphiphilic excipient substance to the glyphosate is between about 1:3 and about 1:100.
  • 118. A concentrate as set forth in claim 117 wherein the amphiphilic excipient substance comprises the liposome forming compound (i) of the formulae:N+(CH2R1)(CH2R2)(R3)(R4)Z−,  (I) N+(R5)(R6)(R7)CH2CH(OCH2R1)CH2(OCH2R2)Z−,  (II) N+(R5)(R6)(R7)CH2CH(OCOR1)CH2(OCOR2)Z−, or  (III) N+(R5)(R6)(R7)CH2CH2—PO4−—CH2CH(OCOR1)CH2(OCOR2)  (IV) wherein R1 and R2 are independently saturated or unsaturated hydrocarbyl groups having about 7 to about 21 carbon atoms, R3, R4, R5, R6 and R7 are independently hydrogen, C1-4 alkyl or C1-4 hydroxyalkyl, and Z is an anion.
  • 119. A concentrate as set forth in claim 117 wherein the amphiphilic excipient substance comprises the quaternary ammonium compound (iii) of the formula:R8—Wa—X—Yb—(CH2)n—N+(R9)(R10)(R11)T−  (V) wherein R8 represents a hydrophobic moiety which is a hydrocarbyl or haloalkyl group having from about 6 to about 22 carbon atoms, W and Y are independently O or NH, a and b are independently 0 or 1 but at least one of a and b is 1, X is CO, SO or SO2, n is 2 to 4, R9, R10 and R11 are independently C1-4 alkyl, and T is an anion.
  • 120. A concentrate as set forth in claim 117 further comprising a second excipient substance selected from the group consisting of:(i) a compound having one hydrophobic moiety which is a hydrocarbyl or haloalkyl group having about 6 to about 22 carbon atoms; (ii) a compound having a plurality of hydrophobic moieties, each of said hydrophobic moieties being a hydrocarbyl or haloalkyl group having more than 2 carbon atoms, said plurality of hydrophobic moieties having a total of about 12 to about 40 carbon atoms; (iii) a compound or mixture of compounds of formula (VII): R14—CO—A—R15  (VII)  wherein R14 is a hydrocarbyl group having about 5 to about 21 carbon atoms, R15 is a hydrocarbyl group having 1 to about 14 carbon atoms, the total number of carbon atoms in R14 and R15 is about 11 to about 27, and A is O or NH; and (iv) a quaternary ammonium compound of formula (VIII): N+(R16)(R17)(R18)(R19)Q−  (VIII)  wherein R16, R17, R18 and R19 are independently C3-6 alkyl groups and Q is an anion.
  • 121. A concentrate as set forth in claim 117 wherein the amphiphilic excipient substance comprises dioleoylphosphatidylcholine (DOPC), dioleoylphosphatidylethanolamine (DOPE), dioleoylphosphatidylglycerol (DOPG), distearyldimethylammonium chloride (DODAC), distearyldimethylammonium bromide (DODAB), N-(2,3-di-(9-(Z)-octadecenyloxy))-prop-1-yl-N,N,N-trimethylammonium chloride (DOTMA), dimyristooxypropyl dimethylhydroxyethylammonium bromide (DMRIE), dioleoyloxy-3-(dimethylammonio)propane (DODAP), or 1,2-bis(oleoyloxy)-3-(trimethylammonio)propane (DOTAP).
  • 122. A concentrate as set forth in claim 117 wherein the amphiphilic excipient substance comprises a lipid selected from the group consisting of a phospholipid, ceramide, sphingolipid, dialkyl surfactant, and polymeric surfactant.
  • 123. A concentrate as set forth in claim 122 wherein the amphiphilic excipient substance comprises a lecithin.
  • 124. A concentrate as set forth in claim 117 wherein the amphiphilic excipient comprises a phosphatidylcholine, hydrogenated phosphatidylcholine, phosphatidylinositol, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylethanolamine, N-acyl phosphatidylethanolamine, a saturated alkanoyl phospholipid, di-C8-22-alkanoylphosphatidylcholine, di-C8-22-alkanoylphosphatidylethanolamine, C9-11 alkylpolyglycoside, alkyl polyglucoside, alkylaryl ethoxylate phosphate ester, alcohol ethoxylate phosphate ester, potassium fluorinated alkyl carboxylate, fluorinated alkyl quaternary ammonium chloride, fluorinated alkyl quaternary ammonium iodide, fluorinated alkanol EO, fluorinated alkyl ester, ammonium C9-10 perfluoroalkyl sulfonate, C1-4 alkyl ester of a C12-18 fatty acid, alkylamine 2EO, alkylamine 5EO, alkylamine 7.5EO, alkylamine 10EO, alkylamine 15EO, potassium dicarboxylate, or alkyl acetate.
  • 125. A concentrate as set forth in claim 117 wherein the amphiphilic excipient substance comprises distearoyl phosphatidylcholine, dipalmitoyl phosphatidylcholine, egg yolk lecithin, soybean lecithin, dipalmitoyl ester of phosphatidylcholine, distearoyl ester of phosphatidylcholine, 3-(((heptadecafluorooctyl)sulfonyl)amino)-N,N,N-trimethyl-1-propaminium iodide, 3-(((heptadecafluorooctyl)sulfonyl)amino)-N,N,N-trimethyl-1-propaminium chloride, butyl stearate, cetyltrimethylammonium bromide, benzalkonium chloride, sodium diisopropyl naphthalene sulfonate, sodium dioctyl sulfosuccinate, isolauryl 10EO thioether, lauramide 5EO, palmitamine oxide, lauramine oxide, dipropyleneglycol monomethyl ether, cyclocarboxypropyl oleic acid, propylene glycol n-butyl ether, tripropylene glycol n-butyl ether, glyceryl oleate, PEG-12 laurate, oleic diethanolamide, nonylphenol 10EO phosphate, cocoamine 2EO, cocoamine 15EO, tallowamine 2EO, tallowamine 15EO, methyltallowammonium chloride 10EO, C11, oxo alcohol 3EO, C11 oxo alcohol 11EO, nonylphenol 4EO, nonylphenol 6EO, nonylphenol 30EO, tallowamine 15EO, PEG-40 stearate, PEG-100 stearate, C11 linear alcohol 12EO, C11 linear alcohol 7EO, C11 linear alcohol 9EO, C12-15 linear alcohol 12EO, C12-15 linear alcohol 20EO, C12-15 linear a 3EO C12-15 linear alcohol 7EO, C12-15 linear alcohol 9EO, C14-15 linear alcohol 13EO, C9-11 linear alcohol 2.5EO, C12-15 linear alcohol ethoxycarboxylate 11EO, amine dodecylbenezene sulfonate, coco diethanolamide, sodium decyl sulfate, sodium sulfonated lignin, heptamethyltrisiloxane EO, heptamethyltrisiloxane 7EO methyl ether, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sodium lauryl EO sulfate, sodium lauryl sulfate, nonylphenol EO phosphate, tetramethyldecyne diol, tetramethyldecyne diol 10EO, C15 branched secondary alcohol 15EO, C15 branched secondary alcohol 20EO, C15 branched secondary alcohol 30EO, C15 branched secondary alcohol 40EO, decyl EO phosphate (free acid), sorbitan monolaurate 20EO, sorbitan monopalmitate 20EO, sorbitan monooleate 20EO, sorbitan trioleate 20EO, cocobetaine, 21PO-7EO-21PO block copolymer, 128EO-54PO-128EO block copolymer, 98EO-67PO-98EO block copolymer, 75EO-30PO-75EO block copolymer, 11EO-16PO-11EO block copolymer, 7EO-21PO-7EO block copolymer, 6EO-39PO-6EO block copolymer, 27EO-39PO-27EO block copolymer, C8 F17SO2NH(CH2)3N+(CH3)3I−, C8F17SO2NH(CH2)3N+(CH3)3Cl−, laureth-23, Ceteth-10, Ceteth-20, Steareth-10, Steareth-20, Steareth-30, Steareth-100, Ceteareth-15, Ceteareth-20, Ceteareth-27, Ceteareth-55, Oleth-2, Oleth-10, or Oleth-20.
  • 126. A concentrate as set forth in claim 117 wherein the amphiphilic excipient substance comprises ceteareth-15, C12-15 linear alcohol 12EO, or sodium lauryl sulfate.
  • 127. A concentrate as set forth in claim 117 wherein the amphiphilic excipient substance comprises ceteareth-20, steareth-10, oleth-10, oleth-20, laureth-23, or lecithin.
  • 128. A concentrate as set forth in claim 117 wherein the amphiphilic excipient substance comprises ceteareth-27 or steareth-20.
  • 129. A concentrate as set forth in claim 117 wherein the amphiphilic excipient substance comprises cocoamine 2EO, cocoamine 15EO, tallowamine 2EO, tallowamine 15EO, methyltallowammonium chloride 10EO, egg yolk lecithin, soybean lecithin, cetyltrimethylammonium bromide, C11 oxo alcohol 3EO, C11 oxo alcohol 11EO, nonylphenol 4EO, nonylphenol 6EO, nonylphenol 30EO, tallowamine 15EO, C11 linear alcohol 12EO, C11 linear alcohol 7EO, C11 linear alcohol 9EO, C12-15 linear alcohol 12EO, C12-15 linear alcohol 20EO, C12-15 linear alcohol 3EO, C12-15 linear alcohol 7EO, C12-15 linear alcohol 9EO, C14-15 linear alcohol 13EO, C9-11 linear alcohol 2.5EO, sodium decyl sulfate, sodium lauryl EO sulfate, C15 branched secondary alcohol 15EO, C15 branched secondary alcohol 20EO, C15 branched secondary alcohol 30EO, C15 branched secondary alcohol 40EO, Ceteth-10, Ceteth-20, Steareth-30, Steareth-100, Ceteareth-55, or Oleth-2.
  • 130. The concentrate of claim 11, wherein said excipient substance is a liposome-forming material that comprises an amphiphilic compound or mixture of such compounds having two hydrophobic moieties, each of which is a saturated alkyl or acyl chain having from about 8 to about 22 carbon atoms; wherein said amphiphilic compound or mixture of such compounds having said two hydrophobic moieties constitutes from about 40 to 100 percent by weight of all amphiphilic compounds having two hydrophobic moieties present in said liposome-forming material.
  • 131. The concentrate of claim 130, wherein the liposome-forming material has a hydrophilic head group comprising a cationic group.
  • 132. The concentrate of claim 131, wherein the cationic group is an amine or ammonium group.
  • 133. The concentrate of claim 37, wherein said excipient substance is a liposome-forming material that comprises an amphiphilic compound or mixture of such compounds having two hydrophobic moieties, each of which is a saturated alkyl or acyl chain having from about 8 to about 22 carbon atoms; wherein said amphiphilic compound or mixture of such compounds having said two hydrophobic moieties constitutes from about 40 to 100 percent by weight of all amphiphilic compounds having two hydrophobic moieties present in said liposome-forming material.
  • 134. The concentrate of claim 133, wherein the liposome-forming material has a hydrophilic head group comprising a cationic group.
  • 135. The concentrate of claim 134, wherein the cationic group is an amine or ammonium group.
  • 136. The concentrate of claim 55, wherein said excipient substance is a liposome-forming material that comprises an amphiphilic compound or mixture of such compounds having two hydrophobic moieties, each of which is a saturated alkyl or acyl chain having from about 8 to about 22 carbon atoms; wherein said amphiphilic compound or mixture of such compounds having said two hydrophobic moieties constitutes from about 40 to 100 percent by weight of all amphiphilic compounds having two hydrophobic moieties present in said liposome-forming material.
  • 137. The concentrate of claim 136, wherein the liposome-forming material has a hydrophilic head group comprising a cationic group.
  • 138. The concentrate of claim 137, wherein the cationic group is an amine or ammonium group.
  • 139. The concentrate of claim 88, wherein said excipient substance is a liposome-forming material that comprises an amphiphilic compound or mixture of such compounds having two hydrophobic moieties, each of which is a saturated alkyl or acyl chain having from about 8 to about 22 carbon atoms; wherein said amphiphilic compound or mixture of such compounds having said two hydrophobic moieties constitutes from about 40 to 100 percent by weight of all amphiphilic compounds having two hydrophobic moieties present in said liposome-forming material.
  • 140. The concentrate of claim 139, wherein the liposome-forming material has a hydrophilic head group comprising a cationic group.
  • 141. The concentrate of claim 140, wherein the cationic group is an amine or ammonium group.
Parent Case Info

This application is a continuation of application Ser. No. 08/958,149 filed Oct. 24, 1997, now U.S. Pat. No. 6,093,681, which the benefit of provisional application serial No. 60/029,317, filed Oct. 25, 1996; provisional application serial No. 60/034,887, filed Jan. 31, 1997; and provisional application serial No. 60/039,789, filed Mar. 4, 1997. Each of those provisional applications is incorporated here by reference.

US Referenced Citations (42)
Number Name Date Kind
3723512 Niederprum et al. Mar 1973 A
3888828 Grossmann et al. Jun 1975 A
3918952 Neumiller Nov 1975 A
4115313 Lyon et al. Sep 1978 A
4235871 Papahadjopoulos et al. Nov 1980 A
4311712 Evans et al. Jan 1982 A
4394149 Szoka et al. Jul 1983 A
4481026 Prisbylla Nov 1984 A
4506831 Ghyczy et al. Mar 1985 A
4567161 Posanski et al. Jan 1986 A
4576626 Bauer et al. Mar 1986 A
4681617 Ghyczy et al. Jul 1987 A
4722749 Lee Feb 1988 A
4822407 Esposito Apr 1989 A
4834908 Hazen et al. May 1989 A
4840659 Franz Jun 1989 A
4855090 Wallach Aug 1989 A
4874553 Hager et al. Oct 1989 A
4902333 Quimby Feb 1990 A
4944791 Schröder et al. Jul 1990 A
5037847 Sutter Aug 1991 A
5084087 Hazen et al. Jan 1992 A
5123950 Homma et al. Jun 1992 A
5131946 Franke et al. Jul 1992 A
5147444 Decor et al. Sep 1992 A
5180416 Katou et al. Jan 1993 A
5264213 Shibahara et al. Nov 1993 A
5308827 Sakamoto et al. May 1994 A
5310724 Kondo et al. May 1994 A
5332573 Yamaguchi et al. Jul 1994 A
5332714 Albrecht et al. Jul 1994 A
5415877 Winston May 1995 A
5466458 Martin et al. Nov 1995 A
5466659 Keeney et al. Nov 1995 A
5468716 Winston Nov 1995 A
5476835 Johnson et al. Dec 1995 A
5482529 Ahlnas et al. Jan 1996 A
5512079 Jahnke et al. Apr 1996 A
5558806 Policello Sep 1996 A
5580567 Roberts Dec 1996 A
5693593 Arnold Dec 1997 A
5821195 Sandbrink et al. Oct 1998 A
Foreign Referenced Citations (103)
Number Date Country
9137382 Jun 1983 AU
6070294 Jul 1995 AU
2081254 Apr 1993 CA
2099631 Jan 1994 CA
32 26 498 Jan 1984 DE
32 47 050 Jun 1984 DE
4 318 673 Jan 1995 DE
0 019 384 Nov 1980 EP
0 068 293 Jan 1983 EP
0 068 294 Jan 1983 EP
0 068 295 Jan 1983 EP
0 082 437 Jun 1983 EP
0 095 071 Nov 1983 EP
0 099 029 Jan 1984 EP
0 124 351 Nov 1984 EP
0 146 238 Jun 1985 EP
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0 579 951 Jan 1994 EP
0 582 561 Feb 1994 EP
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0 648 413 Apr 1995 EP
0 664 954 Aug 1995 EP
0 729 700 Sep 1996 EP
1 337 467 Nov 1973 GB
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67 542 Apr 1995 HU
58-124703 Jul 1983 JP
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02-169546 Jun 1990 JP
02-172950 Jul 1990 JP
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WO 8704595 Aug 1987 WO
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WO 9741730 Nov 1997 WO
WO 9806259 Feb 1998 WO
834882 Feb 1984 ZA
893661 Jan 1990 ZA
Non-Patent Literature Citations (108)
Entry
Anderson & Panetta (1995). Fireweed response to boomspray applications of different herbicides and adjuvants. Plant Protection Quarterly 10(4), 152-153.
Anon. (no date). L1-700. Brochure of Agridyne, Pont-du-Casse, France.
Anon. (1993). 40 CFR § 180.1001, 435-458.
Anon. (1995). McCutcheon's vol. 1: Emulsifiers & Detergents. North American Edition, pp. 4, 8, 9, 42, 48, 149, 163, 164, 316.
Anon. (1996). The right tool for the right job? Adversiement by Loveland Industries, Inc. Farm Chemicals, Oct. 1996, p. 51.
Anon. (1997). Crop protection round-up: adjuvants. Farm Chemicals, Mar. 1997, 56-57.
Baker et al. (1983). Studies of plant cuticle and spray droplet interactions: a fresh approach. Pesticide Science 14, 645-658.
Balneaves (1992). A comparison of surfactants to aid control of gorse and scotch broom with herbicides. Plant Protection Quarterly 7(4), 174-177.
Bayer & Lumb (1973). Penetration and translocation of herbicides. In Van Valkenburg, ed.: Pesticide Formulations, 387-449. New York:Marcel Dekker.
Becher (1973). The emulsifier. In Van Valkenburg, ed.: Pesticide Formulations, 65-92. New York: Marcel Dekker.
Bhattacharya & Subramanian (1996). Synthesis, redox and electrochemical properties of new anthraquinone-attached micelle- and vesicle-forming cationic amphiphiles. Journal of the Chemical Society, Perkin Transactions 2, 2027-2034.
Boothroyd et al. (1993). Alopecurus myosuroides control using fenoxaprop ethyl dose adjustments, adjuvants and mixes. Proceedings, Brighton Crop Protection Conference, vol. 2, 601-606.
Bravais et al. (1993). Influence of triolein ane methyl, ethyl and propyl oleate on the deposit shape and the foliar penetration of phenmedipham and quizalofop-ethyl. Mededelingen Faculteit Landbouwwetenschappen Rijksuniversiteit Gent 58(3a), 803-807.
Bridges (1989). Adjuvant and pH effects on sethoxydim and clethodim activity on rhizome johnsongrass (Sorghum halepense). Weed Technology 3, 615-620.
Bridges et al. (1991). Effect of adjuvant on foliar absorption and activity of clethodim and polar degradation products of clethodim. Weed Science, 39, 543-547.
Bridges et al. (1992). Stability and activity of clethodim as influenced by pH, UV light and adjuvant. In Foy, ed.: Adjuvants for Agrochemicals, 215-223. Boca Raton: CRC Press.
Bruce et al. (1993). Absorption and activity of nicosulfuron and primisulfuron in quackgrass (Elytrigia repens), as affected by adjuvants. Weed Science 41, 218-224.
Coret & Chamel (1993). Influence of some nonionic surfactants on water sorption by isolated tomato fruit cuticles in relation to cuticular penetration of glyphosate. Pesticide Science 38, 27-32.
De Ruiter et al. (1988). Mode of action of a nonionic and a cationic surfactant in relation to glyphosate. In Cross & Scher, ed.: Pesticide Formulations, Innovations and Developments (ACS Symposium Series 371), 44-55.
De Villiers et al. (1996). Optimizing tralkoxydim efficacy with carrier water high in sodium bicarbonate. FRI Bulletin 193 (Proceedings, Fourth Intenational Symposium on Adjuvants for Agrochemicals, 1995), 207-210.
Eberlein et al. (1992). Hairy nightshade (Solanum sarrachoides) control in potatoes (Solanum tuberosum) with bentazon plus additives. Weed Technology 6, 85-90.
Farag & Palta (1989). Ultrastructure and surface morphology of cranberry (Vaccinium macrocarpon Ait.) with reference to Ethrel penetration. Acta Horticulturae 241, 378-384.
Florence (1994). Nonionic surfactant vesicles: preparation and characterization. In Gregoriadis, ed.: Liposome Technology, 2nd ed., vol. 1, pp. 157-176. Boca Raton: CRC Press.
Florence & Whitehill (1980). Some features of breakdown in water-in-oil-water multiple emulsions. Journal of Colloid and Interface Science 79, 243-256.
Foy (1996). Adjuvants—current trends and technology. Pesticide Formulation Adjuvant Technology (Formulations Forum 1994), 323-352, Boca Raton: CRC Press.
Foy & Witt (1993). Effects of methylated crop oils and other selected adjuvants on the herbicidal efficacy and selectivity of imazethapyr in soybeans. Pesticide Science 38, 260-262.
Froment & Cooper (1994). Evaluation of fenoxaprop ethyl alone and in mixtures against blackgrass (Alopecurus myosuroides) in winter wheat. Tests of Agrochemicals and Cultivars 15, 60-61.
Garr & Hanks (1996). Effects of adjuvants on velvetleaf control with chlorimuron and imazethapyr in soybenas. FRI Bulletin 193 (Proceedings, Fourth International Symposium on Adjuvants for Agrochemicals, 1995), 432-436.
Gaskin & Holloway (1992). Some physicochemical factors influencing foliar uptake enhancement of glyphosate-mono(isopropylammonium) by polyoxyethylene surfactants. Pesticide Science 34, 195-206.
Gauvrit & Cabanne (1993). Oils for weed control: uses and mode of action. Pesticide Science 37, 147-153.
Gauvrit et al. (1995). Influence of ester derivatives of oleic-sunflower seed oil on the foliar penetration of herbicides. Mededelingen Faculteit Landbouwwetenschappen Rijsuniversiteit Gent 60(2a), 183-189.
Gimesi (1986). Increasing the phytotoxicity of glyphosate by using subsidiary materials. Novenytermeles 35, 319-324. Abstract in English.
Glass, R.L. (1988). Entrapment of herbicides 14C-picloram and 14C-dicamba in phospholipid vesicles. Pesticide Biochemistry & Physiology 32, 93-96.
Hamilton (1993). Structure and general properties of mineral and vegetable oils used as spray adjuvants. Pesticide Science 37, 141-146.
Harker (1992). Effects of various adjuvants on sethoxydim activity. Weed Technology 6, 865-870.
Hart et al. (1992). Influence of adjuvants on the efficacy, absorption and spray retention of primisulfuron. Weed Techonology 6, 592-598.
Harvey (1989). A guide to agricultural spray adjuvants used in the United States, 1990-91 ed., p. 94. Fresno: Thomson Publications.
Hess (1985). Herbicide absorption and translocation and their relationship to plant tolerances and susceptibility. In Duke, ed.: Weed Physiology, vol. 2, 191-214. Boca Raton: CRC Press.
Hickey (1987). Methyl esters of fatty acids as pesticide formulation and application aids. ASTM Special Technical Publication 968, 67-74.
Israelachvili et al. (1976). Theory of self-assembly of hydrocarbon amphiphiles into micelles and bilayers. Journal of the Chemical Society, Faraday Transactions II, 72, 1525-1568.
Killick et al. (1996). Ethylated esterified seed oils—a second generation of herbicide adjuvants. FRI Bulletin 193 (Proceedings, Fourth International Symposium on Adjuvants for Agrochemicals, 1995), 78-83.
Kirkwood (1991). Pathways and mechanisms of uptake of foliage-applied herbicides with particular reference to the role of surfactants. In Kirkwood, ed.: Target Sites for Herbicide Action, 219-243. New York: Plenum Press.
Kirkwood (1993). Use and mode of action of adjuvants for herbicides: a review of some current work. Pesticide Science 38, 93-102.
Knoche & Bukovac (1993). Interaction of surfactant and leaf surface in glyphosate absorption. Weed Science, 41, 87-93.
Krawczyk (1996). Lecithin: consider the possibilities. Inform 7(11), 1158-1167.
Kwon & Penner (1996). The efffect of piperonyl butoxide and adjuvants on sulfonylurea herbicide activity. Weed Technology 10, 127-133.
Lasic (1997). Liposomes in Gene Delivery. Chap. 6, pp. 67-112. Boca Raton: CRC Press.
Leece (1978). Foliar absorption in Prunus domestica L. I. Nature and development of the surface wax barrier. Australian Journal of Plant Physiology 5, 749-766.
Leskovar & Boales (1996). Azadirachtin: potential use for controlling lepidopterous insects and increasing marketability of cabbage. Horticultural Science 31, 405-409.
Linert & Chasman (1993). The effects of fluorochemical surfactants on recoatability. Leaflet distributed by 3M Company, 2 pp., based on article in American Paint & Coatings Journal, Dec. 20, 1993.
Mack et al. (1996). Effects of several adjuvant classes on two herbicides for weed control. FRI Bulletin 193 (Proceedings, Fourth International Symposium on Adjuvants for Agrochemicals, 1995), 448-453.
Manthey et al. (1989a). Herbicide-oil-water emulsions. Weed Technology 3, 13-19.
Manthey et al. (1989b). Esterified seed oils with herbicides. In Chow et al., ed.: Adjuvants and Agrochemicals, vol. 2, 139-148, Boca Raton: CRC Press.
Manthey et al. (1990). Small grain and grass weed response to BAS-514 with adjuvants. Weed Tecnology 4, 366-370.
Manthey et al. (1992). Foliar absorption and phytotoxicity of quizalofop with lipid compounds. Weed Science, 40, 558-562.
McMullan (1992). Effect of adjuvant and acidifying agent on imazamethabenz efficacy. Canadian Journal of Plant Science 72, 1389-1392.
Miller et al. (1996). The influence orf adjuvants on droplet production. FRI Bulletin 193 (Proceedings, Fourth International Symposium on Adjuvants for Agrochemicals, 1995), 95-102.
Nalewaja (1986). Seed oils with herbicides. Mededelingen Faculteit Landbouwwetenschappen Rijksuniversiteit Gent 51(2a), 301-310.
Nalewaja & Matysiak (1993). Optimizing adjuvants to overcome glyphosate antagonistic salts. Weed Technology 7, 337-342.
Nalewaja et al. (1990). Imazethapyr efficacy with adjuvants and environments. Weed Technology 4, 765-770.
Nandula et al. (1995). Effectiveness of adjuvants with nicosulfuron and primisulfuron for wirestem muhly (Muhlenbergia frondosa), control in no-till corn (Zea mays). Weed Technology 9, 525-530.
Newton et al. (1993). Structured surfactant formulations for pesticides. Pesticide Science 37, 208-209.
Norris, R. F. and Bukovac, M.J., “Structure of the pear leaf cuticle with special reference to cuticular penetration,” American Journal of Botany, vol. 55, No. 8, 1968, 975-83.
Omotosho et al. (1989). Methotrexate transport from the internal phase of multiple w/o/w emulsions. Journal of Microencapsulation 6, 183-192.
Parnham (1996). The importance of phospholipid terminology. Inform 7(11), 1168-1175.
Percival & Baker (1990). Chlorophyll fluorescence—a possible application in plant growth regulator research. Monograph, British Society of Plant Growth Regulation 19, 1-14.
Quinn (1985). The chemico-physical properties of membrane lipids and their relevance to plant growth and protection. In St John, ed.: Frontiers of Membrane Research in Agriculture (Beltsville Symposium 9), 55-75.
Quinn et al. (1986). An evaluation of soya lecithin in crop spray performance. Atomisation and Spray Technology 2, 235-246.
Rahman et al. (1994). Control of phenoxy herbicide resistant nodding thistle (Carduus nutans) in pasture. Proceedings, New Zealand Plant Protection Conference 47, 68-74.
Riederer & Schönherr (1990). Effects of surfactants on water permeability of isolated plant cuticles and on the composition of their cuticular waxes. Pesticide Science 29, 85-94.
Riederer & Schreiber (1995). Waxes—the transport barriers of plant cuticles. In Hamilton, ed.: Waxes: Chemistry, Molecular Biology and Function, 131-156. Dundee: Oily Press.
Rimmer et al. (1992). Nutrient application to potatoes and wheat with various spray adjuvants. Abstracts, Third International Symposium on Adjuvants for Agrochemicals. No page number.
Roberts (1992). Laboratory procedures applicable to the evaluation of spray adjuvants utilizing methylated seed oils. Abstract, Third International Symposium on Adjuvants for Agrochemicals. No page number.
Salakhutdinov et al. (1992). Polymorphous transformations in model membranes caused by amphiphilic fungicides. Doklady Akademii Nauk Respubliki Uzbekistan 1, 45-46.
Santier & Chamel (1996). Penetration of triolein and methly oleate through isolated plant cuticles and their effect on penetration of [14C] quizalofop-ethyl and [14C] fenoxaprop-ethyl. Weed Research 36, 167-174.
Schönherr (1979). Transcuticular movement of xenobiotics. Proceedings, 4th International Congress of Pesticide Chemistry, vol. 3, 392-400.
Schönherr (1993). Effects of monodisperse alcohol ethoxylates on mobility of 2,4-D in isolated plant cuticles. Pesticide Science 38, 155-164.
Schönherr & Baur (1994). Modelling penetration of plant cuticles by crop protection agents and effects of adjuvants on their rates of penetration. Pesticide Science 42, 185-208.
Schönherr et al. (1991). Foliar uptake of pesticides and its activation by adjuvants: theories and methods for optimization. Proceedings, 7th International Congress of Pesticide Chemistry, vol. 1, 237-253.
Schreiber (1994). A mechanistic approach towards effects of nonionic surfactants on mobility of pesticides in reconstituted cuticular wax of barley leaves. Mededelingen Faculteit Landbouwwetenschappen Rijksuniversiteit Gent 59(3b), 1409-1414.
Schrieber et al. (1995). A simple photometric device analysing cuticular transport physiology: surfactant effect on permeability of isolated cuticular membranes of Prunus laurocerasus L. Journal of Experimental Botany 46, 1915-1921.
Serre I. et al. (1993). Seed oil derivatives as adjuvants: influence of methyl to octadecyl oleates on the penetration of herbicides through various plant cuticles. Mededelingen, Faculteit Landbouwwetenschappen Rijksuniversiteit Gent 58(3a), 795-802.
Skelton (1993). Pesticide microemulsion concentrate formulations utilizing fatty acid methyl esters as solvent alternatives. ASTM Special Technical Publication 1183, 114-120.
Skrzypezak & Nalewaja (1987). Influence of various fatty acid formulations on the uptake and translocation of sethoxydim and fluazifop-butyl. Roczniki Nauk Rolniczych, Ser. E 16(2), 143-150. Abstract only.
Souty & Guennelon (1974). The mechanisms of foliar absorption. Annales Agronomiques 25, 883-891. Abstract only.
Stock et al. (1992). Surfactant-enhanced foliar uptake of some organic compounds: interactions with two model polyoxyethylene aliphatic alcohols. Pesticide Science 34, 233-242.
Swietlik (1989). Adjuvants affect the efficacy of glyphosate on selected perennial weeds. Horticultural Science 24, 470-472.
Tadros (1989). Colloidal aspects of pesticidal and pharmaceutical formulations—a overview. Pesticide Science, 26, 51-77.
Tan & Crabtree (1992). Effects of nonionic surfactants on cuticular sorption and penetration of 2,4-dichlorophenoxyacetic acid. Pesticide Science 35, 299-303.
Tan & Crabtree (1994). Cuticular penetration of 2,4-D as affected by interaction between a diethylene glycol monooleate surfactant and apple leaf cuticles. Pesticide Science 41, 35-39.
Tann et al. (1996). Effect of various carbon chain length methyl esters as agricultural tank mix adjuvants. FRI Bulletin 193 (Proceedings, Fourth International Symposium on Adjuvants for Agrochemicals, 1995), 71-77.
Thompson et al. (1996). Adjuvant effects on imazethapyr, 2,4-D and picloram absorption by leafy spurge (Euphorbia esula). Weed Science 44, 469-475.
Townson (1990). Influence of formulation and application variables in relation to the performance of glyphosate and imazapyr for control if Imperata cylindrica (L). Raeuschel. Ph.D. Thesis, University of Bristol. 312 pp.
Turner & Loader (1974). Studies with solubilized herbicide formulations. Proceedings, 12th British Weed Control Conference, vol. 1, 177-184.
Urvoy & Gauvrit (1991). Seed oils as adjuvants: penetration of glycerol trioleate, methanol oleate and diclofop-methyl in maize leaves. Proceedings, Brighton Crop Protection Conference, vol. 1, 337-342.
Urvoy et al. (1992). Seed oils as additives: penetration of triolein, methyl oleate and diclofop-methyl in maize leaves. Weed Research 32, 375-383.
Van Toor et al. (1994). Relationships between the herbicidal activity and foliar uptake of surfactant-containing solutions of glyphosate applied to foliage of oats and field beans. Crop Protection 13, 260-270.
Wallach & Philippot (1993). New type of lipid vesicle: Novasome™. In Gregoriadis, ed.: Liposome Technology, 2nd ed., vol. 1, pp. 141-156, Boca Raton: CRC Press.
Wanamarta & Penner (1989). Foliar absorption of herbicides. Reviews of Weed Science 4, 215-231.
Ward & Osborne (1993). Hydrotropy and penetration enhancement. In Walters & Hadgraft, ed.: Pharmaceutical Skin Penetration Enhancement, pp. 365-388. New York: Marcel Dekker.
Wells, (1989). Adjuvants, glyphosate efficacy and post-spraying rainfall. Plant Protection Quarterly 4(4), 158-164.
Whitson & Adam (1990) Leafy spurge (Euphorbia esula L.) control with various adjuvants combined with picloram and fluroxypyr. Proceedings, Western Society of Weed Science 43, 37.
Wills et al. (1993). Evaluation of the effect of a paraffinic petroleum oil-based adjuvant and an organosilicone-modified methylated vegetable oil-based adjuvant on the efficacy of imazethapyr herbicide as applied in conventional and ultra-low volumes. Pesticide Science 38, 280-282.
Woznica & Messersmith (1994). Evaluation of adjuvants for glyphosate. Materialy Sesji Naukowej Instytutu Ochrony Roslin 34(2), 98-101. Abstract in English.
Woznica & Messersmith (1995). Glyphosate retention and absorption by cattail (Typha X glauca Godr.) as influenced by nonionic surfactants. Roczniki Nauk Rolniczych, Ser. E 24, 87-91.
Wyrill, J.B. & Burnside, O.C. (1977). Glyphosate toxicity to common milkweed and hemp dogbane as influenced by surfactants. Weed Science 25, 275-87.
Yaduraju & Ahuja (1995). Response of herbicide resistant Phalaris minor to pre- and post-emergence herbicides, herbicide mixtures and adjuvants. Proceedings, Brighton Crop Protection Conference, vol. 1, 225-230.
Young (1983). Glyphosate plus adjuvants. Proceedings, Northeastern Weed Science Society 37, 250-254.
Provisional Applications (3)
Number Date Country
60/039789 Mar 1997 US
60/034887 Jan 1997 US
60/029317 Oct 1996 US
Continuations (1)
Number Date Country
Parent 08/958149 Oct 1997 US
Child 09/534772 US