MXPA98001562A - Pesticial compositions - Google Patents

Abstract

The present invention relates to pesticidal compositions. In particular, the present invention relates to pesticidal compositions comprising a pesticide and a redispersion polymer, and even method for controlling the pest in agriculture by applying to the pest or site thereof a pesticidal composition comprising a pesticide and a pesticide. redispersi polymer

Description

PESTICIDE COMPOSITIONS The present invention relates to pesticidal compositions. In particular, the present invention relates to pesticidal compositions comprising a pesticide and a redispersion polymer. The present invention also relates to a method for controlling the pest in agriculture, by applying to the pest or site thereof a pesticidal composition comprising a pesticide and a redispersion polymer. The compositions with which the pest is intended to be controlled in agriculture are typically applied by spraying a composition comprising the pesticide using water as the carrier liquid. For this reason, pesticide compositions are provided to the farmer in formulations intended to be dissolved or dispersed in water. These formulations may be liquid formulations such as aqueous solutions or emulsifying concentrates, or solid formulations such as wetting powders or granular formulations. Solid formulations have many advantages over liquid formulations in terms of cost, storage and packaging, including the packaging container. The biological effectiveness of pesticides is influenced by many factors, particularly the residence time of the pesticide on the treated surface, which is usually the leaf surface of a plant. A major factor influencing the residence time is the degree to which the pesticide resists washing / disposal caused by rain, that is, the constancy of rainfall. With liquid formulations, the constancy of rainfall can be improved by including ingredients in the formulation or by adding said ingredients to the spray tank (mixed in the tank) which, during drying, provides a water resistant bond between the pesticide and the substrate. For example, water insoluble or emulsified oil polymers, prepared in emulsion, have been used to improve the constancy of rain with the liquid formulation. A widely used material is a formulation comprising a carboxylated synthetic latex emulsion polymer, an alkylated, primary aliphatic, oxyalkylated alcohol, and water. This material has been shown to improve the effectiveness of a variety of pesticides. However, because it is a liquid formulation, it can not be used as a component for a solid pesticidal formulation. Solid formulations present a different set of competent problems, when compared to liquid formulations. For the solid formulations to be easily dispersed in water, water-resistant additives can not be used in the formulation. In fact, high levels of water-soluble dispersants are typically required for the solid formulation to be dispersed in the spray tank. Although water insoluble or emulsified oil polymers, prepared in emulsion, have been used with liquid formulations or in mixtures in tanks, none have been described that address the problem to improve the constancy of solid formulations in the rain, without have to require a tank mix additive separately. This is both inconvenient and problematic for the farmer who wants to use a solid dry pesticide formulation. Dry solid formulations are particularly important since they can be stored, packaged and transported more easily than their liquid counterparts. Therefore, there is a continuing need for additives that are compatible with the solid pesticidal formulations. We have discovered that redispersion polymers can be used as pesticide additives. Redispersion polymers are solid compositions incorporating water insoluble polymers prepared in a combined emulsion, before drying, with water soluble polymers. Said compositions are typically isolated through spray drying, and the products are called redispersion powders. The water soluble polymer is critical in the redispersion of the water insoluble polymer. These polymers overcome many of the problems associated with the use of emulsion polymers as auxiliaries in solid pesticidal formulations. further, these provide a surprising increase in the effectiveness of many pesticides, and improved resistance to washing / disposal caused by rain. Thus, this invention provides a pesticidal composition, comprising: (a) one or more pesticides; and (b) one or more redispersion polymers, comprising: (1) one or more water-insoluble polymers, prepared in emulsion; and (2) one or more water soluble polymers. The composition may further comprise other ingredients to help the pesticide to disperse in the water, to modify the surface tension of the spray and to promote the adhesion of the water-insoluble polymers. The term "pesticide" means a chemical that is intended to mitigate a pest, including insects, weeds, fungi and related organisms. For purposes of this invention, a pesticide may also include viruses, bacteria or other organisms that can control pests and that are or can be modified to form a stable particle. The pesticide preferably comprises from 5 to 90% by weight of the pesticidal composition. The pesticide of the composition of this invention can take the form of a pure active ingredient, a technical grade of the active ingredient or an active ingredient formulated with one or more agronomically acceptable carriers. By "agronomically acceptable carrier" is meant any substance that can be used to assist the dispersion of the active ingredient in the composition in water without harming the effectiveness of the active ingredient, and which by itself has no significant harmful effect on the earth, the equipment, desirable plants or the agronomic environment. Pesticides in the form of particles are preferred. Particles that are within the range of 0.1 to 20 microns in diameter are even more preferred. The term "redispersion polymer" means a free flowing dry powder, comprising one or more water-insoluble polymers and one or more water-soluble polymers, produced by drying an emulsion polymer dispersion, which is easily redispersed in water, but when it dries a second time, it forms a water resistant film. Redispersion polymers are well known in the art. For example, in the US patent no. 3,784,648 (RE 28,780) (synthetic resins insoluble in water with a condensation product, soluble in water, of melamine and formaldehyde, which contains sulfonate groups); US patent no. 5,536,779 (polymer powder derived from unsaturated monomers, and at least one added product of starch degradation); US patent no. 5,519,084 (acrylic emulsion polymers and polyvinyl alcohol); German Patent DE 4,402,408 (unsaturated copolymers and protective colloids subsequently added); Japanese document JP 7,053,730 (acrylic emulsion polymers and colloid prepared from sodium styrene sulfonate and a polymerizing emulsifying agent); European Patent EP 632096 (acrylic and vinyl emulsion polymers, with amino functional polyvinyl alcohol); US patent no. 5,252,704 (acrylic vinyl emulsion polymers, with polyvinyl pyrrolidone); US patent no. 5,225,478 (emulsion polymers of olefinically unsaturated monomers with water-soluble metal salts of formaldehyde / phenolsulfonic acid condensates); and EP 723975 (emulsion copolymers of styrene and alkyl (meth) acrylates with water-soluble colloids). Many redispersion polymers are two-step emulsion polymers, formed when a water-soluble polymer, of the second stage, forms a "shell" or shell around a discrete domain or "core" of the water-insoluble polymer of the first stage. . Examples of such core-shell polymers are shown in U.S. Pat. 4,916,171 and 5,403,894. In these examples, the water soluble polymer is a copolymer of methacrylic acid which is neutralized with a base. U.S. Patent No. 4,876,313 also teaches the use of polyfunctional compounds to link or partially graft water-insoluble and water-soluble polymers. One embodiment of this invention provides a composition "comprising a pesticide, formulated as a wetting powder, ash or granule that is dispersed, and a redispersion powder comprising one or more water-insoluble polymers prepared in emulsion and one or more soluble polymers. in water, such as those disclosed in the above references. Another embodiment of this invention provides a wetting powder, ash or pesticidal formulation in dispersed granules, comprising one or more pesticides and one or more resispersion polymers, wherein the formulation is prepared by a process comprising the following steps: ) combining a dispersion of the pesticide in water with one or more water-insoluble polymers formed in emulsion, and one or more water-soluble polymers, and b) drying the combination. Another embodiment of this invention provides a dry pesticidal auxiliary comprising one or more redispersion polymers comprising: (1) one or more water-insoluble polymers prepared in emulsion; and (2) one or more water soluble polymers. Yet another embodiment of this invention provides a method for controlling a pest, which comprises applying to the pest, the site of the pest or a food source thereof, a pesticidal composition comprising: (a) one or more pesticides; and (b) a redispersion polymer comprising: (1) one or more water insoluble polymers, prepared in emulsion; and (2) one or more water soluble polymers.

Yet another embodiment of this invention provides a method for controlling a pest, which comprises applying to the pest, the site of the pest or a food source of the pest, a pesticidal composition comprising: (a) one or more pesticides; and (b) a redispersion polymer comprising: (1) one or more water insoluble polymers, prepared in emulsion; and (2) one or more water soluble polymers. Preferred water-insoluble polymers are emulsion polymerized and have an emulsion particle size of 0.1 to 5 microns. To obtain the proper balance of properties, the preferred water-insoluble polymers are selected from one or more homopolymers and copolymers independently comprising polymer units derived from: (1) one or more acrylic ester monomers; Acrylamides or substituted acrylamides; styrene or substituted styrenes; butadiene; vinyl acetate or other vinyl esters; vinyl monomers such as vinyl chloride, vinylidene chloride, N-vinyl pyrrolidone; acrylonitrile and methacrylonitrile, wherein the water-insoluble polymer has a glass transition temperature between 0 and 60 degrees Celsius (° C), preferably between 0 and 40 ° C, and (2) vinyl and ethylene esters, wherein the water-insoluble polymer has a glass transition temperature between -20 and 40 ° C. Acrylic ester monomers include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, acrylate 2- ethylhexyl, decyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate. Preferred water-insoluble polymers comprise monomer units derived from 2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, styrene and vinyl acetate. When the water-insoluble polymer comprises units derived from vinyl acetate, a more preferred form of the polymer has more than 3% of the vinyl acetate units hydrolyzed by the addition of an inorganic base. The water-insoluble polymer preferably comprises from 5 to 80% by weight of the pesticidal composition. Preferred water soluble polymers are nonionic polymers, wherein the nonionic polymer has a molecular weight greater than 2,000 amu such as, for example, polymers and copolymers comprising units derived from one or more of: polyvinyl alcohol, methacrylate of methyl and methacrylic acid. Polyvinyl alcohol or partially hydrolyzed copolymers of vinyl esters, for example, vinyl acetate, are preferred nonionic polymers. The water soluble polymer preferably comprises from 1 to 40% by weight of the pesticidal composition. The compositions of this invention usually benefit from the presence of an added surfactant. An expert in the art will recognize the circumstances in which the surfactants are typically combined with the pesticide to be applied. We have found that in some cases the combination of the surfactant and the redispersion polymer provides an increase in the biological activity of the pesticide, contrary to what might be expected based on the biological activity of the pesticide in the presence of the surfactant or the redispersion polymer alone. . One possible explanation for this phenomenon is that the redispersion polymer provides improved resistance against washing / eliminating the pesticide / surfactant mixture. The surfactants that can be used in combination with redispersion polymers include one or more nonionic, anionic and amphoteric surfactants. Examples of nonionic surfactants that are useful include the polyalkylene glycol ethers and condensation products of alkyl phenols, aliphatic alcohols, aliphatic amines and fatty acids with ethylene oxide, propylene oxide or mixtures thereof, such as phenols of ethoxylated alkyl or polyaryl and ethoxylated aryl phenols, and carboxylic esters solubilized with a polyol or polyoxyethylene. Anionic surfactants include salts of sulfonic acids of alkyl aryl, sulphonated polyglycol ethers, salts of sulfosuccinic acid esters with hydrophobic such as 2-ethylhexanol, salts of phosphonated polyglycol ethers, salts of alkyl sarcosine, salts of alkyl isethionate , and taurine derivatives. The additional benefit is provided by surfactants that improve the adhesive character of the redispersion polymer. The solid surfactants are more preferred, they can be dry blended with the redispersion / pesticide polymer composition. Examples of such surfactants include dioctyl sodium sulfosuccinate, sodium lauryl sulfate and N-methyl-taurine fatty acid amides. To further promote the formation of a film containing the pesticide, on the surface to which the pestleide is applied, one or more additional film-forming auxiliaries may be added to the composition. Said auxiliaries include low molecular weight solids that are soluble in both water and polymer. Preferred film-forming auxiliaries include caprolactam and neopentyl glycol. Some solid surfactants, such as dioctyl sodium sulfosuccinate, can also serve as film-forming auxiliaries. The compositions of this invention can be prepared in a variety of ways. One method is to mechanically combine the pesticide with the redispersion polymer, both components in the form of solids. This mixing process can vary from a simple procedure in which the two solid materials are physically mixed together, to a complex process in which the two components are mixed together with additional components and form a granular material, where the granular particles contain both components . Alternatively, the redispersion powder can be mixed with a redispersion granule, forming a surface coating on the granule. The compositions can also be prepared by combining an aqueous dispersion of the pesticidal component containing at least one of the water-insoluble polymers with the water-soluble polymer, and then drying to the solid form. The redispersion polymer itself can also be added to the spray tank before or after the addition of the pesticide. For some applications, one or more pesticides may be combined in the compositions of the present invention, from which additional benefits and effectiveness are provided, including less total pesticide applications, than if the pesticides were applied separately. When mixtures of pesticides are employed, the relative proportions of each in the composition will depend on the relative efficacy and the desired rate of application of each pesticide with respect to the crops and / or weed to be treated. Those skilled in the art will recognize that mixtures of pesticides can provide advantages such as a broader spectrum of activity, than a pesticide used alone. Examples of pesticides that can be combined in the compositions of the present invention include: (1) fungicides such as, for example, (a) dithiocarbamates and derivatives such as: ferric dimethyldithiocarbamate (ferbam), zinc dimethyldithiocarbamate (ziram), ethylenebisdithiocarbamate manganese (maneb) and its coordination product with zinc ion (mancozeb), zinc ethylenebisdithiocarbamate (zineb), zinc propylenebisdithiocarbamate (propineb), sodium methyldithiocarbamate (metam), tetramethylthiuram disulfide (thiuram), the zineb complex and polyethylene thiuram disulfide, 3, 5-dimethyl-l, 3, 5-2H-tetrahydrothiadiazine-2-thione (dazomet); and mixtures thereof, and mixtures with copper salts; (b) nitrophenol derivatives such as: dinitro- (1-methylheptyl) phenyl crotonate (dinocap), 2-sec-butyl-4,6-dinitrophenyl-3, 3-dimethylacrylate (binapacryl), and isopropyl carbonate 2 -sec-butyl-4,6-dinitrophenyl; (c) heterocyclic structures such as: N-trichloromethyl thiotetrahydroftalimide (captan), N-trichloromethyl thiophthalimide (folpet), 2-heptadecyl-2-imidazole acetate (glyodine), 2-octylisothiazolone-3,4,4-dichloro-6- ( o-chloroanilino) -s-triazine, diethyl phthalimidophosphorothioate, 4-butyl-l, 2,4-triazole, 5-amino-l-8bis (dimethylamino) phosphinyl) -3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-l, 2,4-thiadiazole, 2,3-dicyano-1,4-dithiaanthroquinone (dithianone), 1,3-dithiolo- (4,5-b) quinoxaline-2- thione (thioquinox), ethyl 1- (butylcarbamoyl) -2-benzimidazole carbamate (benomyl), 2-4 '- (thiazolyl) benzimidazole (thiabendazole), 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone , 3- (3,5-dichlorophenyl) -5-ethenyl-5-methyl-2,4-oxazolidinedione (vinolozoline); 3- (3,5-dichlorophenyl) -N- (1-methylethyl) -2,4-dioxo-1-imidazolidenecarboxamide (iprodione); N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide (procymidone; beta (4-dichlorophenoxy) -alpha- (1,1-dimethylethyl) -l "Hl, 2,4-triazole -l-ethanol (triadimenol); 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone (triadimefon); beta- ( 1,1'-biphenyl) -4-yloxyl) -alpha- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (bitertanol); 2,3-dichloro-N- (4 -fluorophenyl) maleimide (fluoromide); l- (2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl) -1"H-1,2,4-triazole; pyridine-2-thiol-l-oxide, 8-hydroxyquinoline sulfate and metal salts thereof; 2,3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin, alpha (phenyl) -alpha- (2, -dichlorophenyl) -5-pyrimidinylmethanol (triarimol), cis-N- (1, 1,2,2-tetrachloroethyl) thio) -4-cyclohexane-1,2-dicarboximide, 3- (2- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxy) glutarimide (cycloheximide), dehydroacetic acid, N- (1,1,2,2-tetrachloroethylthio) -3a, 4,7,7-tetrahydrophthalimide (captafol) , butyl-2-ethylamino-4-hydroxy-6-methylpyrimidine (etirimol), 4-cyclodecyl-2,6-dimethylmorpholine acetate (dodemorf), 4- (3- (4-chlorophenyl) -3- (3 , 4-dimethoxyphenyl) cryloyl) morpholine (dimethomorph), trifluzamide and 6-methyl-2-oxo-l, 3-dithiolo (4,5-b) -quinoxaline (quinomethionate); (d) various halogenated fungicides, such as: tetrachloro-p-benzoquinone (chloranil), 2-3-dichloro-l, 4-naphthoquinone (diclone), 1,4-dichloro-2,5-dimethoxybenzene (chloroneb), acid 3, 5t 6-trichloro-o-anisic (tricamba), 2,4,5,6-tetrachloroisophthalonitrile (TCPN), 2,6-dichloro-4-nitroaniline (dichloro), 2-chloro-l-nitropropane, polychloronitrobenzenes such as pentachloronitrobenzene (PCNB), and tetrafluorodichloroacetone; (e) fungicidal antibiotics such as: griseofulvin, kasugamycin and strepto icine; (f) copper-based fungicides, such as copper hydroxide, cuprous oxide, basic cupric chloride, basic copper carbonate, copper terphthalate, copper naphthenate and Bordeaux mixture; and (g) various fungicides, such as: diphenyl, sulfone, dodecylguanidine acetate (dodine), sodium tris-o-ethyl phosphonate (fosethylal), N- (2,6-dimethylphenyl) -N- (methoxyacetyl) alanine- methyl ester (methoxy) and other alkaline fungicides, phenylmercuric acetate, N-ethylmercury-1, 2,3,6-tetrahydro-3,6-endomethane-3,4,6,7,7,7-hexachlorophthalimide, lactate phenylmercuric monoethanol ammonium, p-dimethylaminobenzene sodium sulfonate, methyl isothiocyanate, l-thiocyano-2,4-dinitrobenzene, 1-phenylthiosemicarbazide, nickel-containing compounds, calcium cyanamide, lime sulfur, 1,2-bis- (3, -methoxycarbonyl-2-thioureido) benzene (thiophanate-methyl), and 2-cyano-N- (ethylamino) carbonyl) -2- (methoxyimine) acetamide (cymoxanil); as well as acylalanines such as furalazil, ciprofuram, ofurace, benalaxil and oxadixil; fluazinam, flumetover, phenylbenzamide derivatives such as those disclosed in EP 578586 Al, amino acid derivatives, such as the valine derivatives disclosed in EP 550788 Al, methoxy acrylates such as (E) -2- (2- (6- ( Methyl 2-cyanophenoxy) pyrimidin-4-yloxy) phenyl) -3-methoxyacrylate; S-methyl ester of benzo (1, 2, 3) thiadiazole-7-carbothioic acid: propamocarb; imazalil; carbendazim; myclobutanil; fenbuconazole; tridemorf; pyrazophos; fenarimol; fenpiclonil; pyrimethanil; and tin fungicides; (2) herbicides, such as, (a) carboxylic acid derivatives, including benzoic acids and their salts; carboxylic acids substituted with phenoxy and phenyl, and their salts; and trichloroacetic acid and its salts; (b) Carbamic acid derivatives, including N,. di (n-propyl) thiolcarbate ethyl and pronamide; (c) substituted ureas, (d) substituted triazines, (e) diphenyl ether derivatives, such as oxyfluorfen and fluoroglycofen, (f) anuides, such as propanil, (g) oxyphenoxy herbicides, (h) uracils, (i) nitriles and (j) other organic herbicides such as dithiopi and thiazaopyr; and (3) insecticides, including acephate, acetyl, acetoxy, aldicarb, aldoxicarb, aldrin, aletrin, alixicarb, alpha-cypermethrin, amidition, amitraz, amlure, anethole, azetion, azinphos-ethyl, azinphos-methyl, azocyclotin, bacillus thuringiensis, BCPE, bendiocarb, bensultap, benzoximate, benzyl acetate, benzyl benzoate, BHC, bifenthrin, binapacril, bomil, BPMC, bromophos, bormofos-ethyl, bro opropylate, bufencarb, buprofezin, butacarb, butocarboxim, butonato, butoxicarboxim, calcium arsenate , carbaryl, carbofuran, carbophenotion, carbosulfan, cartap, chlordane, chlordecone, chlomeform, chlorfenotol, chlorfenson, chlorfensulf ro, chlorfenvinphos, chlormethyl, chlorobenzilate, chloropenozide, chloropropylate, chlorfoxim, chlorpyrifos, chlorpyrifos-methyl, chlortiofos, clofentezine, CPCBS, CPMC, crotoxifos, crufomato, criolita, cufraneb, cyanofenfos, cyanofos, cyantoate, cyfluthrin, cyhexatin, cypermethrin, cyphenotrin, cyromazine, DAEP, DDT, DDVP, deltamethrin, demeton, demeton-S-methyl, demeton -O-methyl , demeton-S sulfur oxide, demeton-S-methyl, demephion-O, demephion-S, dialifor, diazinon, dicapton, diclofention, dicofol, dicrotophos, dieldrin, dienochlor, diflubenzuron, dihydrorotenone, dimefox, dimethane, dimethoate, dimetriña , dinex, dinitrophenol, dinobuton, dinocap, dioxabenzofos, dioxacarb, dioxation, disparlure, disulfoton, DMCP, DNOC, d-trans-allethrin, endosulfan, endotion, endrin, entice, EPBP, EPN, esfenvalerate, etiofencarb, etion, ethoate-methyl , etoprop, etrimfos, fenamifos, fenazaflor, fenbutatin-oxide, fenitrotion, fenoxicarb, fenpropatrina, fenson, fensulfotion, fention, fenvalerate, flubenzimina, flucitrinato, fluenetilo, flufenoxuron, fluvalinate, fonofos, formetanato hydrochloride, formotion, fosmetilan, fostietan, furatiocarb , furetrin, grandlure, heptachlor, HEPT, hexythiazox, hydramethylnon, hydroprene, IPSP, isazophos, isobenzan, isophenphos, isoprotab, isoprothiolane, isothioate, isoxation, jodfenfos, quinoprene, conductive arsenate, leptofos, letano, lindane, lit idation, malathion, mazidox, mecarbam, mecarfon, menazon, mephosphoea, methamidophos, metidation, methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl parathion, methyl phencapton, mevinphos, mexacarbate, MIPC, mirex, monocrotophos, MTMC, naled, nicotine, nonachlor, ometoate, ovex, oxamyl, oxideprofs, oxidisulfoton, oxythioquinox, paraoxon, parathion, green paris, permethrin, pertan, fencapton, phenoate, phorate, fosalone, fosfolan, fosmet, fosniclor, phosphamidon, phoxim, pirimicarb, pirimiphos-ethyl , pirimiphos-methyl, plifenate, profenofos, promecarb, propargite, propetamfos, propoxur, protidation, protiofos, protoate, PTMD, pyridaben, pyridafention, "quinalfos, resmetrin, ronnell, rotenone, riania, s-bioallethrin, salition, scradan, fluosilicate sodium, sofamide, sulfotepp, sulprofos, tebufenozide, tefluthrin, temephos, TEPP, terbufos, tetrachlorvinfos, tetradifon, tetramethrin, tetrasul, thallium sulfate, thiocarboxime, thiocylamide hydrogenoxalate, thiometon, tolclofos-methyl, toxafe no, triazamate, triazophos, trichlorfon, trichloronate, triflumuron, trimetacarb, vamidothion and xylilcarb. The compositions of the present invention can be applied to the foliage of a plant in the form of aqueous sprays by means of commonly used methods, such as conventional hydraulic sprinklers of high content in liters, sprinklers of low content in liters, air injection and air sprinklers. The dilution and rate of application will depend on the type of product used, the method and frequency of application desired, the rate of application of the pesticide and the pests that will be controlled. Although the use of redispersion polymers reduces the need for other auxiliaries, it may be desirable to include additional auxiliaries in the spray tank. Such auxiliaries include surfactants, dispersants, blowing agents, adhesion agents, antifoaming agents, emulsifiers and other similar materials described in McCutcheon's Emulsifiers and Detergents, McCutcheon's Emulsifiers and Detergents. Detergent / Functional Materials "(Emulsifiers and Detergents / Materials Functional Materials of McCutcheon) and "McCutcheon's Functional Materials" all published annually by the McCutcheon Division of the MC Publishing Company (New Jersey). The compositions of the present invention can also be mixed with fertilizers or fertilizer materials, before application. In a type of solid fertilizer composition, the particles of a fertilizer or fertilizer ingredients, such as ammonium sulfate, ammonium nitrate or ammonium phosphate, can be covered with one or more compositions. The compositions and the solid fertilizer material can also be mixed in the mixing equipment or can be incorporated with fertilizers into granular formulations. Any relative proportion of fertilizer can be used, which is suitable for the crops and weeds to be treated. The compositions of the invention will usually comprise from 5% to 50% of the fertilizer composition. These compositions provide fertilizer materials that promote rapid growth of desired plants, and at the same time control pests. The emulsion polymers used in the redispersion polymers of this invention can be prepared by polymerization in addition to one or more ethylenically unsaturated monomers such as, for example, acrylic ester monomers including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate; Acrylamide or substituted acrylamides; styrene or substituted styrenes; butadiene; vinyl acetate or other vinyl esters; vinyl monomers such as vinyl chloride, vinylidene chloride, N-vinyl pyrrolidone; and acrylonitrile or methacrylonitrile. Low levels of copolymerized monomers of ethylenically unsaturated acid such as, for example, 0.1% to 7%, by weight, based on the weight of the emulsion polymerized polymer, acrylic acid, methacrylic acid, crotonic acid, phosphoethyl methacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinyl sulfonate, itaconic acid, fumaric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate and maleic anhydride. Preferred acrylic copolymers with styrene contain from 10% to 60% styrene, based on the total weight of the polymer. The polymers can be single-stage or multi-stage polymers.

Emulsion polymerization techniques used to prepare redispersion emulsion polymers are well known in the art. See, for example, US Patent no. 5,346,954. Multistage polymers are well known in the art and are disclosed, for example, in US Pat. Nos. 4,325,856, 4,654,397 and 4,814,373. Surfactants such as, for example, anionic and nonionic emulsifiers such as alkali or ammonium alkali sulfates, alkyl sulfonic acids, fatty acids and oxyethylated alkyl phenols can be used in this type of polymerizations. The amount of surfactant used is usually from 0.1% to 6% by weight, based on the weight of the total monomer. Depending on the specific redispersion polymer to be prepared, processes can be used, either redox initiation or thermal processes. Conventional free radical initiators such as, for example, hydrogen peroxide, t-butyl hydroperoxide, alkali and ammonium persulfates, typically at levels of 0.05% to 3% by weight, based on the weight of the total monomer, can be used. . The redox systems "using the same initiators coupled with a suitable reducing agent such as, for example, isoascorbic acid and sodium bisulfite, can be used at similar levels. The particular procedure to be used depends on the particular polymer that is prepared; Not all conditions work in all cases. However, a person skilled in the art can easily determine the appropriate conditions without undue experimentation.

Proceed in or for the preparation, polymer, or dispersion. The following procedure describes the preparation of the redispersion polymer, designated as Powder III in the following examples. A five-liter four-necked round bottom flask with a mechanical stirrer, thermocoupler, condenser and nitrogen sprayer was charged with: (a) 3000 grams of 55 percent by weight of the polymer solids, an aqueous emulsion of an emulsion copolymer having a monomer composition of 19.1 weight percent, butyl acrylate, 80.65 grams of vinylacetate and 0.25 weight percent sodium vinylsulfonate, and (b) 363 grams of an aqueous solution of polyvinyl alcohol (17.3% by weight, Vinol ™ 203, Air Products Company). Next, the mixture was heated at 85 ° C for two hours. The hydrolyzed product was then cooled and filtered through a mesh screen 100. The filtered hydrolyzed product was spray-dried using a Bowen BLSA laboratory spray dryer. The inlet air temperature was set at 122 ° C, and the outlet air temperature was 57 ° C, regulated by the feed rate. The resulting product had a residual moisture level of less than 4%, and was a free flowing white powder that was easily redispersed in the water.

Procedure for evaluating __L e ec o _l = 1__S polymer additives in the resistance of pesticidal formulations against washing / disposal caused by the asua. One method to evaluate the effectiveness of a pesticide auxiliary is to measure its effect on the ability of the pesticidal composition to resist washing / removing a surface. One skilled in the art will recognize that a pesticide that remains on the surface of a plant is expected to have an increased efficiency. A suspension of the pesticidal formulation was prepared by adding a pre-mix of water and surfactant, with or without the polymer additives, followed by vigorous shaking by hand of the mixtures. Fragments of laboratory film Parafilm ™ M, which is a very soft, flexible and hydrophobic film, were tied with tape to plastic petri dishes. The suspensions were sprayed with an automated sprinkler, while the petri disks with the stuck film were moved at a standard index below the sprinkler. The spray residues were allowed to dry, and a second spray application was applied. A set of films was exposed, at an inclination of 45 degrees, to approximately 25 mm. of water applied by a spray bar (equipped with TX4 cone-type spray nozzles) that was moved from one side to the other on the samples for a period of about one hour. The exposed films were allowed to dry. Another movie game was not exposed to water. The infra-red spectrum of the films was obtained by means of an Attenuated Total Reflection (RTA) technique. The films were pressed against a Selenide Zinc crystal that had been previously cleaned with methanol. The spectra were recorded with an infra-red Fourier Transform Spectrometer of Related Systems of the Spectrum Technique, and stored in a computer. The peaks associated with the pesticide residues were identified by an inspection, and the peak areas were computed by computer (Peak Pesticide Area, "PA"). A corresponding area for a peak of Parafilm ™ as similar as possible in the size and peak location (in the same spectrum) was calculated (Peak Area of the Film, "FA"). Similar calculations were conducted for a spectrum of the film that had not been sprayed with pesticide, giving corresponding reference peak areas "RPA" and "RFA". From the following calculation a pesticide measure was derived on the surface "P": P = PA / FA - RPA / RFA. Next, a relative measure of the amount of pesticiada that remained after the previous exposure to water was derived from the following calculation: Remaining relative amount = 100 (PA / FA - RPA / RFA) for the exposed film (PA / FA - RPA / RFA) for the unexposed film.

Although the intensity of the spectral peaks recorded with the RTA technique is very dependent on the details of contact with the film, obtaining a peak index of the pesticide at the peak of the film in the same spectral record, different spectra can be compared with the details of contact with those who are compensated, since they will have similar effects on the intensity of the pesticide and film absorption. The intensity of the peak of the pesticide relative to the peak of the film will depend on the degree of coverage of the film by the pesticide. To maximize coverage, the spray was conducted twice. In addition, a wetting agent (surfactant) was included in the premix to promote wetting of the film by means of spray droplets. Since exposure to water can result in the redistribution of the pesticide, as well as a wash / dispose of the pesticide, the measure of the remaining amount is only relative. When there is a little washing / removal, the redistribution effect can make the above index greater than 100. The following table shows the details of the spray mixtures and spray conditions, as well as the IR bands for the pesticide and the Parafilm ( reference) used to measure the amount of the pesticide present. In all cases, a measured quantity of the pesticide was mixed with 270 grams of deionized water and 30 grams of 0.5% Silwet L-77 surfactant. This pre-mix was divided into 50 gram portions. A portion was sprayed without the addition polymer. For mixtures containing polymer, 66.6 milligrams of polymer powder or 1.32 grams of a 5% dilution of solids of the emulsion polymer was added to the 50 grams of the pre-mix. The following pesticides and types of pesticide were evaluated: (1) fungicides; 80% of mancozeb in wetting powder (PH), 80% of maneb PH, 76% of ziram in granule of dispersion (GD), 82.5% of chlorothalonil GD, 77% of copper hydroxide PH, 40% of myclobutanil PH, 75 % of fenbuconazole PH, 50% of captano PH, (2) insecticides; flowable carbaryl (FLO), 50% of cartap PH, carbofuran four pounds per gallon FLO, 70% of tebufenozide PH, 50% of dicofol PH, dinocap PH; and (3) herbicides; 80% propanil GD, and 75% oxyfluorfen FLO.

Pesticide Grams used Condition Infrared bands used in the spray premix Pesticide Parafilm mancozeb 2.4 A 1287 1231 maneb 2.4 A 1287 1231 ziram 2.4 A 1518 1231 chlorothalonil 2.4 A 1549 1231 copper hydroxide 2.4 A 698 725 myclobutanil 2.4 A 1096 1231 fenbuconazole 2.4 A 1030 1231 captano 2.4 A 1015 1231 carbaryl 4..2 A 1115 725 cartap 3. .8 A 1675 1470 carbofuran 4. .3 A 1717 1470 tebufenozide 2. .7 B 1648 1470 dicofol 3. .8 A 768 725 dinocap 9,. 5 A 1581 1231 propanil 2, .4 B 1546 1470 oxyfluorfen 2 .5 B 1081 1231 Spray condition A: TX-2 nozzle, 12 inches above the laboratory film. 58 psi (delivery 150 cc / minute). The lab film moves at one mile per hour. Spray condition B: Fan nozzle, 14 inches above the laboratory film. 29 psi (spray 15 ce with two passes over the lab film at an index that gives 25 gallons per acre).

Three different solid redispersion polymers were evaluated: Powder I, an ethylene / vinyl acetate copolymer with polyvinyl alcohol (Airflex ™ redispersion powder RP-245 from Air Products Company, a cement modifier); Powder II, a copolymer of styrene / butyl acrylate with polyvinyl alcohol (redispersion powder Vinnapas ™ LL-564 from Wacker Chemical Company, a cement modifier); and Powder III, a redispersion powder prepared as described in the above synthesis example. An aqueous emulsion polymer of a type that is used as a spray tank additive was included as a reference: EmulsionlV, a copolymer of styrene butadiene with surfactant (Rovene ™ 4150 emulsion from Mallard Creek Polymers Company, an interlining adhesive of carpet). "% of AI retained after the rain of" sprayed by bar "of one inch" Powder Free Powder Powder Emulsion Polymer Pesticide II III IV P DE P P P P P mancozeb 21 3 76 33 124 23 77 6 107 4 maneb 16 2 76 8 108 1 86 13 103 6 ziram 60 3 88 5 111 5 94 11 104 12 Chlorothalonil 2 16 1 54 6 4 4 12 4 hydroxide 20 23 22 19 80 36 21 23 11 copper myclobutanil 13 2 56 2 77 11 44 25 74 3 fenbuconazole 9 8 63 16 82 1 48 16 83 3 captan 41 8 75 12 68 9 51 11 69 11 carbaryl 25 1 31 3 32 9 27 5 40 7 cartep 4 1 5 6 8 2 8 2 3 1 carbofuran 3 1 39 1 23 1 16 2 9 1 tebufenozide 40 18 71 23 67 14 40 25 59 9 dicofol 18 1 76 12 62 1 62 13 95 27 dinocap 3 < 1 49 24 47 17 19 4 40 6 propanil 9 38 27 21 18 oxy fl uorfen 17 1 66 10 137 52 55 1 152 30 P = average DE = standard deviation These data indicate that the redispersion polymers develop in the same way as the emulsion polymer.

Evaluation? __ l control «___ diseased age in grapes and peanuts, using mancozeb fungicide. With respect to the grape, plots of simple plants with three replicates per treatment were treated in seven-day intervals, with a total of seven applications. The treatments were spray mixtures, water based, mancozeb with or if polymer additives added to the water a little before spraying. The mixtures were applied with a backpack sprayer using carbon dioxide pressure atomization (45 psi) with one arm with three D3 nozzles (cone), at an index of 640 liters per hectare. The treatments included a control without applied fungicide, a complete index of mancozeb without additive (2.8 kg of active ingredient per hectare) and an average index of mancozeb (1.4 kg of active ingredient per hectare) with or without additives. The polymer additives were used in 1/3 kg. of additive solids per kilogram of the active ingredient. The formulation of mancozeb was a moisturizing powder with 75% active ingredient.

The evaluation of the percentage of infection (of villous blight of the grape caused by the Plasmopara vi tícola) of the leaf was made seven days after the treatment # 7 (7DAT # 7). These evaluations are calculated below. The data were analyzed by Duncan's multiple index test, using P = 0.5 (averages that do not have a common letter are significantly different from a 95% probability). The peanuts were evaluated the same as the grapes except that the plots were one meter by five meters (one strip), with four replicates per treatment, there were nine applications, the arm had five D2 nozzles (C45), the complete mancozeb index was 1.6 kg. of active ingredient per hectare, the final assessment was 23 days after treatment # 9 (23DAT # 9), and the prevailing disease at that time was Cercospora arachidicola (Leaf Spot Premature). Three different solid redispersion powders were evaluated; Powders I and II of the previous example and Powder V, in all acrylic copolymers (redispersion powder Drycryl ™ DP-2904, a cement modifier from Rohm and Haas Company). Three different emulsion polymers were evaluated for comparison; Emulsion IV of the previous example; Emulsion VI, an emulsion of poly (vinylacetate) (Rovace ™ 117 emulsion from Rohm and Haas Company, used as an adhesive component for general purposes); and Emulsion VII, an acrylic emulsion polymer (Rhoplex ™ 2438 emulsion from Rohm and Haas Company, a component of elastomeric wall coatings). In several of the evaluations, a surfactant was added to the spray mixture. When used, the surfactant was a solid powder of 90% dioctyl sodium sulfosuccinate and 10% sodium benzoate (Aerosol®OTB surfactant from Cytec Company).

Results of the field tests of the grape and the peanut. where Mancozeb is compared in a medium index with or without additives Infection Infection in Additive Additive index the peanut grape using mancozeb polymer surfactan. 23DAT # 9 7DAT # 7 None none 68.8 to 91.7 a Complete none 27.5 cd 41.7 cd Half none 41.3 b 63.6 b Half Emulsion VI no 22.5 ef 43.3 cd Half Emulsion VI yes 13.8 h 31.7 fg Half Dust II no 32.5 c 43.3 cd Half Powder II yes 17.5 g 28.3 g Half Powder V no 22.5 ef 46.7 c Half Emulsion IV no 25.0 of 38.3 of Half Emulsion VII no 21.3 f 41.7 cd Half Powder I no 23.8 ef 46.7 c The results of these evaluations indicate that all polymer additives significantly improved the efficacy (reduced infection) of the average mancozeb index, giving an efficacy as good as the complete index without additives. Another significant improvement in efficiency resulted when the surfactant was used in addition to the polymer. The improvement in efficiency with redispersion polymers of different compositions was similar to that of two of the emulsion polymers (Emulsions VI and VII), and almost as good as that of the other emulsion polymer (Emulsion IV). These data demonstrate the effect of the surfactant added on the efficacy of mancozeb, both in the presence and in the absence of an auxiliary redispersion polymer. The data indicate that, at an appropriate level, the surfactant provides an increase in efficacy.

Evaluation ___1 control __ the, worm S_ = beet in the rice, using Tebufenozida. Rice plants grown in pots were sprayed with one of two different versions of a suspension of 300 parts per million (based on the level of active ingredient) of tebufenozide in water. In one version, tebufenozide was supplied as a Mimic® 10W insecticide, a wetting powder, from Rohm and Haas Company. In the second version, approximately 30% by weight of the carrier in the Mimic® 10W insecticide was replaced with the Powder V of the previous examples, and approximately 10% by weight of the clay carrier was replaced by the surfactant Aerosol® OTB . A portion of each of the sprayed plant samples was subjected to approximately 25 millimeters of water, applied by means of a spray bar to simulate that it was raining. The plants were cut and fed to the larva of the Beetroot Worm. The percentage of mortality was then evaluated.

Mortality (%) of the Beetworm Without rain With rain Tebufenozide 90 28 Tebufenozide with Powder V 100 65 Evaluation of control of the worm, beet, under field conditions. Each of the two different plots of Chinese cabbage grown under typical field conditions was treated with one of the two formulations of tebufenozide, described above, at an application rate of 300 grams of tebufenozide per hectare in 750 liters of water per hectare . The mortality rate of the beet rootworm in each plot was compared with an untreated control plot.

Control of beetworm (%) Tebufenozide 35 Tebufenozide with Powder V 67 These data indicate that the redispersion polymer provides pesticidal compositions with improved efficiency as compared to an identical composition that does not contain the polymer.

Claims (12)

Claims

1. A solid pesticidal composition, "comprising: a) one or more pesticides; and b) one or more redispersion polymers, comprising: (1) one or more water insoluble polymers; and (2) one or more water soluble polymers.

2. The use of a redispersion polymer, comprising: (1) one or more water-insoluble polymers; and (2) one or more water-soluble polymers, as an adjunct to the pesticide.

3. A method for controlling pests, which comprises applying to the pest, to the site of the pest or a food source of the pest, the solid pesticidal composition according to claim 1.

4. The solid pesticidal composition, according to the claim 1, comprising: a) from 5 to 90% by weight of one or more pesticides; b) from 5 to 80% by weight of at least one water-insoluble polymer; and c) from 1 to 40% by weight of at least one water-soluble polymer.

5. The pesticidal composition according to claim 1, wherein the composition is dispersed in water in particles less than 40 microns in size.

6. The composition according to claim 1, wherein the water insoluble polymer comprises units derived from one or more of the group consisting of vinyl esters and ethylene, and wherein the polymer has a glass transition temperature between -20 and 40 ° C. The composition according to claim 1, wherein the water insoluble polymer is selected from one or more homopolymers and copolymers comprising, independently, polymer units derived from one or more of: acrylate - ethylhexyl, butyl acrylate, ethyl acrylate, methyl acrylate and vinyl acetate, wherein the water-insoluble polymer has a glass transition temperature between 0 and 60 ° C. The composition according to claim 7, wherein the water insoluble polymer has a glass transition temperature between 0 and 40 ° C. The composition according to claim 7, wherein more than three percent of any of the units derived from vinyl acetate, which are present, has been hydrolyzed. The composition according to claim 1, wherein the pesticide is selected from the group consisting of wetting powders and dispersing granules. The composition according to claim 1, wherein the pesticide is selected from the group consisting of mancozeb, maneb, ziram, chlorothalonil, copper hydroxide, myclobutanil, fenbuconazole, captan, carbaryl, cartap, carbofuran, tebufenozide, dicofol, dinocap, propanil and oxyfluorfen. 12. A solid composition that is dispersed in water in particles less than 40 microns, comprising: a) from 5 to 90% by weight of at least one pesticide; b) from 5 to 80% by weight of at least one polymer of high molecular weight, insoluble in water, prepared in emulsion; and c) from 1 to 40% by weight of at least one water-soluble polymer with a molecular weight greater than 2,000 amu; wherein the composition, when sprayed on a hydrophobic substrate, has improved resistance against washing / removal caused by rain, relative to the composition without the polymers.