Patent Grant
9045720
The present invention relates to herbicidal compositions comprising aminophosphate or aminophosphonate salts, particularly to herbicidal compositions comprising a high amount and aminophosphate or aminophosphonate salts and a betaine surfactant and an amine oxide surfactant.
Among various presentations of compositions comprising glyphosate, concentrated liquid compositions that can be diluted by the end-user (typically a farmer) are of interest. Usually, the higher the glyphosate concentration is, the better it is, because the end-user can set the use concentration (the amount of active applied to the field) by adjusting the dilution rate, and can avoid handling much product (for example the higher the concentration is, the lower the weight is).
Concentrated compositions can comprise a high amount of glyphosate, water, and at least one surfactant compound that can be useful as a formulation aid (dispersion, dissolution and/or stability of the glyphosate in water), and/or as a biological activator (for example increasing the efficacy of glyphosate salt, for example by encouraging wetting of a weed to be eliminated, or by encouraging penetration of the glyphosate into the weed). The amount of glyphosate, the nature of surfactant(s), the amount thereof, and possible further ingredients might have also an effect onto the rheological properties of the composition (for example viscosity, or ability to be spread), as such, or upon dilution. The rheological properties of the composition as such or upon dilution are important for handling and spreading purpose.
Where the concentration of glyphosate is high, crystallization is to be avoided. Crystallization can occur at different temperatures, at different glyphosate concentrations, or when diluting with water. The crystallization is characterized by formation of small solid particles comprising glyphosate. These small particles can have the bad impact of filters clogging, nozzles clogging, creating unnecessary hazardous waste problems to dispose off the crystals, loss of activity (bioefficacy), and/or bad repartition of the active on the field.
Compositions comprising glyphosate and ethoxylated fatty amines surfactants are known. However these compounds are believed to be rather ecotoxic, irritant or slightly biodegradable. There is a need for replacing these compounds or for reducing the amount thereof in the compositions.
Document WO 01/17358 (Monsanto) describes compositions comprising a high amount glyphosate isopropylamine salt and a mixture of surfactants comprising a surfactant of formula R—CO—NR′—(CR′2)n—COOM. The mixture of surfactants is taught enhancing herbicidal effectiveness. The surfactant is however expensive and there is a need for other solutions.
Document WO 03/063589 (Rhodia) describes compositions comprising 360 g/L of glyphosate isopropylamine salt (as glyphosate acid equivalent, 783 g/L as salt concentration), a betaine surfactant, and at least one further compound such as optionally ethoxylated amines or etheramines. There is a need for other solutions, especially for composition that are considered as less ecotoxic, and/or less sensitizing, and/or for composition that have improved bioefficacy.
There is a constant need for new compositions comprising an aminophosphate or aminophosphonate salt, especially a glyphosate salt, that can allow:
The invention addresses at least one of the needs or concerns above. Thus the invention relates to a herbicidal composition comprising:
wherein:
According to another aspect the invention relates to a process for preparing the composition.
According to another aspect the invention relates to the use of a surfactant system comprising the betaine surfactant and the amine oxide surfactant in a herbicidal composition comprising the aminophosphate or aminophosphonate salt.
According to another aspect the invention relates to a surfactant blend comprising:
wherein:
According to another aspect the invention relates to the use of the surfactant blend, as a part of or as the whole surfactant system, in a herbicidal composition comprising the aminophosphate or aminophosphonate salt.
The invention also relates to the use of the composition.
In the present specification, unless otherwise provided, the amounts of aminophosphate or aminophosphonate salt, preferably a glyphosate or gluphosinate salt, are expressed as acid equivalents.
In the present specification, unless otherwise provided, the amounts of surfactant system or ingredients being used (such as betaine surfactant composition of matter, amine oxide surfactant composition of matter, surfactant blend), are the amounts “as is”. These are the total amounts of a mixture or association, as opposed to amounts as active matter, dry matter amounts (solid content), or the like.
In the present specification, unless otherwise provided, the amounts of surfactant active matter (or “active surfactant matter”), for a surfactant ingredient or system (such as betaine surfactant composition of matter, amine oxide surfactant composition of matter, surfactant blend), are defined as the dry matter amount of the surfactant ingredient or system, minus the total amount of salt in the surfactant ingredient or system.
In the present specification, “chloride based salts” refer to any salt having Cl−, particularly KCl or NaCl. The amounts thereof can be determined by conventional means. The amounts, unless otherwise provided, relate to amounts by weight in the herbicidal composition.
In the present specification, “substantially no sodium cation” refers to amounts of sodium cations of lower than 1% by weight, preferably lower than 0.1%, preferably lower than 0.01%.
In the present specification, a “surfactant system” refers to an association or mixture of surfactants which are provided separately in the composition or as a mixture prepared before introduction. The mixture can be for example a surfactant blend.
In the present specification the “surfactant blend” refers to a composition of matter comprising water, the betaine surfactant and the amine oxide surfactant. It does not comprise the aminophosphate or aminophosphonate salt. It is possible that the blend comprise at least one different surfactant, but it is not preferred. In the present specification a “blend adduct” refers to a surfactant blend obtained by preparing the betaine surfactant and the amine oxide surfactant in the same course of process, typically in a single reactor (batch). In the present specification a “blend mix” refers to a surfactant blend obtained by mixing a betaine surfactant (typically a betaine surfactant composition of matter) and an amine oxide surfactant (typically an amine oxide surfactant composition of matter) both prepared previously separately.
Surfactants are usually reaction adducts comprising several different compounds. These different compounds can have effects on the herbicidal composition. Hence it is referred to surfactant compositions of matter, and to surfactant blend if several surfactants (usually surfactant compositions of matter) are mixed. Thus in the present specification a betaine surfactant composition of matter is understood as a mixture comprising water, optionally a chlorine based salt, the betaine surfactant active molecule(s), and optionally further compounds such as pH buffers. In the present specification an amine oxide surfactant composition of matter is understood as a mixture comprising water, optionally a chlorine based salt, the amine oxide surfactant active molecule(s), and optionally further compounds such as pH buffers.
The ingredients of the composition are described below. Any combination thereof and therein can be implemented to defined, and/or prepare the composition according to the invention, and/or to use according to the invention.
Aminophosphate or Aminophosphonate Salt
Aminophosphate or aminophosphonate salts are known by the one skilled in the art.
Preferred salts are glyphosate or gluphosinate salts.
Glyphosate refers to N-(phosphonomethyl)glycine.
Gluphosinate refers to 4-[hydroxy(methyl)phosphinoyl]-DL-homoalanine.
The salts include:
Preferred glyphosate salts for herbicidal application that can be cited are glyphosate potassium (K) salt, glyphosate sodium (Na) salt isopropylamine (IPA) salt, monoethanolamine (MEA) salt, trimethylsulphonium salt, potassium salt, ammonium (NH3) salt, and mixtures or associations thereof, for example as taught in documents WO01/26469 (Nufarm) and WO03/013241 (Nufarm).
In the present invention isopropylamine containing salts are preferred. Thus in a preferred embodiment the salt is a glyphosate isopropylamine salt. In a preferred embodiment, the ratio between the cation such as the cation of isopropylamine and glyphosate is of about 1/1. However the ratio can of higher than 1/1. Such a ratio provides compositions having higher pH. The higher the pH, the lower the crystallization. pH can be also managed by using any other basic compound, for example KOH or other buffers.
Surfactant System
The surfactant system comprises the betaine surfactant, the amine oxide surfactant, optionally at least one surfactant different from the betaine and the amine oxide. The different surfactant(s) can be provided in the herbicidal composition as a separate ingredient; it can be thus referred to an association. In another embodiment, at least one of the different surfactant(s) can be provided as a mixture with the betaine surfactant and/or with the amine oxide surfactant and/or surfactant blend, it can be thus referred to a mixture or a blend. In that embodiment the different surfactant can be prepared separately and simply mixed with the betaine surfactant and/or amine oxide surfactant and/or surfactant blend. The different surfactant can also be prepared in the same course of process of the preparation of the betaine surfactant and/or amine oxide and/or surfactant blend, typically the blend adduct. Some useful different surfactant(s) are described below as further ingredients and as further surfactants.
Amine Oxide Surfactant
The amine oxide surfactant is:
The amine oxide has preferably R2 being a methyl group.
R1 is preferably an alkyl group. This group is usually actually a mixture of different groups having different numbers of carbon atoms, being linear or branched, and optionally having some insaturations. These mixtures come from the reagents used to prepare them, which are actually distillation cuts and/or have a natural origin. In the present specification the number of carbon atoms in the R1 group refers to the number of carbon atoms of the two most represented species.
Preferably:
Amine oxides of formula (III) are preferred. They are often referred to as alkyl amine oxides, and are preferably an alkyldimethyl amine oxide based surfactant, for example lauryl dimethyl amine oxide based surfactant (R2 is a methyl group, R1 is a lauryl C12 group). Amine oxides of formula (IV) are often referred to as alkyl amidoalkyl amine oxides.
Such surfactants are known by the one skilled in the art and are commercially available. Processes for preparing amine oxide surfactants are known by the one skilled in the art. Processes usually involve reacting an amine of formula R1NR2R2 and/or R1—CO—NH—R4—NR2R2 with an oxidizing agent such as hydrogen peroxide H2O2, optionally in the presence of a complexant such as EDTA, and optionally regulating pH with a base such as NaOH or KOH. In the present invention the amine oxide surfactant is in an amine oxide surfactant composition of matter that preferably comprises substantially no sodium cation.
The amine oxide can be provided as an amine oxide surfactant composition of matter comprising water, the amine oxide and optionally a salt such as a potassium (preferred) or sodium based salt of chloride or hydroxide (preferred). The amine oxide surfactant composition of matter can typically comprise at least 25%, preferably at least 30%, by weight as active surfactant matter of the amine oxide, and preferably substantially no betaine (lower than 1% by weight as active matter, preferably lower than 0.1%, or even less, to none). The amine oxide surfactant composition of matter can also be a desalted surfactant composition of matter, comprising substantially no salt (lower than 1% by weight, preferably lower than 0.1%, or even less, to none). Processes for desalting surfactants are known by the one skilled in the art and are for example taught in document WO 00/38523.
Betaine Surfactant
The betaine surfactant is:
The betaine has preferably R2 being a methyl group.
R1 is preferably an alkyl group. This group is usually actually a mixture of different groups having different numbers of carbon atoms, being linear or branched, and optionally having some insaturations. These mixtures come from the reagents used to prepare them, which are actually distillation cuts and/or have a natural origin. In the present specification the number of carbon atoms in the R1 group refers to the number of carbon atoms of the two most represented species.
Betaines of formula (I) are preferred. They are often referred to as alkyl betaines, and are preferably an alkyldimethyl betaine based surfactant, for example lauryl dimethyl betaine based surfactant (R2 is a methyl group, R1 is a lauryl C12 group). Betaines of formula (II) are often referred to as alkyl amidoalkyl betaines.
Such surfactants are known by the one skilled in the art and are commercially available. Processes for preparing betaine surfactants are known by the one skilled in the art. Processes usually involve reacting an amine of formula R1NR2R2 and/or R1—CO—NH—R4—NR2R2 with monochloroacetic acid (MCA) or potassium (preferred) or sodium monochloroacetate (KMCA preferred or SMCA), and optionally regulating pH with a base such a NaOH or KOH (preferred). In the present invention the betaine is preferably in a betaine surfactant composition of matter that preferably comprises substantially no sodium cation.
The betaine can be provided as a betaine surfactant composition of matter comprising water, the betaine and optionally a salt such as potassium (preferred) or sodium based salt of chloride (preferred) or hydroxide. Preferably the betaine composition of matter is a potassium based surfactant composition of matter, for example obtained with using KMCA and/or KOH. The betaine surfactant composition of matter can typically comprise at least 25%, preferably at least 30%, by weight as active surfactant matter of the betaine, and preferably substantially no amine oxide (lower than 1% by weight as active matter, preferably lower than 0.1%, or even less, to none). The betaine surfactant composition of matter can also be a desalted surfactant composition of matter, comprising substantially no salt (lower than 1% by weight, preferably lower than 0.1%, or even less, to none). Processes for desalting surfactants include are known by the one skilled in the art and are for example taught in document WO 00/38523.
Betaine Surfactant Composition of Matter
The betaine surfactant composition of matter can advantageously comprise:
The betaine is a main surfactant compound of the betaine surfactant composition of matter. It is preferably the main surfactant compound of the surfactant system or surfactant blend. It is also referred to as the main surfactant. By main surfactant compound it is meant that said surfactant compound represents the highest surfactant active matter compared to optional other surfactant(s). For example, in a mixture or association comprising 40 parts as active of surfactant 1, 30 parts as active of surfactant 2, and 30 parts as active of surfactant 3, surfactant 1 would be considered as main surfactant even if it represents lower than 50% of all surfactants.
Preferably the betaine active matter represents at least 30% by weight, preferably at least 50%, of the total surfactant active matter of the betaine surfactant composition of matter, preferably of the surfactant blend or system in the composition.
Advantageously the betaine surfactant composition of matter comprises:
Preferably the betaine surfactant composition of matter comprises:
The betaine surfactant composition of matter can be obtained by, and is preferably obtained from, a process comprising the following steps:
step 1) reacting a compound of formula R1R2R2N with monochloroacetic acid, to obtain a reaction product;
step 2) adding potassium hydroxide to increase the pH,
step 3) optionally adding some further ingredients or adjusting the concentration or pH.
It is mentioned that step 1 and step 2 can also be performed simultaneously, by adding potassium hydroxide during reaction completion or by adding progressively chloroacetic acid and potassium hydroxide.
In another embodiment potassium chloroacetate is used in step 1) instead of chloroacetic acid, and step 2) is optional.
In a preferred embodiment, the process does not comprise any desalination step or ion exchange step. Thus the process is cost effective, and therefore the herbicidal composition can also be cost interesting.
Betaine and Amine Oxide Associations and/or Surfactant Blends
Compositions comprising an association in the surfactant system, for example as a surfactant blend, of a betaine of formula (I) and of an amine oxide of formula (III) are preferred.
Advantageously:
Preferably the weight ratio between the betaine surfactant and the amine oxide surfactant as per active surfactant matter is of from 30/70 to 70/30, preferably from 50/50 to 70/30. This ratio can be applied to the composition, to the surfactant system, or to the surfactant blend
In one embodiment the betaine surfactant is provided as a betaine surfactant composition of matter comprising the betaine(s) and water, separately from the amine oxide surfactant, the amine oxide being optionally provided as an amine oxide surfactant composition of matter.
In another embodiment the betaine surfactant and the amide oxide surfactant are provided as a surfactant blend, comprising the betaine(s), the amine oxide(s), and water. The surfactant blend can be a blend adduct or a blend mix. The blend mix can be typically obtained by mixing a betaine surfactant composition of matter, preferably a potassium based one or a desalted one, and an amine oxide surfactant composition of matter.
The surfactant blend is preferably a potassium based blend, for example obtained from a potassium based betaine surfactant composition of matter, or obtained as a blend adduct from a preparation involving using KMCA and/or KOH, and preferably comprising substantially no sodium cation and/or obtained with using substantially no SMCA and/or NaOH. The surfactant blend can also be a desalted surfactant blend comprising substantially no salt (lower than 1% by weight, preferably lower than 0.1%, or even less, to none), for example obtained by mixing desalted or substantially salt-free surfactant compositions of matters, and by mixing surfactant compositions of matter then desalting. Processes for desalting surfactants are known by the one skilled in the art and are for example taught in document WO 00/38523.
Advantageously the surfactant blend comprises at least 1% by weight, preferably at least 2%, preferably at least 3%, of a potassium salt, preferably of potassium chloride salt.
Advantageously the surfactant blend comprises at least 20%, preferably at least 25%, preferably at least 30%, by weight as active surfactant matter of the betaine together with the amine oxide, and at least 2% by weight of potassium chloride, and preferably substantially no sodium cation.
As explained above the surfactant blend can be prepared by a mixture route. Alternatively the surfactant blend can be obtained as a blend adduct in the same course of process by preparing first the betaine then the amine oxide in the same reactor from an amine of formula R1NR2R2 and/or R1—CO—NH—R4—NR2R2, or by preparing first the amine oxide then the betaine in the same reactor from an amine of formula R1NR2R2 and/or R1—CO—NH—R4—NR2R2, or by preparing simultaneously the amine oxide and the betaine in the same reactor from an amine of formula R1NR2R2 and/or R1—CO—NH—R4—NR2R2. In these processes it is possible to load an excess of the amine for a part of it to be reacted during first stage, and the remaining to be reacted during the second stage. It is also possible to load some amine for the first stage and some amine for the second stage, with optionally changing the amine at each step. Each stage can be substantially carried out as described above for individual betaine surfactant and amine surfactant.
The ratios between the betaine and the amine oxide can be controlled by controlling the amounts of reagents.
A particularly interesting process for preparing a surfactant blend comprises the steps of:
Preferably in steps 1) or 2′), monochloroacetic acid (MCA) and KOH (preferred) or NaOH can be used, with introducing MCA first and then introducing progressively or at end of reaction KOH (preferred) or NaOH. Alternatively KMCA (preferred) or SMCA can be used, with further optionally KOH (preferred) or NaOH being introduced progressively at the end of the reaction.
Advantageously:
pH can be adjusted with a potassium based compound such as KOH or any other compound.
pH of the surfactant blend is preferably of from 7 to 9, as is.
Further Ingredients
The herbicidal composition can comprise further ingredients, such as:
The one skilled in the art knows further ingredients that can be used for managing some properties or features of the composition and/or for adding benefits.
The formulations can for example comprise for example:
The amount of these additives listed above is normally less than 10% by weight, preferably 1% by weight or less, advantageously 0.1% by weight or less compared with the composition weight.
Other Surfactants
The herbicidal composition can comprise a further surfactant, different from the betaine of the betaine surfactant composition matter. This further surfactant can provide further advantages or synergies in term of costs, and/or bioefficacy, and/or rheology management, and/or environment concerns and/or sensitivity concerns.
Examples of further surfactants include:
The fatty amines or ethoxylated fatty amines can comprise at least one hydrocarbon group containing 2 to 24 carbon atoms, optionally polyalkoxylated.
The fatty amines or ethoxylated fatty amines can more particularly be selected from amines comprising at least one linear or branched, saturated or unsaturated group containing 2 to 24 carbon atoms, preferably 8 to 18 carbon atoms, optionally comprising 2 to 30 oxyethylene groups, or a mixture of a plurality thereof. Examples include ethoxylated tallow amines.
The fatty amines or ethoxylated fatty amines can be selected from ethoxylated fatty amines comprising at least one linear or branched, saturated or unsaturated groups containing 6 to 24 carbon atoms, preferably 8 to 20 carbon atoms, comprising 2 to 30 oxyethylene groups, or a mixture of a plurality thereof. Examples include the compounds having the following formula:
wherein R represents a linear or branched, saturated or unsaturated hydrocarbon group containing 6 to 24 carbon atoms, preferably 8 to 20 carbon atoms; OA represents an oxypropylene group; and n, n′, which may or may not be identical, represent a mean number in the range 1 to 30.
Examples of such amines that can be cited are amines derived from copra and containing 5 oxyethylene (OE) motifs, oleic amines containing 5 OE, amines derived from tallow containing 5-20 OE, for example 10, compounds corresponding to the above formula, in which R is an alkyl group containing 12 to 15 carbon atoms, the number of OE motifs being in the range 20 to 30.
The amount of fatty amines or ethoxylated fatty amines can be of from 0 (none) to 120 g/l of the composition, preferably of from 0 (none) to 60 g/l.
The ether carboxylate has preferably formula R(OCH2CH2)nOCH2CO2−, wherein R is a linear or branched alkyl, alkenyl, alkylphenyl or polypropyleneoxy group having from 6 to 20, for example 8 to 14, aliphatic carbon atoms and n is of from 1 to 30, preferably of from 2 to 20. The ether carboxylate has preferably a counter ion being ammonium or potassium, or obtained from an amine or alkanolamine having up to 6 carbon atoms.
The acid or non acid mono- and di-ester phosphate, optionally polyalkoxylated is selected from acid or non acid phosphate mono- or di-esters, optionally polyalkoxylated, with the formula below:
(AO)3-mP(═O)(OM)m
wherein:
The acid or non acid mono- and di-ester phosphate, optionally polyalkoxylated can be in the form of a monoester, a diester, or a mixture of these two esters.
The amount of acid or non acid mono- and di-ester phosphate, optionally polyalkoxylated can be of from 0 (none) to 120 g/l of the composition.
Process for Preparing the Herbicidal Composition
The composition of the invention can be prepared by mixing their different ingredient with moderate stirring.
This operation preferably takes place at a temperature in the range 15° C. to 60° C., preferably at a temperature close to ambient temperature (15-30° C.).
The surfactant system, for example the surfactant blend, is preferably only added once the other constituents have been mixed.
Thus the process can comprise the step of mixing the aminophosphate or aminophosphonate salt with the betaine surfactant and the amine oxide surfactant, and the optional different surfactant(s). The betaine surfactant and the amine oxide surfactant can be provide in any form, separately, preferably as a betaine surfactant composition of matter comprising water and as an amine oxide surfactant composition of matter comprising water. The can be also provided together as a surfactant blend comprising the betaine surfactant and the amine oxide surfactant and water. Hence a useful process for preparing the composition comprises:
Step a) preparing a surfactant blend as mentioned above
Step b) mixing with the other ingredients.
Herbicidal Composition Preferred Features
Advantageously the composition is an aqueous composition, and:
Advantageously the surfactant system is provided with comprising water, in an amount “as is” of at least 80 g/L, preferably of at least 100 g/L.
Advantageously the amount of surfactant as per active surfactant matter of the surfactant system is of at least 25% by weight of the surfactant system.
Advantageously the betaine with the amine oxide represents at least 30% by weight as per active surfactant matter, preferably at least 50%, of the total surfactant active matter of the surfactant system in the composition.
Advantageously the composition comprises at least 80 g/L as is, preferably at least 100 g/L:
Thus the betaine with the amine oxide, provided as surfactant compositions of matter or as surfactant blend can represent all or a part of the surfactant system in the composition.
Advantageously the composition comprises:
Advantageously the composition comprises:
Some compositions can typically comprise:
Some other compositions can typically comprise:
At high loads of glyphosate salt, especially with salts different from potassium salts, for example with glyphosate isopropylamine salt, the invention allows among other handling less composition (higher load), with a good stability (no crystals) with an interesting bioefficacy and/or ecotoxic profile. The composition can allow also good compatibility with other herbicides used for example to address some weed resistances.
At low loads of glyphosate salt, especially with salts different from potassium salts, for example with glyphosate isopropylamine salt, the invention allows among other a good stability (no crystal) with an interesting bioefficacy and/or ecotoxic profile.
Use of the Composition
The herbicidal composition of the invention can be thus used to treat plants, normally after diluting with water. The diluted composition can be applied onto a field by any appropriate mean.
The dilution, and the application onto the field, can be for example such that the amount of aminophosphate or aminophosphonate salt, preferably glyphosate salt, is of from 500 g acid equivalent/ha to 1500 g acid equivalent/ha, typically from 600 to 1200 g/ha.
Upon dilution the end-user can admix other herbicides, pesticides, fertilizers, fungicides. For example the end-user can combine the glyphosate salt with other herbicides to address some weed resistances to glyphosate. The composition according to the invention, especially with glyphosate salt different from potassium salt, for example with glyphosate isopropylamine salt, provides a good compatibility with other herbicides. The invention can allow high loads of glyphosate salts with good compatibility.
Some details or advantages of the invention will appear in the non-imitative examples below.
The following raw materials are used:
Procedure:
Step 1: in a batch mix the water, lauryidimethyl amine and the MCA and add KOH upon formation of gel and/or to control pH in the range 7-9, at temperature of about 90° C., until a conversion ratio of MCA of about 99% is achieved.
Step 2: Cool the batch to about 70° C., add the EDTA solution, and slowly introduce the H2O2 solution and in a way to avoid excessive exotherm with holding the reaction at about 70° C. until amine residue and hydrogen is of about 1%.
The product obtained has the following characteristics:
Example 1 is reproduced with varying the amounts of MCA and H2O2 reagents to obtain a product having the following characteristics:
The following compositions are prepared:
The following characteristics are measured/evaluated:
This shows that the compositions according to the invention have a good physical stability without crystallization, at high loads of glyphosate IPA.
Activity tests are performed for the compositions of the invention and for comparative compositions:
Results (Formulation×Rate)
Composition of example 3.3 is slightly more efficient than comparative composition Roundup® CT, but is considered as bioequivalent, at 70 & 140 g ai/ha. See table 1 below.
Composition of example 3.6 is more efficient than comparative composition Roundup® CT, and is considered as bioequivalent to comparative composition Roundup® PowerMAX. See table 2 below.
Composition of example 3.6 can show better compatibility with other herbicides than comparative composition Roundup PowerMAX.
This application is the U.S. national phase of International Application No. PCT/EP2005/014146, filed Dec. 30, 2005, published in French as International Publication No. WO 2006/069794 A2 on Jul. 6, 2006, and claims priority of U.S. Application No. 60/640,300, filed Dec. 30, 2004, each hereby expressly incorporated by reference in its entirety and each assigned to the assignee hereof.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2005/014146 | 12/30/2005 | WO | 00 | 10/25/2007 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2006/069794 | 7/6/2006 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3225074 | Cowen et al. | Dec 1965 | A |
| 3527593 | Bland et al. | Sep 1970 | A |
| 3723357 | Hansen | Mar 1973 | A |
| 3882051 | Hansen | May 1975 | A |
| 4011388 | Murphy et al. | Mar 1977 | A |
| 4107328 | Michaels | Aug 1978 | A |
| 4117107 | Shapiro et al. | Sep 1978 | A |
| 4122159 | Madrange et al. | Oct 1978 | A |
| 4137191 | Lohr | Jan 1979 | A |
| 4243549 | Messenger et al. | Jan 1981 | A |
| 4452732 | Bolich, Jr. | Jun 1984 | A |
| 4477365 | Verboom et al. | Oct 1984 | A |
| 4585846 | Schulz et al. | Apr 1986 | A |
| 4607076 | Schulz et al. | Aug 1986 | A |
| 4650848 | Schulz et al. | Mar 1987 | A |
| 4703797 | Djabbarah | Nov 1987 | A |
| 4708998 | Schulz et al. | Nov 1987 | A |
| 4742135 | Schulz et al. | May 1988 | A |
| 4788247 | Schulz et al. | Nov 1988 | A |
| 4822847 | Schulz et al. | Apr 1989 | A |
| 4831092 | Bock et al. | May 1989 | A |
| 4835234 | Valint et al. | May 1989 | A |
| 4882405 | Schulz et al. | Nov 1989 | A |
| 4996045 | Leighton et al. | Feb 1991 | A |
| 5153289 | Schulz et al. | Oct 1992 | A |
| 5164120 | Borland et al. | Nov 1992 | A |
| 5180414 | Darchy et al. | Jan 1993 | A |
| 5258358 | Kocur et al. | Nov 1993 | A |
| 5292942 | Aigner et al. | Mar 1994 | A |
| 5338793 | Loftin | Aug 1994 | A |
| 5341932 | Chen et al. | Aug 1994 | A |
| 5354906 | Weitmeyer et al. | Oct 1994 | A |
| 5385206 | Thomas | Jan 1995 | A |
| 5439317 | Bishop et al. | Aug 1995 | A |
| 5464806 | Kassebaum et al. | Nov 1995 | A |
| 5551516 | Norman et al. | Sep 1996 | A |
| 5580856 | Prestrelski et al. | Dec 1996 | A |
| 5612285 | Arnold | Mar 1997 | A |
| 5686400 | Urfer et al. | Nov 1997 | A |
| 5700760 | Magin et al. | Dec 1997 | A |
| 5703016 | Magin et al. | Dec 1997 | A |
| 5747416 | McArdle et al. | May 1998 | A |
| 5863863 | Hasebe et al. | Jan 1999 | A |
| 5874394 | Thomas et al. | Feb 1999 | A |
| 5888934 | Townson et al. | Mar 1999 | A |
| 5897699 | Chatterji et al. | Apr 1999 | A |
| 5912209 | Kassebaum et al. | Jun 1999 | A |
| 5985798 | Crudden | Nov 1999 | A |
| 5998332 | Sato et al. | Dec 1999 | A |
| 6030928 | Stahl et al. | Feb 2000 | A |
| 6036638 | Nwawka | Mar 2000 | A |
| 6127318 | Sato et al. | Oct 2000 | A |
| 6165939 | Agbaje et al. | Dec 2000 | A |
| 6210476 | Chatterji et al. | Apr 2001 | B1 |
| 6284854 | Bowers et al. | Sep 2001 | B1 |
| 6288010 | Rose et al. | Sep 2001 | B1 |
| 6302209 | Thompson et al. | Oct 2001 | B1 |
| 6329322 | Reierson | Dec 2001 | B1 |
| 6346588 | Fench et al. | Feb 2002 | B1 |
| 6369122 | Subramanyam | Apr 2002 | B1 |
| 6376566 | Bergeron et al. | Apr 2002 | B1 |
| 6407042 | Ward et al. | Jun 2002 | B1 |
| 6417268 | Zhang et al. | Jul 2002 | B1 |
| 6432878 | Brigance | Aug 2002 | B1 |
| 6432884 | Lachut | Aug 2002 | B1 |
| 6451731 | Agbaje et al. | Sep 2002 | B1 |
| 6500784 | Mille et al. | Dec 2002 | B1 |
| 6566408 | Cotrell et al. | May 2003 | B1 |
| 6642178 | Woznica et al. | Nov 2003 | B2 |
| 6645912 | Mille et al. | Nov 2003 | B1 |
| 6645914 | Woznica et al. | Nov 2003 | B1 |
| 6653257 | Mille et al. | Nov 2003 | B2 |
| 6770268 | Hall et al. | Aug 2004 | B1 |
| 6770594 | Bickers et al. | Aug 2004 | B2 |
| 6831108 | Dahanayake et al. | Dec 2004 | B2 |
| 6881707 | Howat et al. | Apr 2005 | B2 |
| 6992046 | Bramati et al. | Jan 2006 | B2 |
| 7135437 | Pallas et al. | Nov 2006 | B2 |
| 7316990 | Tank et al. | Jan 2008 | B2 |
| 8236730 | Bramati et al. | Aug 2012 | B2 |
| 8263529 | Suzuki et al. | Sep 2012 | B2 |
| 8383137 | Modaressi et al. | Feb 2013 | B2 |
| 20020187917 | Lazarowitz | Dec 2002 | A1 |
| 20030118540 | Charlton et al. | Jun 2003 | A1 |
| 20040097372 | Abraham et al. | May 2004 | A1 |
| 20040110644 | Halliday et al. | Jun 2004 | A1 |
| 20040121917 | Pakulski | Jun 2004 | A1 |
| 20050003965 | Xiao et al. | Jan 2005 | A1 |
| 20050010009 | Schulz et al. | Jan 2005 | A1 |
| 20050020454 | Francini et al. | Jan 2005 | A1 |
| 20050130842 | Fleute-Schlachter | Jun 2005 | A1 |
| 20050170965 | Bramati et al. | Aug 2005 | A1 |
| 20060019830 | Xu et al. | Jan 2006 | A1 |
| 20060060354 | Lewis et al. | Mar 2006 | A1 |
| 20070155628 | Pazhianur et al. | Jul 2007 | A1 |
| 20070282075 | Koch et al. | Dec 2007 | A1 |
| 20080312083 | Gioia et al. | Dec 2008 | A1 |
| 20090018018 | Gioia et al. | Jan 2009 | A1 |
| 20100069269 | Prat et al. | Mar 2010 | A1 |
| 20100093874 | Monin et al. | Apr 2010 | A1 |
| 20100140531 | Prat et al. | Jun 2010 | A1 |
| 20110009269 | Gioia et al. | Jan 2011 | A1 |
| 20110015071 | Kisenwether et al. | Jan 2011 | A1 |
| 20120040833 | Kisenwether et al. | Feb 2012 | A1 |
| 20120165195 | Iskandar et al. | Jun 2012 | A1 |
| Number | Date | Country |
|---|---|---|
| 2554335 | Aug 2005 | CA |
| 0370338 | May 1990 | EP |
| 0373851 | Jun 1990 | EP |
| 0 274 369 | Sep 1990 | EP |
| 0449159 | Oct 1991 | EP |
| 0483095 | Apr 1992 | EP |
| 0508022 | Oct 1992 | EP |
| 0573118 | Dec 1993 | EP |
| 0810239 | Dec 1997 | EP |
| 10183176 | Jul 1998 | JP |
| 11-349826 | Dec 1999 | JP |
| 9212637 | Aug 1992 | WO |
| 9214907 | Sep 1992 | WO |
| 9701281 | Jan 1997 | WO |
| 9706230 | Feb 1997 | WO |
| 9736489 | Oct 1997 | WO |
| 9814060 | Apr 1998 | WO |
| 9903895 | Jan 1999 | WO |
| 9915610 | Apr 1999 | WO |
| WO 9927048 | Jun 1999 | WO |
| 9945780 | Sep 1999 | WO |
| 9962338 | Dec 1999 | WO |
| WO 0038523 | Jul 2000 | WO |
| 0067571 | Nov 2000 | WO |
| 0067573 | Nov 2000 | WO |
| WO 0108482 | Feb 2001 | WO |
| 0117358 | Mar 2001 | WO |
| 0126463 | Apr 2001 | WO |
| 0126469 | Apr 2001 | WO |
| 0189302 | Nov 2001 | WO |
| 0226036 | Apr 2002 | WO |
| 03049813 | Jun 2003 | WO |
| 2004107861 | Dec 2004 | WO |
| 2004107862 | Dec 2004 | WO |
| 2007003112 | Jan 2007 | WO |
| Entry |
|---|
| Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., vol. A 10, Edited by Gerhartz et al., pp. 176-177, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, 1987. |
| “Application Guide for Household & Industrial Markets”; McIntyre Group Ltd., Copyright 2002, (Jan. 2003), obtained online @ http://www.dewolfchem.com/pdf/Mcintyre—HI&I—Application—Guide.pdf, (downloaded Mar. 6, 2012). |
| Surfactants by Albright & Wilson (Australia Limited ACN 004 234 137)—5 pp Feb. 1994. |
| Empigen BB-AU alkyl betaine by Albright & Wilson Australia Limited (Incorporated in Victoria) Product Handling & Safety Bulletin—4 pp, 1983. |
| Basheva et al.; Role of Betaine as Foam Booster in the Presence of Silicone Oil Drops; Langmuir 2000, 16, 1000-1013; Received Jun. 16, 1999; 2000 American Chemical Society Published on Web Dec. 8, 1999. |
| Number | Date | Country | |
|---|---|---|---|
| 20080103047 A1 | May 2008 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60640300 | Dec 2004 | US |
