Patent Application
20110251070
Any foregoing applications and all documents cited therein or during their prosecution (“application cited documents”) and all documents cited or referenced in the application cited documents, and all documents cited or referenced herein (“herein cited documents”), and all documents cited or referenced in herein cited documents, together with any manufacturer's instructions, descriptions, product specifications, and product sheets for any products mentioned herein or in any document incorporated by reference herein, are hereby incorporated herein by reference, and may be employed in the practice of the invention.
Citation or identification of any document in this application is not an admission that such document is available as prior art to the present invention.
The invention relates to agrochemical compositions comprising oils and alkylpolysiloxanes of high silicone character (HSCAS) with good oil compatibility which improve the spreading behavior and reduce surface tension of oil-based agricultural formulations, and optionally comprising agrochemically active ingredients such as fungicides, insecticides or herbicides and/or inert ingredients such as emulsifiers and other agrochemically acceptable components.
Improving the spreading coverage of agricultural sprays on plant surfaces is desirable and well known as beneficial to the efficacy of agricultural treatments. It is particularly desirable that agricultural pesticide sprays applied to plants are rapidly and uniformly distributed in order to improve protection and enhance penetration of the active ingredient into the plant, therefore gaining improved coverage and adhesion, to control unwanted weeds, insect and mite infestations, and to control plant diseases.
As many pesticides have limited water solubility, oils often serve as the carriers to deliver the active ingredient to the target plant or pest. The increasing cost of oils, problems with phytotoxicity and environmental concerns related to pesticidal compositions create a pressure to reduce the use of spray oils, which is however not possible due to the critical role they play in the agricultural spray formulation.
It is therefore desired to have adjuvants which can reduce the bulk surface tension of liquid oil-containing sprays, and, thereby improving the wetting and spreading of the oils and active ingredients, and therefore allowing for reduction of the amount of spray oils.
For the agrochemical compositions of the invention, the alkylpolysiloxanes of high silicone character (HSCAS) contained therein are defined herein as having blocks of unmodified polydimethylsiloxane segments in their molecular structure, i.e. at least 10 uninterrupted D groups (—Me2SiO—) on average, and having hydrocarbon radicals providing good compatibility with the oil.
The HSCAS reduce the surface tension of the agricultural spray oils and improve the spread coverage on foliage, including those leaves with hydrophobic surfaces and/or corrugated surfaces or those which are positioned other than horizontally, thereby enhancing the performance of the agrochemical compositions. However, the state of the art had not taught the use of HSCAS in agrochemical compositions.
In 1993, Stevens prepared the first extensive review on the use of “Organosilicone Surfactants as Adjuvants for Agrochemicals.” It was suggested that oil spreading for insect control and improved foliage coverage might be enhanced by organosilicones, but no studies were referenced nor were any oils cited. Pesticide Science, pp. 103-122, 1993(38).
Policello et al. reported the use of low molecular weight alkyloligosiloxanes as additives for spray oil applications with vegetable and mineral oils (see Policello et al., Alkylsilicones for Agricultural Oils and Oil-Based Formulations, Fourth International Symposium on Adjuvants for Agrochemicals, Melbourne, Australia, 3-6 Oct. 1995, FRI Bulletin No. 193), pgs 303-307.) However, the alkyloligosiloxanes described therein were of low molecular weight (350-500 g/mol) with short silicone chains such as trisiloxanes, which are known to be key structural elements of silicone polyethers effective as adjuvants for aqueous spreading, whereas higher siloxane chains are generally known in the art to be less effective for spreading of aqueous compositions. Also, the described alkyloligosiloxanes do not have high silicone character.
Gaskin et al. reported the effect of unspecified alkylsiloxanes for improved spreading and efficacy of oil-based insecticidal sprays (Gaskin et al., Enhancement of plant and petroleum-derived spray oils with alkylsilicone surfactants, Spray Oils—Beyond 2000, pgs. 56-61, University of Western Sydney (2002). However, the alkylsiloxanes required relatively high use rates; further more no indication was there that the special effects of HSCAS were considered or investigated.
Murphy et al. (U.S. Pat. No. 5,561 ,099) refer to increasing the spreading properties of oil-containing compositions by adding to the composition a linear alkylsilicone of the formula:
(CH3)3Si—O—(Si(CH3)2O)x—Si(CH3)(R)O)y—Si(CH3)3
or a cyclic alkylsilicone compound:
where x is an integer from 0 to 20, y is an integer from 1 to 10, m is an integer from 0 to 4, n is from 1 to 5 provided that m+n is from 3 to 5, and R is an alkyl group. These alkylsilicone compounds are used as adjuvants in preparing agricultural formulations which contain mineral or vegetable oils.
However, the compounds specified in detail are low molecular weight siloxanes with a low silicone character and as such not optimized for mineral oil-containing sprays.
U.S. Pat. No. 5,658,851, discloses lipophilic siloxanes which decrease the surface tension of oils. These siloxanes have the following general formula:
RaMe(3−a)Si{OSiMe2}x—{OSiMeR}y—OSiMe(3−a)Ra
where R is a lipophilic group selected from the group consisting of aryl, substituted aryl, aralkyl, alkyl phenyl ether, substituted phenylether, or alkyl alkyleneoxide groups; a is 0 or 1; x and y is 0 to 4 depending upon a, provided that the sum of x and y is greater than or equal to 6. Those siloxanes are referred to be adjuvants in oil-based herbicidal, disease treatment, or insecticidal compositions.
However, again the compounds described are low molecular weight siloxanes with a low silicone character which are not optimized for mineral oil containing sprays.
Finally, Murphy et al. (U.S. Pat. No. 5,658,852) disclose that one can increase the spreading properties of oil-containing pesticidal compositions by adding to the composition a linear alkylsilicone of the formula:
(CH3)3Si—O—(Si(CH3)2)O)x—(Si(CH3)(R)O)y—Si(CH3)3
wherein x=0 to 20, y=1 to 10 and R and alkyl or alkyl ester group containing 6 to 18 carbons.
However, this as well as the previous patents does not recognize the benefit of alkylpolysiloxanes with high silicone character in mineral oil-containing formulations; the siloxanes referred to in Murphy are only effective in relatively high consumption rates, and do not perform well with mineral oils.
Kennedy et al. (U.S. Pat. No. 6,669,949) refers to asymmetrical polyether alkyl polysiloxanes with good oil compatibility and spreading. However, these asymmetrical alkyl polyether siloxanes are uneconomical to use due to difficult and cost intensive manufacturing processes such as those requiring expensive alkyllithium reagents, and they provide only moderate benefits in the spreading of mineral oils.
In 2004, Gaskin et al. reported the used of alkylsilicone adjuvants with a vegetable oil and potash to improve the evenness and efficiency of drying sultana grapes and reported that alkylsilicone adjuvants could reduce surface tension of a vegetable-based drying oil and increase the spreading of an oil emulsion on grapes (see Gaskin et al., Proceeding of the 7th International Symposium on Adjuvants for Agrochemicals (ISAA 2004), 8-12 Nov. 2004 (Cape Town, South Africa) pgs. 24-29).
However, the drying compositions of Gaskin are not suitable for general agrochemical use as the drying compositions required the use of potash which significantly increased the pH of the composition. Moreover, the degree of spreading was dependent on the ratio of potash to oil and the emulsion compositions of Gaskin required that the alkylsilicone adjuvant be mixed with oil prior to emulsification with water. Pesticidal oil compositions or mineral oil-based compositions were not considered in this study.
Nakanishi et al. (US Patent Application Publication 2005/0261133) refers to low molecular weight siloxanes with a low silicon character and hydrophilic glycerol substituents for enhanced oil spreading.
Sieverding et al. (US Patent Application Publication 2005/0244357) refer to a solvent-containing emulsifiable formulation substantially free of water, comprising at least one or more organic solvents, one or more emulsifier and one or more agriculturally acceptable active agents, and a formulation synergist comprising one or more polyether or alkyl modified siloxanes. It was discovered that low molecular weight polyether modified siloxanes without unmodified polydimethylsiloxane units were especially efficient. Siloxanes with high silicone character were not investigated, and no effort was done to find adjuvants which are especially efficient in mineral oil-containing formulations.
Therefore, a need still exists in the art for oil-based, e.g. mineral oil or vegetable oil-based agrochemical compositions which produces a decrease in surface tension and increase in spreading, minimize the amount of oil used while retaining the effectiveness of their agrochemical effects, and maintains an agrochemically acceptable pH.
Surprisingly, the problem of developing a oil-based, especially mineral oil-based, agrochemical composition which maximizes the efficiency of oil use is solved by practicing the instant invention.
The invention describes agrochemical oil compositions comprising:
In one embodiment of the invention, the agrochemical oil compositions are free of potash.
In another embodiment of the invention, the pH of the oil composition is about 4.0 to about 9.0.
As noted above, the alkylpolysiloxanes of high silicone character (HSCAS) refer to alkylpolysiloxanes which have blocks of unmodified polydimethylsiloxane segments in their molecular structure, i.e. at least 10 uninterrupted polydimethylsiloxane groups (—Me2SiO—) on average, and having hydrocarbon radicals providing compatibility with the oil.
In one embodiment of the invention, the alkylpolysiloxanes of high silicone character are represented by the siloxane (a) of formula (I):
R″3Si—O—(SiR2O)u—(SiRR′O)v—SiR″3 (I)
wherein:
Alkylpolysiloxanes of siloxane (a) are characterized by a ratio of unmodified to modified polydimethylsiloxane unit of greater or equal to 10:1, e.g. 10:1 to 25:1; 10:1 to 50:1 or 10:1 to 100:1, ensuring that on average the polymer contains uninterrupted block as of at least 10 unmodified polydimethylsiloxane units in the polymer distribution, which is a key factor to providing low surface tension and good spreading behavior to the agrochemical oil composition.
In one embodiment of the alkylpolysiloxanes of siloxane (a), the radicals R and R″ are methyl, R′ is 14-18 alkyl, u is 50-150, v is 3-10. In another embodiment of the alkylpolysiloxanes of formula (I), the ratio u/v is selected from the group consisting of about 15 to about 25; about 12 to about 50 and about 10 to about 150.
In alkylpolysiloxanes of siloxane (b), the high silicone character necessary for good spreading and low surface tension is imparted by the uninterrupted unmodified polydimethylsiloxane chain of the divinylsiloxane crosslinker (III), while the alkyl modified branches provide good compatibility with the oil.
One embodiment of the alkylpolysiloxanes of siloxane (b) is derived by complete conversion of the remaining SiH groups of the primary reaction product in a transition metal-catalyzed hydrosilylation reaction with monounsaturated linear or branched aliphatic olefins with 8-24 carbon atoms. In another embodiment of the invention, the terminal olefins have 12-18 carbon atoms. In still another embodiment of the invention, the terminal olefins have 16-18 carbon atoms. In still another embodiment, the transition metal catalyst is a platinum derivative.
In another embodiment the alkylpolysiloxanes of siloxane (b) is derived by complete conversion of the remaining SiH groups of the primary reaction product in a transition metal-catalyzed hydrosilylation reaction with a mixture of at least 80 mol % monounsaturated linear or branched aliphatic olefins with 8-24 carbon atoms, and up to 20 mol % of alkyl or alkynylfunctional aromatic compounds selected from the group of unsaturated hydrocarbons, unsaturated olefins bearing 1-4 additional substituents selected from he group of hydroxy groups, halogen groups, alkoxy groups, aminogroups, alkylsubstituted amino groups or ester groups, allyl-functional or vinyl-functional polyethers comprised of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, with the free end groups selected from the group of saturated alkyloxy, free hydroxy or hydroxy groups esterified with C1-C4 alkanoic acids.
In still another embodiment, the transition metal catalyst is a platinum derivative.
In another embodiment of the alkylpolysiloxanes of siloxane (b), R1 is methyl, a is 10 to 100, b is 2 to 30, c is 0; and d is 30-300.
In one embodiment of the invention, the HSCAS reduces the surface tension of the oil by more than 5 mN/m.
In another embodiment of the invention, the HSCAS increases area spread coverage on hydrophobic surfaces such as polymer films or plant foliage by a factor of about 2 or more compared to the corresponding compositions comprising no siloxane. In another embodiment of the invention the increase in area spread coverage is from selection from the ranges consisting of about 2 to about 15, about 2 to about 5, about 2 to about 3.5 and about 5 to about 15.
In an additional embodiment of the invention, compositions comprising HSCAS increase the foliage coverage which allows for the oil component in the composition to be reduced by 10-60% compared to a composition with HSCAS. In a further embodiment, compositions comprising HSCAS, the spray volume is reduced by 5 to 50% as compared to a necessary spray volume to achieve coverage of a composition without HSCAS.The agrochemical oil composition of the invention also comprise at least one mineral oil from the group of paraffinic, isoparaffinic, cycloparaffinic or naphthenic oils. Although not intended to be totally inclusive, exemplary mineral oils are those marketed under the tradenames BANOLE® from Total, ORCHEX® from Calumet, SUNSPRAY® from SUNOCO, SPRAYTEX® from TEXACO, EXXSOL® and ISOPAR® from Exxon Chemical, blends of mineral oils and emulsifiers such as STYLET-Oil® from JMS Flower Farms.
In another embodiment of the invention, if the (i) at least one alkylpolysiloxane of high silicone character is an alkylpolysiloxane of siloxane (b), then (ii) may further encompass other oils such as plant oils like soybean oil, coconut oil, canola oil, castor oil, palm oil, palm kernel oil, olive oil, corn oil, cottonseed oil, peanut oil, sesame oil, avocado oil, linseed oil, sunflower oil, jojoba oil, rapeseed oil, safflower oil, and the like, methylated and ethylated seed oils such as methyl cocoate, methyl palm kernel oil, methyl sunflowerate, palm oil methyl ester, methyl rapeate, methyl canolate, methyl soyate, methyl oleate, ethylated oleic acid, ethylated palmitic acid, methylated and ethylated soybean oil, canola oil, coconut oil, sunflower oil, corn oil, cottonseed oils.
Mixtures of mineral, vegetable and/or alkylated oils may be used when the at least one alkylpolysiloxane of high silicone character is an alkylpolysiloxane of formula (II).
The agrochemical composition described herein may optionally comprise one or several agrochemically active ingredients, such as acaricides, algicides, amino acid synthesis inhibitors, attractants, repellents, bactericides, biostimulants, cell wall inhibitors, fertilizers, fungicides, growth promoters, growth regulators, herbicides, insecticides, lipid biosynthesis inhibitors, miticides, molluscicides, nematicides, photosynthesis inhibitors, pigment inhibitors, plant growth regulators, rodenticides, safeners, sterilants, synergists, viricides, and which are used alone or in combinations thereof.
Chemical classes, compounds of active ingredients or organisms which are agriculturally acceptable are, together with their use or uses, are listed for example in The Pesticide Manual, 14th edition, 2006, The British Crop Protection Council, in The Manual of Biocontrol Agents, 3rd edition, 2004, The British Crop Protection Council, and in other there cited literature; these documents are also herein incorporated by reference.
The following are representative, but nonlimiting examples of agrochemically active compounds that can be used in the compositions of the invention. Examples of herbicidally active materials include but are not limited to acetochlor, acifluorfen, aclonifen, acrolein, alachlor, ametryne, aminopyralid, amitrole, asulam, atrazine, benazolin, bensulfuron-methyl, bentazon, benzobicyclon, benzofenap, bialaphos, bifenox, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil, chlomethoxyfen, chloramben, chloroacetic acid, chlorbromuron, chlorimuron-ethyl, chlorotoluron, chlomitrofen, chlorotoluron, chlorthal-dimethyl, clomazone, clodinafop, clopyralid, clomeprop, cyanazine, 2,4-D, 2,4-DB, daimuron, dalapon, desmedipham, desmetryn, dicamba, dichlobenil, dichloroprop, diclofop, difenzoquat, diflufenican, dimefuron, dimethachlor, dimethametryn, dimethenamid, dinitramine, diquat, diuron, endothall, ethametsulfuron-methyl, ethofumesan, fenac, fenclorim, fenoxaprop, fenoxaprop-ethyl, flamprop-methyl, flazasulfuron, fluazifop, fluazifop-p-butyl, flumetsulam, flumiclorac-penyl, fluoroglycofen, flumetsulam, flumeturon, flumioxazin, flupoxam, flupropanate, fluridone, fluroxypyr, flurtamone, fomasafen, fosamine, glufosinate, glyphosate and its salts thereof, (such as alkyl ammonium or group I metal salts), haloxyfop, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, isoproturon, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPB, mecoprop, mefenacet, mesotrione, metazachlor, methabenzthiazuron, metalachlor, methylarsonic acid, metolachlor, metobenzuron, metosulam, metamitron, naproanilide, naptalam, neburon, nicosulfuron, nonanoic acid, norflurazon, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, picloram, picolinafen, pretilachlor, prodiamine, prometon, prometryn, propachlor, propazine, propisochlor, propyzamide, pyrazolate, pyrazolynate, pyrazosulfuron-ethyl, pyributicarb, pyridate, quinclorac, quizalofop-ethyl, quizalofop-P, quinclorac, rimsulfuron, siduron, simazine, simetryn, sulcotrione, sulfamic acid, a sulfonylurea, 2,3,6-TBA, tembotrione, terbumeton, terbuthylazine, terbutryn, trichloroacetic acid, triclopyr, trietazine, thenylchlor, thiazopyr, tralkoxydim, trietazine, trifuralin, salts thereof, or a mixture thereof.
Examples of fungicidally active compounds include but are not limited to aldemorph, azoxystrobin, benalaxyl, benomyl, bitertanol, borax, boscalid, bromocuonazole, sec-butylamine, captafol, captan, calcium polysulfide, carbendazim, chinomethionat, chlorothalonil, chlozolinate, copper and its derivatives, copper sulfate, cyprodinil, cyproconazole, dichlofluanid, dichlorophen, diclomezine, dicloran, diethofencarb, difenoconazole, dimethomorph, diniconazole, dithianon, epoxiconazole, famoxadone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenpiclonil, fenpropidin, fenpropimorph, fentin, fluazinam, fludioxonil, fluoroimide, fluotrimazole, fluqinconazole, flusulfamide, flutolanil, folpet, fosetyl, furalaxyl, guazatine, hexachlorobenzene, hexaconazole, hydroxyquinoline sulfate, imibenconazole, iminoctadine, ipconazole, iprodione, kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, mercuric chloride, metam, metalaxyl, metconazole, metiram, myclobutanil, nabam, nickel bis(dimethyldithiocarbamate), nuarimol, oxadixil, oxine-copper, oxolinic acid, penconazole, pencycuron, phthalide, polyoxin B, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon, quintozene, spiroxamine, sulfur, tebuconazole, tecloftalam, tecnazene, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tridemorph, trifloxystrobin, triforine, triticonazole, vinclozolin, zineb, ziram, salts thereof, or a mixture thereof.
In one embodiment of the invention, the fungicides are selected from the group consisting of aromatic fungicides, conazole fungicides (including triazole and imidazole fungicides), morpholine fungicides, polymeric dithiocarbamate fungicides, pyrimidine fungicides, spiro-ring containing fungicides, and strobilurin fungicides.
In yet another embodiment of the invention, the fungicides are selected from the group consisting of bitertanol, chlorothalonil, difenoconazole, epoxiconazole, mancozeb, maneb, propriconazole, pyrimethanil, spiroxamine, tebuconazole and tridemorph.
Examples of insecticidally actives compounds include but are not limited to abamectin, acephate, acetamiprid, acrinathrin, amitraz, azadirachtin, azamethiphos, azinphos-methyl, azocyclotin, bensultap, bifenthrin, bromopropylate, buprofezin, butoxycarboxim, cartap, chlorantriniliprole, chlorfenapyr, chlorfenson, chlorfluazuron, clofentezine, coumaphos, cyfluthrin, beta-cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, theta-cypermethrin, cyromazine, DDT, deltamethrin, diafenthiuron, dicofol, dicrotophos, difenthiuron, diflubenzuron, dimethoat, emamectin benzoate, endosulfan, esfenvalerate, etoxazole, fenazaquin, fenbutatin oxide, fenoxycarb, fenpyroximate, fipronil, fluazuron, flubendiamide, flucycloxuron, flufenoxuron, tau-fluvalinate, formetanate, furathiocarb, halofenozide, gamma-HCH, hexaflumuron, hexythiazox, hydramethylnon, hydrogen cyanide, imidacloprid, lufenuron, methamidophos, methidathion, methiocarb, methomyl, methoxychlor, mevinphos, milbemectin, mineral oils, monocrotophos, nicotine, nitenpyram, novaluron, omethoate, organophosphorus compounds, oxamyl, oxydemeton-methyl, pentachlorophenol, phosphamidon, pymetrozin, permethrin, profenofos, pyridaben, rape seed oil, resmethrin, rotenone, spinetoram, spinosad, sulfluramid, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tetrachlorvinphos, tetradifon, tetramethrin, thiamethoxam, thiocyclam, thiodicarb, tralomethrin, trichlorfon, friflumuron, trimethacarb, vamidothion, and salts thereof, or a mixture thereof.
Examples of plant growth chemicals include but are not limited to 6-benzylaminopurine, chlorflurenol, chlormequat, chlorphonium, cimectacarb, clofencet, cloxyfonac, cyanamide, cyclanilide, daminozide, dikegulac, ethephon, flumetralin, fluriprimidol, forchlorfenuron, gibberilic acid, inabenfide, indolylbutyric acid, 2-(1-naphthyl) acetamide, mefluidide, mepiquat, paclobutrazol, N-phenylphthalamic acid, thidiazuron, trinexapac-ethyl, uniconzole, salts thereof, or a mixture thereof.
The agrochemical composition described herein may optionally comprise other agrochemically acceptable ingredients commonly found in agrochemical compositions, such as emulsifiers, organic surfactants, viscosity modifiers, antifoams, solvents and the like and be in any form which can lead to spraying of the agrochemical composition of the invention. These agrochemically acceptable ingredients are described in standard reference texts such as Chemistry and Technology of Agrochemical Formulations, ed. D. A. Knowles, Kluwer Academic Publishers (1998) and Controlled-Release Delivery Systems for Pesticides, Herbert B. Scher, Marcel Dekker, Inc. (1999).
The current invention can be used with liquid formulation types which can be prepared essentially without water, such as emulsifiable concentrates (EC), suspension concentrates for direct application (SD), spot application (SA) or pour on (PO) formulations, oil dispersible powder (OP) formulations, oil miscible liquid (OL) formulations, oil miscible flowable concentrate (OF) formulations, oil dispersion (OD) or suspo-emulsion (SE) formulations, the formulation types are described by Crop Life International: Catalogue of pesticide formulation types and international coding system. Technical Monograph nr. 2, 5th edition. (http://www.croplife.org/library/documents/technical%20monographs/technical%0monograph%20N%C2%B02-%20March%202002.pdf) Accessed Nov. 17, 2003.
Surfactants and emulsifiers which may be optionally present in compositions according to this invention can be nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric, zwitterionic, polymeric surfactants or any mixtures thereof.
The useful nonionic surfactants include alkoxylates, especially alkoxylated alcohols, alkoxylated fatty acids, especially ethoxylates and their derivatives including ethoxylated C8 to C24 saturated and unsaturated, linear and branched fatty acids or fatty alcohols, alkoxylated block copolymers, alkoxylated arylalkylphenols, especially ethoxylates and their derivates including alkylphenolethoxylates, alkoxylated amines, alkoxylated oils, fatty esters, especially polyethyleneglycol mono- and diesters of C8 to C24 saturated and unsaturated, linear and branched fatty acids, sorbitan derivatives including esters and ethoxylates, alkylpolyglucosides, and the like.
Typical ionic surfactants include alkylarylsulfonates, alkylarylsulfonic acids, carboxylated alcohol ethoxylates and alkylphenol ethoxylates, carboxylic acids/fatty acids, diphenylsulfonate derivatives, olefin sulfonates, phosphate esters, phosphorous organic derivatives, quaternary surfactants, sulfates and sulfonates of oils and fatty acids, sulfates and sulfonates of ethoxylated alkylphenols, sulfates of exthoxylated alcohols, sulfates of fatty acids, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalene and alkylnaphthalene, sulfonates of petroleum, sulfosuccinamates, alkanolamides, alkoxylated amines, N-acylsarocinates and the like.
An embodiment of the emulsifiers for this application are alkoxylated alcohols, alkoxylated alkylarylphenols and alkoxylated fatty acids, preferably of from 4 to about 50 ethylene oxide units and from 4 to 18 carbon atoms. Representative samples of ethoxylated arylalkyphenols are the TERGITOL® NP products from Dow-Union Carbide, of ethoxylated alcohols are TEGOALKANOL® TD products from Evonik-Goldschmidt, and of ethoxylated fatty acids is AROSURF® 8-190 from Evonik-Goldschmidt.
The agrochemical compositions according to this invention may comprise 0.01 to 99 vol. % of one or more of the alkylpolysiloxanes of siloxane (a) or siloxane (b), 1 to 99.99 vol. % of one or more oils, 0 to 30 vol. % of one or more agrochemically active ingredients, 0 to 15 vol. % of one or several emulsifiers, 0 to 95 vol. % of water and 0 to 50 vol. % of other inert ingredients.
A preferred range of agrochemical compositions according to this invention may comprise 0.1 to 5 vol. % of one or more alkylpolysiloxanes of siloxane (a) or siloxane (b), 10 to 60 vol. % of one or several oils, 0.5 to 20 vol. % of one or several agrochemically active ingredients, 0.1 to 6 vol. % of one or several emulsifiers, 20 to 85 vol. % of water.
A further preferred range of agrochemical compositions according to this invention may have reduced oil content and comprise 0.1 to 1 vol.% of one or more alkylpolysiloxanes of siloxane (a) or siloxane (b), 15 to 30 vol.%, of one or more paraffinic oil, vegetable oil or methylated vegetable oil, 2 to 15 vol. % of one or more agrochemically active ingredients, 0.1 to 3 vol. % of one or more emulsifiers, and 60-80 vol. % water.
As a result of the improved spreading and oil coverage of the HSCAS-comprising compositions of the present invention, a further embodiment of this invention is that reduced spray volumes can be achieved without reduced efficacy.
The agrochemical compositions according to this invention may be an emulsion (e.g. oil-in-water (O/W), water-in-oil (W/O), (W/O/W), (O/W/O), Pickering, microemulsion and nanoemulsions). In one embodiment of the invention, the emulsion is an O/W emulsion.
Preparation and types of emulsions are described in chapters 2 (“Emulsions—Properties and Production”) and 3 (“Microemulsions, Vesicles and Liposomes”) of Mollet et al., Formulation Technology—Emulsions, Suspensions, Solid Forms, Wiley-VCH, (2004), which is incorporated herein by reference.
The alkylpolysiloxanes of high silicone character may be present in the mixture of ingredients before the emulsification process or may be added to prepared emulsions of the other ingredients at a later time.
Alternatively, the agrochemical composition according to this invention may be a neat oil composition which is free of water or contains water in a range selected from the group consisting of less than 1%, less than 0.1%, less than 0.01% and less than 0.001% (all figures in vol. %)
In the method of producing the agrochemical compositions of the invention, the components can be added by any conventional means known in the art.
In another embodiment of the invention, the agrochemical compositions of the invention are especially useful for spraying mineral oil-containing agrochemical formulations by sprayers, which include but are not limited to handheld sprayers or via aerial application on plants.
Another embodiment of the invention is directed toward a method of treating plants against unwanted pests which comprises of administering a pesticidally effective amount of the agrochemical composition of the invention.
Another embodiment of the invention is directed toward a method of controlling unwanted weeds or treating plants against unwanted insects or disease, for example fungal, which comprises of administering a herbicidally, insecticidally or fungicidally effective amount of the agrochemical composition of the invention.
In another embodiment of the method of controlling unwanted weeds or treating plants, the agrochemical composition of the invention is administered on the stems, leaves, seeds or flowers of the unwanted weed or treated plant.
In yet another embodiment of the method of controlling unwanted weeds or treating plants, the agrochemical composition of the invention is administered on the leaves of the unwanted weed or treated plant.
In still another embodiment of the method of controlling unwanted weeds or treating plants, the agrochemical composition of the invention is administered on the leaves of the unwanted weed or treated plant which have a hydrophobic surface.
Leaves with hydrophobic corrugated surfaces can be difficult to wet and can hinder the full spreading of an agrochemical formulation over the whole leaf. The presence of alkylpolysiloxanes with high silicone character in the agrochemical compositions of the invention, provided a surprising and unexpected improvement in spreading as compared to previously used alkylpolysiloxanes and allows good coverage of the leaf.
In still another embodiment of the method of treating plants, the treated plant is of the genus Musa (e.g. bananas and plantains).
In still another embodiment of the invention, the agrochemical oil composition is administered to solid agrochemically active ingredients such as fungicides, herbicides, insecticides or fertilizers, to improve the handling properties and reduce the level of airborne particles.
In still another embodiment of the invention, the agrochemical oil composition is administered to treat seeds or to pesticidally treated seeds to enhance the coating properties.
It is well known in the art that improved coverage is beneficial for the efficacy of the spray. The presence of alkylpolysiloxanes with high silicone character in the compositions according to this invention may allow the reduction of the oil or active ingredient contents in the spray formulation with significant economical and ecological benefits without negatively affecting the biological effect, or the reduction of the overall spray volume.
The invention is further described by the following non-limiting examples which further illustrate the invention, and are not intended, nor should they be interpreted to, limit the scope of the invention.
BANOLE® HV oil, paraffinic distillate from hydrocracking process, Total Fluids, 76430 (Oudalle, France).
ORCHEX® 796 oil, hydrotreated light paraffinic distillate, Calumet Lubricants Co. (Indianapolis, Ind.).
SUNSPRAY® 6N oil, severely solvent refined heavy and/or only light paraffinic petroleum oils, Sunoco, Inc. (Philadelphia, Pa.).
STYLET-OIL®, severely hydrotreated paraffinic oil plus nonionic emulsification system, JMS Flower Farms, Inc., Vero Beach, Fla.
AGNIQUE® ME 18 S-U, methyl soyate, Cognis Corporation, (Cincinnati, Ohio).
DITHANE® 60 SC is a commercial mancozeb fungicide provided by Dow Agrosciences (San Jose, Costa Rica).
CALIXIN® 86 OL is a commercial tridemorph fungicide provided by BASF Costa-Rica
TERGITOL™ NP-7 is a commercial nonylphenol ethoxylate available Dow-Union Carbide Corporation (Danbury, Conn.).
AROSURF® 8-190 is a commercial oleic acid ethoxylate available from Evonik-Goldschmidt Chemical Corporation (Hopewell, Va.).
Digital Image Camera, Model DC200 from DAGI-MTI (Michigan City, Ind.).
For the purposes of the present invention, interfacial tension is measured by the Wilhelmy plate method using a Krüss Processor Tensiometer K12 at 25° C.
HSCAS-1 is a siloxane (a) with high silicone character according to this invention, having a structure according formula (I) wherein R and R″ is methyl, R′ is hexadecyl, u is 83 and v is 5, wherein u/v is 16.6, which can be prepared in a method analogous to that described in U.S. Pat. No. 6,669,949, comparative example 7, by hydrosilylation of the corresponding SiH-functional siloxane (0.75 val/kg hydrogen) with 1-hexadecene in the presence of hexachloroplatinic acid.
HSCAS-2 is a siloxane (b) with high silicone character according to this invention, having a structure wherein R1 is methyl, which can be prepared in a method analog to that described in EP 1 679 335 (U.S. Patent Application Publication 2006-155090), example 2, by sequential hydrosilylation of a SiH-functional siloxane (3.5 val/kg hydrogen) with a) a vinylsiloxane of the structure CH2═CH—SiMe2—O—[SiMe2—O]348—SiMe2—CH═CH2, and b) 1-hexadecene, in the presence of a platinum catalyst.
Low Molecular Weight Siloxane (LMAS-1) is the siloxane described as AMS-1 in U.S. Pat. No. 5,561,099, example 1.
LMAS-2 is a low molecular weight alkylsiloxane commercially available from Momentive under the tradename Silwet 560, which is covered by U.S. Pat. Nos. 5,561,099 and 5,658,852 and corresponding foreign patents.
LSCAS-1 is a Low Silicone Character Alkylsiloxane (i.e. having a ratio of u/v of less than 10), with a structure according to formula I, wherein R and R″ is methyl, R′ is hexadecyl, u is 2, v is 2, having a ratio of u/v of 1, which can be prepared analogous to the conditions described in example 1 of this invention from the corresponding SiH-functional siloxane and 1-hexadecene in the presence of a platinum catalyst.
LSCAS-2 is a Low Silicone Character Alkylsiloxane (i.e. having a ratio of u/v of less than 10), with a structure according to formula I, wherein R and R″ is methyl, R′ is hexadecyl, u is 75, v is 25, having a ratio of u/v of 3, which can be prepared analogous to the conditions described in example 1 of this invention from the corresponding SiH-functional siloxane and 1-hexadecene in the presence of a platinum catalyst.
APES-1 is a mixture containing asymmetrical alkyl/polyether-modified siloxanes and is prepared as described in U.S. Pat. No. 6,669,949, example 8.
PES-1 is a is a commercial superspreading polyether-modified trisiloxane surfactant, available from Evonik-Goldschmidt Chemical Corporation (Hopewell, Va.) under the tradename BREAK-THRU® S 240, and covered by U.S. 2005/0244357 A1.
PES-2 is a commercial silicon polyether surfactant available from Evonik-Goldschmidt Chemical Corporation (Hopewell, Va.) under the trade name BREAK-THRU® OE 441, and covered by U.S. 2005/0244357 A1.
This example exhibits the solubility of the oil spreaders and demonstrates that alkyl siloxanes with high silicone character (HSCAS) show excellent reduction of the surface tension of typical mineral oils to a significantly greater extent than for alkyl siloxanes with low molecular weight (LMAS) and/or low silicone character (LSCAS).
The siloxanes were mixed with the BANOLE HV and ORCHEX 796 at a concentration of 0.5 wt. % or with SUNSPRAY 6N at 1 wt. %.
The upper row in each field denotes the compatibility (clear=fully compatible), the second row the interfacial tension in mN/m.
This example exhibits the solubility of the oil spreaders and demonstrates that alkyl siloxanes with high silicone character (HSCAS) show an excellent reduction of the surface tension of methylated vegetable oils, to a significantly greater extent than for alkyl siloxanes with low molecular weight (LMAS) and/or low silicone character (LSCAS).
The siloxanes were mixed with the methyl soyate at 1 wt. %.
The upper row in each field denotes the compatibility (clear=fully compatible), the second row the interfacial tension in mN/m.
This example demonstrates that HSCAS exhibit excellent compatibility and reduction of the surface tension of mineral and methylated vegetable oils, and to a significantly greater extent than observed with polyether siloxanes according to U.S. 2005/0244357 A1.
The siloxanes were mixed with the BANOLE HV and ORCHEX 796 at a concentration of 0.5 wt. % and with SUNSPRAY 6N and methylated vegetable oil at 1 wt. %.
The upper row in each field denotes the compatibility (clear=fully compatible), the second row the interfacial tension in mN/m.
The polyether siloxanes according to U.S. 2005/0244357 A1 are incompatible with the paraffinic mineral oils. In methylated vegetable oil, these polyether siloxanes reduce the surface tension significantly less efficiently than achieved in compositions comprising HSCAS.
The spreading performance of compositions of the invention with a mineral oil is evaluated on polyester transparency film from Hewlett Packard (HP C3834A). Spreading is determined by applying 50 μL drops of the mineral oil composition onto the side with coarser texture of the film sheet using a micropipette and measuring the spread diameter. For the BANOLE HV paraffin oil, spread diameters are measured with a ruler after 15 minutes and the data is tabulated in TABLE 4.
It is demonstrated that mineral oil compositions comprising HSCAS have excellent spreading properties and are superior compared to compositions comprising PES, APES, and LSCAS siloxanes.
The spreading performance of compositions of the invention with a methylated vegetable oil is evaluated on polyester transparency film from Hewlett Packard (HP C3834A). Spreading is determined by applying 50 μL drops of the methylated vegetable oil composition onto the side with coarser texture of the film sheet using a micropipette and measuring the spread diameter. For the methylated vegetable oil, spread diameters are measured with a ruler after 10 minutes and the data are tabulated in TABLE 5.
It is demonstrated that compositions comprising alkylated vegetable oils and HSCAS have excellent spreading properties and are superior compared to compositions comprising PES and LSCAS siloxanes.
Organic JMS Stylet-Oil® is a paraffinic oil registered for control of aphids, mites and other insects. The surface tension reduction and spreading performance of Stylet-oil compositions of this invention is presented in this example. The spreading performance is determined by applying 50 μL drops of the oil composition using a micropipette onto the underside of the polyester transparency film sheet (Hewlett Packard (HP C3834A)) and measuring the spread diameter with a ruler after 15 minutes. This information is compiled in Table 6.
It is demonstrated that insecticidal oil compositions comprising HSCAS show reduced surface tension and excellent spreading properties, and are superior compared to compositions comprising LSCAS and APES.
Mineral oils provide protection against pests and disease in agrochemical applications. The improved spreading performance of mineral oil compositions of this invention on banana leaves is presented in this example. Spreading is determined by placing 0.5 μL drops of a blend of 0.5% siloxane in ORCHEX 796 oil between the veins of a banana leaf with a micropipette and capturing photos of the spread from a fixed camera at one minute intervals.
In following TABLES no. 7, 8, 9, 11, 13, 15, 17 and 21 the area of spread is calculated by printing both images of comparative photographs in the same scale, followed by measuring the relative area of the drop as a rectangle in square millimeters. Due to the channeling effect of the raised veins of the leaf, the spreading of the compositions of this invention is generally rectangular in appearance. Based on the averaged values for each material evaluated, the following relative spread factors are provided:
These data demonstrate the excellent spreading of oil compositions comprising mineral oils and HSCAS on corrugated leaf surfaces such as banana leaves, superior compared to compositions comprising LSCAS or LMAS.
Mineral oils provide protection against pests and disease in agrochemical applications. The improved spreading performance of paraffinic oil compositions of this invention on banana leaves is presented in this example. Spreading is determined by placing 0.5 μL drops of a blend of 0.5% siloxane in ORCHEX 796 oil between the veins of a banana leaf with a micropipette and capturing photos of the spread from a fixed camera at one minute intervals.
These data demonstrate the excellent spreading of oil compositions comprising mineral oils and HSCAS on corrugated leaf surfaces such as banana leaves, superior compared to compositions comprising LMAS, APES or polyethermodified siloxanes.
This ability of HSCAS-1 and HSCAS-2 to promote spreading of a methylated vegetable oil on a leaf surface is demonstrated in this example. Spreading is determined by placing 0.5 μL drops of a blend of 1% siloxane in methylated vegetable oil between the veins of a banana leaf with a micropipette and capturing photos of the spread from a fixed camera at one minute intervals.
Photographs recorded at 2 minute intervals where HCAS-1 and HSCAS-2 are compared against Low Molecular Weight Siloxanes (LMAS-1 and LMAS-2).
These data demonstrate the excellent spreading of oil compositions comprising methylated vegetable oils and HSCAS on corrugated leaf surfaces such as banana leaves, superior compared to compositions comprising low molecular weight alkylsiloxanes.
Oil sprays for protection of banana plants may be aqueous emulsions of oil and one or more fungicides to control diseases such as black sigatoka. This example demonstrates that the alkyl siloxanes with high silicone character improve spreading of mineral oil emulsions containing fungicides. With HSCAS incorporated into the emulsions, the oil amount may be reduced by up to 50% without impairment of the spreading or leaf coverage of the fungicide and oil.
Table 10 lists the ingredients, order of addition and quantities for the emulsions tested for spreading capability. BANOLE HV oil, TERGITOL NP-7 emulsifier, CALIXIN® 86 OI tridemorph fungicide, and HSCAS-1 are first thoroughly blended with stirring, and then the water is slowly charged. The emulsion is agitated until uniform and ready for application.
Spreading of these oil/fungicide emulsions is determined by placing 0.1 μL drops between the veins of a banana leaf with a micropipette and capturing photos from a fixed camera at five minute intervals.
Incorporating a ruler with millimeter markings for reference, photographs confirm that addition of HSCAS-1 improves the spread area of the oil over the leaf surface and even surpasses the spread of a standard emulsion with twice the oil content.
These data demonstrate the excellent spreading of emulsions comprising mineral oils, pesticides and HSCAS. The incorporation of a small amount of HSCAS unexpectedly provides superior spreading and leaf coverage even for compositions comprising a significantly reduced oil volume compared to typical oil compositions without HSCAS.
Oil sprays for protection of banana plants may be aqueous emulsions of oil and one or more fungicides to control diseases such as black sigatoka. This example demonstrates that oil emulsions comprising HSCAS spread to a greater extent than comparative compositions with LMAS, or compositions with twice the oil content. The composition of the oil and fungicide emulsions for this example are provided in Table 12 compared to LMAS-1. The emulsion compositions in Table 12 were prepared by the method described in Example 10.
Spreading is determined by placing 0.1 μL drops of the oil/fungicide emulsion between the veins of a freshly excised banana leaf with a micropipette and capturing photos of the spread from a fixed camera at five minute intervals.
Incorporating a ruler with millimeter markings for reference, photographs confirm that addition of HSCAS-1 and HSCAS-2 improves the spread area of the oil over the leaf surface and significantly surpasses the spreading of a standard emulsion with twice the oil content or the spreading of an emulsion with LMAS.
These data demonstrate the excellent spreading and leaf coverage of emulsions comprising mineral oils, pesticides and HSCAS, superior to compositions comprising LMAS.
Oil sprays for protection of banana plants may be aqueous emulsions of oil with one or more fungicides to control diseases such as black sigatoka. This example demonstrates that the alkylsiloxanes with high silicone character improve spreading of oil emulsions with mancozeb fungicide on banana leaves.
The emulsions compositions for this example are provided in Table 14. The BANOLE HV paraffinic oil is blended with the siloxane and TERGITOL NP-7 emulsifier. Water 1 is added to prepare the emulsion, and the DITHANE 60 SC mancozeb fungicide is then slowly dispersed. The second water aliquot is added, and the emulsion is mixed continuously to suspend the mancozeb prior to application.
Spreading is determined by placing a 0.1 μL drop of the oil/fungicide emulsion between the veins of a freshly excised banana leaf with a micropipette and capturing photos of the spread from a fixed camera at five minute intervals.
Incorporating a ruler with millimeter markings for reference, photographs confirm that addition of HSCAS-1 and HSCAS-2 improves the spread area of the oil over the leaf surface and surpasses the spread of a standard emulsion with twice the oil content.
The data show that alkyl siloxanes with high silicone character are highly effective for spreading of fungicidal oil emulsions with reduced oil content.
The enhanced spreading with HSCAS successfully compensates for the oil reduction of 50% in the emulsions.
Oil sprays for protection of banana plants may be aqueous emulsions of oil containing one or more fungicides to control diseases such as black sigatoka. This example demonstrates that the alkyl siloxanes with high silicone character improve spreading of oil with emulsions which contain a combination of tridemorph and mancozeb fungicides.
The emulsion compositions of this example and the order of addition of the additives are listed in Table 16.
Spreading is determined by placing 0.1 μL drops of the oil/fungicide emulsion between the veins of a freshly excised banana leaf with a micropipette and capturing photos of the spread from a fixed camera at five minute intervals. The fresh leaf was fixed to a glass plate which was positioned at an angle of 10 degrees.
Incorporating a ruler with millimeter markings for reference, photographs confirm that addition of HSCAS-1 improves the spread area of the oil over the leaf surface and surpasses the spread of the standard emulsion with twice the oil content.
This example demonstrates the excellent spreading and leaf coverage of pesticidal oil compositions with reduced oil volume, comprising HSCAS, on corrugated and non-flat leaf surfaces. It was unexpectedly observed that the finally covered leaf area extended upslope from the position of the original droplet on an angled leaf surface.
This example demonstrates that HSCAS may be blended into fungicidal/oil compositions at different addition points without adversely affecting improved oil spreading performance. In Blend A in TABLE 10, the HSCAS-1 siloxane is added after the oil is first emulsified in water. In Blend B, it is present in the oil prior to emulsification in water.
Spreading is determined by placing 0.1 μL drops of the oil/fungicide emulsion between the veins of a freshly excised banana leaf with a micropipette and capturing photos of the spread from a fixed camera at five minute intervals. Using the millimeter scale on the reference ruler in these photos, differences in the spreading of the oils and fungicides are indistinguishable, so HSCAS-1 may be incorporated into the emulsions at multiple addition points.
The data show that the addition sequence of the HSCAS in the preparation of the fungicidal oil emulsions has no effect on the spreading performance.
This example demonstrates that fungicidal oil compositions may be prepared with nonionic emulsifiers. The emulsion compositions and the order of introduction of components is presented in TABLE 20.
Spreading is determined by placing 0.1 μL drops of the oil/fungicide emulsion between the veins of a freshly excised banana leaf with a micropipette and capturing photos of the spread from a fixed camera at five minute intervals. With the millimeter scale as reference in these photos, spreading of the oil and fungicide composition with AROSURF 8-190 is comparable to the composition with TERGITOL NP-7 with HSCAS-1 present at 1 vol. %. AROSURF 8-190 is a suitable as an emulsifier for these compositions.
The results show that emulsified oil compositions comprising HSCAS, nonionic emulsifiers (such as fatty acid ethoxylates or nonylphenol ethoxylates) pesticides, and a reduced oil volume show excellent spreading and leaf coverage, significantly higher than even for compositions comprising twice the amount of oil but without HSCAS.
A field trial was conducted to evaluate the performance of oil sprays with
HSCAS-1 siloxane of high silicone character and the fungicides THANE® 60 SC (mancozeb) and CALIXIN® 86 OL (tridemorph) on banana plants for control of black sigatoka disease. The rainfall intensity, particularly in the first 12 weeks of the 15 week trial, resulted in heavy black sigatoka disease pressure. This example demonstrates that incorporation of HSCAS into fungicidal sprays for bananas allows for oil reductions of up to 50% while maintaining control of black sigatoka disease.
The field trials and disease pressure evaluations were performed by a skilled experimenter. All treatments were applied weekly with a backpack sprayer at a 20 liters/hectare spray volume. A single row protocol of 10 banana plants was employed: however, only plants in the middle of the row were selected for weekly evaluation of disease. A row of 10 banana plants with no spray treatment was designated as the control.
The pesticide formulation contained 40% mineral oil (Spraytex M), 7.5% DITHANE 60 SC and 2.5% CALIXIN 86 OL. Cocktails which contained HSCAS-1 were comprised of 20% mineral oil and the same fungicide levels of mancozeb and tridemorph as the standard formulation. For reference, emulsions of 20% SPRAYTEX were prepared with the commercial levels of DITHANE 60 SC and CALIXIN 86 OL, but absent the HSCAS-1. The cocktails compositions and Row Number of Treatment are provided in TABLE 22.
Assessments of black sigatoka disease severity were recorded by a skilled experimenter using the Stover Scale modified by Gaulh (Gauhl F. 1994. Epidemiology and Ecology of Black Sigatoka (Mycosphaerella fijiensis Morelet) on Plaintain and Banana in Cost Rica, Central America. Translation of a 1989 PhD thesis originally in German, Unversitat Gottingen, Gottingen Germany). Evaluations started when the first treated leaf reached position number 4 and every 7 days thereafter until a week after the last application. Phytoxicity was also monitored qualitatively. Disease severity is the most reliable parameter to measure differences between treatments. In the following tables, disease severity is determined by AUC (area under the curve). A statistical analysis using Tukey's multiple range test was performed, and, in the following table, averages with the same letter in the rating are not statistically different (P=0.05).
The disease severity and rating data show that there is an increase in black sigatoka disease when the oil is reduced from 8 liters to 4 liters/hectare in the spray emulsion. However, disease severity is significantly lower in formulations comprising reduced mineral oil content and HSCAS-1. These data demonstrate that HSCAS-1 allows for reduced oil content in fungicidal spray emulsions for control of black sigatoka disease in banana plants without negative effect on disease control.
Having thus described in detail various embodiments of the present invention, it is to be understood that the invention defined by the above paragraphs is not to be limited to particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope of the present invention.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP09/61385 | 9/3/2009 | WO | 00 | 6/27/2011 |
| Number | Date | Country | |
|---|---|---|---|
| 61106307 | Oct 2008 | US |
