AU723486B2 - Emulsion concentrates of water-insoluble film-forming polymers and uses therefor - Google Patents

Description

p.d S F Ref: 295436D1

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

0 *0*0 0 Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: ISP Investments Inc.

818 Washington Street Wilmington Delaware 19801 UNITED STATES OF AMERICA Kolazi S. Narayanan.

Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Emulsion Concentrates of Water-Insoluble Film-Forming Polymers and Uses Therefor The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845 1 EMULSION CONCENTRATES OF WATER-INSOLUBLE

FILM-FORMING

POLYMERS AND USES THEREFOR BACKGROUND OF THE INVENTION A significant problem in the use of agriculturally active chemicals is that since they are applied to soil and plant surfaces, they are susceptible to being washed off by rain and/or water spray used for irrigation. This adversely affects the efficience of the chemicals, since the longer the chemical remains in contact with the plant or soil surface, the more effective it is.

*o Certain types of polymers exhibit film-forming properties and when dissolved in an organic solvent, can be applied for the purpose of providing a waterresistant coating on a substrate. Usually, the film-forming polymer in the solvent is 0 10 applied to the particular substrate to be coated, and the solvent is allowed to evaporate or removed leaving a film of the polymer.

*00 Generally, however, such water-resistant, film-forming polymers are soluble only in organic solvents, i. they are substantially insoluble in water. The use of such organic solvents generally is undesirable since they exhibit environmentally adverse properties, are often hazardous or flammable, and are generally expensive. In order to avoid the environmentally adverse effects of such organic solvents as well as to reduce the cost involved with using such solvents, rather complicated solvent recovery procedures must be used.

-2- Typical of such polymers are copolymers of N-vinylpyrrolidone with o-olefins, vinyl acetate, styrene, acrylates, acrylic acids, amides, maleic acid, mono and diesters of maleic acids, and the like.

SUMMARY OF THE INVENTION I have discovered a method for providing a stable microemulsion of a particular class of water-insoluble film-forming polymers in water. The microemulsions thus formed can be utilized to produce films of the particular film-forming polymer on a given substrate. For example, the microemulsion can be used as a coating for substrates, such as, wood, metal, glass, and the like. In addition, various 10 active ingredient, fungicides, preservatives, insecticides, insect repellents, pheromones, radiation absorbents, dyes, and the like, can be included in the composition.

I have discovered a class of emulsion concentrates of water-insoluble filmforming polymers which comprise a water-insoluble oVooo: polymer, an agriculturally active chemical, and an organic solvent for the agriculturally active chemical.

Accordingly, there is provided according to a first embodiment of the invention an emulsion concentrate comprising: a) an effective amount of an agriculturally active chemical; b) a solvent for the agriculturally active chemical; and c) a water-insoluble film forming polymer being a graft polymer of N-vinylpyrrolidone and an c-olefin wherein the a-olefin is present in an amount of at least 5 wt based on the weight of the graft polymer.

According to a second embodiment of the invention there is provided an emulsion concentrate comprising: a) 2 to 90% by weight of a solvent selected from the group consisting of long-chain alkyl pyrrolidones, synthetic or naturally occurring hydrophobic oils, and mixtures thereof; b) 1 to 60% by weight of a water-insoluble graft polymer of N-vinylpyrrolidone and an aolefin wherein the N-vinylpyrrolidone is present in at least 20% on a weight basis; and c) 1 to 85% by weight of an oil-soluble surfactant.

According to a third embodiment of the invention there is provided a composition for application to agricultural crops comprising an emulsion of the emulsion concentrate of the first embodiment diluted at least 2-fold with water.

2 According to a fourth embodiment of the invention there is provided a method for producing a water-dispersible granule of an agriculturally active ingredient comprising charging an agriculturally active ingredient and the emulsion concentrate of the first embodiment to a granulator to form granules, and drying the granules.

The water-insoluble polymers used in the present invention are graft polymers of 2.5 vinylpyrrolidone and a-olefin wherein the N-vinylpyrrolidone is present in more than about 5 percent on a weight basis. Preferably, the weight percent of N-vinylpyrrolidone is about 10 percent. The aolefin should preferably contain from 8 to 30, and more preferably, from 16 to 20 carbon atoms.

The emulsion concentrate of the present invention provides a stable emulsion upon dilution with water. Thus, the emulsion concentrate of the invention is particularly suitable for use with an so agriculturally active chemical or ingredient (hereinafter, sometimes referred to as The diluted inventive concentrate of the film-forming polymer may include an agriculturally active chemical or ingredient, such as, pesticides, herbicides, and the like. This composition may then be applied to plants, or soil, in the usual manner. I have found that the inventive composition, thus used, forms a film incorporating the a.i. on the leaf, soil or seeds and can prevent wash-out of the agriculturally active ingredient due to rain. Thus, for example, the composition with an agriculturally [R:\LIBFF]O8778speci.doc:njc 3a active ingredient forms a film on the particular substrate, the plant or soil, which results in improved retention and enhanced bioactivity of the agricul-

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a Q

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[R\LI BFF]OS77 8speci.doc:njc -4rurally active ingredient and also provides superior rainfastness for such ingredients on leaf and substrate surfaces.

The inventive compositions are particularly convenient for use with oil-based concentrates, commercial Prowl, Fusilade, and Thiadiazuron. However, they can also be used in aqueous-based hydrophobic active ingredients, e.g, aqueous emulsions or dispersions of carbaryl (Sevin).

10 DETAILED DESCRIPTION OF THE INVENTION As used herein, the following terms have the meaning indicated: macroemulsion" means an emulsion of water-in-oil or oil-in-water wherein the interior phase is in the form of visually discernable droplets and the overall emulsion is cloudy, and wherein the droplet diameter is greater than about millimicrons (1 micron), and usually greater than 1000 millimicrons (about microns).

"microemulsion" means an oil-in-water or water-in-oil, transparent thermodynamically stable dispersion of two or more immiscible liquids or a solid in a liquid wherein the dispersed phase consists of small droplets with diameters in the range of about 10 to 100 millimicrons. Such microemulsions are clear and appear as a single phase to the naked eye.

"single phase" as applied to a liquid means that to the naked eye, the liquid is homogeneous and does not appear to contain any other separatable liquid phase.

"clear" or "transparent" as applied to a liquid means that the liquid appears as a single phase without any particulate or colloidal material or a second phase being present when viewed by the naked eye.

"substantially insoluble" or "insoluble" means that for all practical purposes, the solubility of the compound in water is insufficient to make the compound practicably usable in an agricultural end use without some modification either to increase its solubility or dispersability in water, so as to increase the compound's bioavailability or avoid the use of excessively large volumes of solvent.

10 "High degree of loading in the concentrate" means an agriculturally active ingredient content of at least about 5 percent by weight.

"agriculturally active chemical or ingredient" (AAC or means compounds and mixtures thereof which can be used as agricultural fertilizers, nutrients, plant growth accelerants, herbicides, plant growth controlling chemicals, and chemicals which are effective in killing plants, insects, microorganisms, fungi, bacteria and the like which are commonly referred to as insecticides, bactericides, fungicides, nematocides, fumigants, synergists, compounds which when used in conjunction with other AAC's enhance their activity and the like, as well as any other chemicals having properties which are suitable for agricultural uses in terms of application to plants or domestic uses for controlling insects and pests.

-6- Long-chain N-alkylpyrrolidones suitable for use as a solvent in the present invention have the formula 0 R3 wherein R 2 is hydrogen or alkyl having from 6 to 14 carbon atoms and R 3 is alkyl having from 6 to 14 carbon atoms with the proviso that at least one of R 2 or R 3 must contain at least 6 carbon atoms and the sum of the carbon atoms in R 2 and R 3 cannot exceed 14. Preferably,

R

2 is hydrogen and R 3 is C 8 or C 1 2 Mixtures of two longchain alkylpyrrolidones may also be used. N-methyl pyrrolidone may also be included along with long chain N-alkylpyrrolidones in an amount effective to help maintain the solubility of the long chain alkylpyrrolidones.

The solvent may be an organic diluent which is a synthetic or naturally occurring oil having a high hydrophobic character or having a fractional dispersive 0 *-solubility parameter of greater than 70 and preferably greater than 85 and a molar volume of greater than 90 cm 3 /mole. These properties are defined in the C.R.C. Handbook referred to hereinabove. Typical diluents include soybean oil, rapeseed oil, long chain alcohols, long chain ketones, long chain esters, and ethers.

As used herein, "long chain" means with 6 or more carbon atoms. Also suitable as the organic diluent are aromatic petroleum oils including those which are commercially available distillates from crude oils having an average boiling point greater than 120"C. Typical of such materials are those sold under the trademarks Exxon 200 or Texaco 400. Of course, such aromatics should be approved for use as a carrier for agriculturally active chemicals.

The composition of the aromatic petroleum oil is generally: Heavy aromatic solvent naphtha about Middle distillate solvent extractant about Normally, these oils contain predominantly the C9-C15 aromatic hydrocarbons and primarily the C10-C12 hydrocarbons having a flash point of about 203 F.

0 10 When a surfactant is used, because of the nature of the active ingredient, the concentration of the active ingredient desired, and the like, suitable surfactants include both water and oil-soluble surfactants, ethoxylated alkyl phenols, linear aliphatic polyesters, linear aromatic polyesters, polyalkenyloxyalcohol, linear aliphatic ethoxylates, polyethoxylated castor oil, polyethoxylated carboxylates, and polyethoxylated alkylamines. Oil and water-soluble anionic surfactants may be used as the emulsifier and include phosphate esters and their salts, alkyl sulfates, sulfonates, and their salts, salts of sulfate nonylphenoxypoly(ethyleneoxy) ethanol, salts of alkylbenzene sulfonates, the sodium, calcium and alkylammonium salts, salts of alkylnaphthalene sulfonate, and sulfonated aliphatic polyesters and their salts. Also suitable are complex phosphate esters of nonionic 8 surfactants of the ethylene oxide type which are mixtures of diesters of phosphoric acid. (See, for example, McCutcheon's, Emulsifiers and detergents (1989), published by McCutcheon's Division of M.C. Publishing Co., Glen Rock, New Jersey.) Polymers particularly suitable for use in the present invention include polymers, such as, Ganex 516, which is copolymer of an a-olefin and N-vinylpyrrolidone (50/50 percent mixture), copolymers of vinyl pyrrolidone and olefins. Typically, such olefins contain up to 20 carbon atoms, and preferably contain 16, carbon atoms. The weight average molecular weight of such polymers is generally greater than about 10,000. Particularly suitable are water-insoluble polymers, such as, Agrimer (International Specialty Products (ISP) Corporation), which is a copolymer of an a-olefin having the io formula C14H 29

CH=CH

2 and N-vinyl-pyrrolidone and Agrimer AL30 (ISP Corporation), which is a copolymer of an a-olefin having 20 carbon atoms and N-vinylpyrrolidone Co-polymers of N-vinylpyrrolidone and vinyl acetate should preferably contain at least about 10% Nvinylpyrrolidone and have a weight based on the total average molecular weight of at least about 10,000.

Typically, the inventive concentrate comprises from about 2 to 90 percent, more preferably from to 85 percent, and most preferably, from about 30 to 80 percent by weight N-alkyl pyrrolidone organic solvent or both from about 2 to 30 and more preferably, from about 8 to 15 percent by weight surfactant, and from about 1 to

*S

o *oi o oo* o* [R:\LI BFF18778speci.doc: njc -9and preferably from about 5 to 30 percent, and most preferably, 10 to 25 weight percent of the water insoluble polymer. If a surfactant is present, water may be present in an amount from 1 to 85 and, preferably, from 3 to 70 percent, and most preferably, from about 5 to 60 percent by weight.

All percents herein are percent by weight based on the total weight of the composition.

The inventive compositions are particularly suitable for end use applications wherein films of water-insoluble polymers are formed on substrates.

The films may be formed for adhesive, protective, decorative, lubricating, to impart hydrophobicity or hydrophilicity, and the like, purposes. Since it is desirable to avoid organic solvents due to their cost and adverse toxicological and environmental properties, the use of water as a solvent for the film-making procedure is preferred.

With the inventive composition, it becomes possible to place such ordinarily waterinsoluble film-forming polymers in an aqueous based vehicle, solution, emulsion 15 or dispersion-solubilizing liquid, which can be handled and utilized in the same manner as a true solution of the polymer to form a film therewith. Thus, the inventive composition in microemulsion form may be coated as is, or after further dilution with water, if desired, onto a substrate. The water is then removed as by evaporation to leave the polymer film remaining.

I have further discovered that the rainfastness of agriculturally active ingredients, and in particular, pesticides, can be substantially improved by formulating the pesticides in the inventive composition including the water insoluble filmforming polymer. Thus, many pesticides, and particularly water soluble agriculturally active chemicals, are washed off by rain after they have been applied to the plants or soil. For effective pest and weed control, it takes from a few hours to three weeks for the pesticide to penetrate into the biological system. The present invention assures that the agriculturally active ingredient will be retained for a sufficiently long time to allow it to be effective and avoid or reduce rain wash-off.

10 In use, the inventive composition is diluted with water and applied to the crop, plants, or soil. Normally, this dilution is carried out at the field site. As *used here:. rainfast resistant, rainfast or rainfastness in connection with the inventive compositions means that a film formed from the composition exhibits increased resistance to removal by water washing as compared to the same composition which does B. 15 not contain the film-forming polymer under the test procedures as described hereinafter.

Pesticides which can be used with the present invention, may be characterized by their physical properties, depending on their physical state at normal or ambient conditions, between 40*F and 90F and their solubility or miscibility with water or other common organic solvents, aromatics, such as, toluene, xylene, methylated and polyalkylated naphthalenes, and aliphatic solvents.

11 Based on the physical properties, the pesticides may be classified into three groups: The first group includes those which are oily liquids at ambient temperatures and are immiscible with water. Specific pesticides include: Common esters of 2 4 -dichlorophenoxyacetic acid, Common esters of 2 4 ,5-trichlorophenoxyacetic ac-id, Common esters of 2 -(2,4-dichlorophenoxy) propionic acid, Common esters of 2 2 4 ,5-trichlorophenoxy) propionic acid, Common esters of 2 ,4-dichlorobutyric acid, Common esters of 2 ,methoxy-3,6-dichlorobnzoc acid, Common esters of 2 -methyl-4-chlorophenoxyacetic acid, *~Piperonyl butoxide 3 4 -methylenedioxy6propyl benzyl n-butyl diethylene glycol ether, Bromophos ethyl: 0,0-diethyl.-0-2 -dichloro-4-bromophenyl thionophosphate, N-(2-mercaptoethyl) benzene-sulfonaniide

(BETASANO),

Isolbornyl Thiocyanoacetate loxynil ester of octanoic acid, Molinate S-ethyl hexahydro 1 H azepine- I -carbothioate, PP 511 O,-dimethyl-(2-dietliylamine 4-methyI-6-pyrirnidinyl) carbamate, PP 211 0,0-diethyl

O-(

2 -diethylamine-4-methyI6- pyruniidinyl) phosphorocarbamate, 5-Ethoxy-3-(trichlorometyl)- 1,2 ,4-thiadiazole

(TERRAZALEI&),

Ethyl-s-s-dipropyl-phosphodithioate

(MOCAP),

12 S-Ethyl dipropyithiocarbamate

(EPTAMO),

S-Ethyl diisobutylthiocarbamate

(SUTANO),

S-n. propyl-di-n-propylthiocarbamate

(VERNAMO),

S-propyl butylethylthiocarbarnatae

(TILLAMID),

S-ethyl ethylcyclohexylthiocarbaxnate (RO-NEETs), Malathion (S-(1I,2-dicarboxyethyl)-O,O-dimeffiyI phosphorodithioate), Diazinon (0,0-diethyl 2 -isopropyl-4-methyl-6- pyrimaidinyl) phosphorothioate, O-Ethyl-S-phenyl.ethylphosphonoydjthj 0 at (DYFONATEt), Toxaphene (Octachiorocamphene), Bromoxynil 3 ,5-dibromo-4-hydroxy benzoniitrile ester of fl.octanojc acid, 2 -chloro-N- 2 ,6diethylphenyNmethoxmethyataide

(LASSO*),

Diallate S-2, 3-dichloroallyl N, N-diisopropylthiolcarbamate Triallate S-2, 33-trichioroallyl N, N-diisopropylthiolcarbamate.

The second group comprises those pesticides which are solids at ambient temperatures and for all practical purposes, insoluble in water.

2,4, 5-T (2,4 ,S-trichlorophenoxy acetic acid) Monuron (3-(p-chlorophenyl)- 1, 1 -dimethyl urea) D iuron ,4-dichlorophenyl)- 1,1-dimethyl urea) Bromacil (5 bromo-3-sec. butyl-6-methyl uracil) Isocil (5 bromo-3-isopropyl-6-methyl uracil) Linuron dichlorophenyl)-l-methoxy-1 methyl urea 13 Atrazine 2 -chloro-4-ethylamino-6 isopropylaxnino-s- triazine) Simazine (2-chioro- 4,6,-bis (ethylaxnino)-s-triazine Dodine (n-dodecylguanidine acetate) Thiram (tetramethyithiuram disulfide) N-(mercaptomethyl)phthalimide s-(o,6 dinlethylphosphorodithioate)

(IMDAN(D)

Lindane (gamma 1,2,3,4,5,6 hexachlorocyclohexane) Folpet (N-trichloromethylphthaliniide) Manazon (s-(4,6-diamino- 1, 3,5-triazin-2-yl rnethyl)dimethyl phosphorothiolthionate) Barban (4-chloro-2 butynyl m-chlorocarbanilate) Tricumba 2 -methoxy-3,5,6-trichlorobenzoic acid Trifluraim (2 ,6-dinitro-N ,N-dipropyl-4-trifluoromethylaniline) (2,3 carboxanilido-6-methyl- 1,4-oxathiin) (VITA VAXO) .2 2,4-dichorophenoxyacetic acid 4-(4-chloro-2 methyiphenoxy) butyric acid 15 2-(2 ,4-dichlorophenoxy) propionic acid loxymil: 3,5 diiodo-4-hydroxybenzonitrile Bromoxynil: 3,5 dibromoA4-hydroxybenzonitrile Methoxychlor: 2,2, -Bis(P-methoxyphenyl)- 1,1-trichloroethane PP 781: 4(2-chloro PP 675: 5-butyl-2-dimethylamino-4-hydroxy-6methyI pyrimidine* PP 062: 5,6-dimethyl-2-dimethylamino.4 pyrimidinyl dimethylcarbamate* PP 149: 5-n-butyl-2 ethylamino-4-hydroxy-6 methylpyrimidine* *Macrured by Us~erii Ohemxcl Endomms Lamned 14 C 6313 4 -bromo- 3 -chlorophenyl)Nmetoxy-N..methylurea C 6989 2,4 'dinitroA-trifluoromethyl4Jiphenylether Chioroxuron N' -4-(chlorophenoxy) phenyl-NN-dimethylurea Dichiobenil 2 ,6-dichlorobenzornjtrile Diphenarnid NN-dimethy1-2,2-diphenylaceamide Fenac. 2,3 6 -trichlorophenylacetic acid Fluometuron N 3 -trifluoromethylphenyl).NN.dimelylurea GS 14260 4 -ethylan no-2-methylthio-6-t-butyl.amino-.1,3 PCP Pentachiorophenol.

~10 Lenacil 3-cyclohexyl-6 ,7-d ihydro- 1H-cyclo-pentapyrimidine.2 ,4-(3H1,5H)-dione Pyrazon 5-amino- 4 -chloro-2-phenyl-3pyrdazone Metrobromuron N' 4 -bromophenyl)-N-methoxy.Nmethylurea Metoxymarc N-(4-methoxybenzoyl)-N-(3 ,4-dichloropheny1)-N' -dirnethylurea Neburon N-butyl-N 4 -dichlorophenyl-N-methylurea 15 NIA 11092 1 ,1-dimethy1-3-[3-(n-t-butyl carbaxnyloxy)phenylj urea Mecoprop 2-(4-chloro-2 methylphenoxy)propionic acid Monolinuron N 4 -chloropheny)-N-metboxy-N-mefiylurea Nitrofen 2 ,4-dichlorophenyl 4 -nitrophenylether Propanil N-(3 4 -dichlororphenyl)propionainide Pyriclor 2 3 ,5-trichloro-4-pyridinol Solan 3' -chloro-2-methyI-p-valerotoluidide Terbacil 5-chloro-3-t-butyl-6-methyluraciI UC 22463 (SIRMATE)-3 ,4-dichlorobenzyl N-methylcarbamate 15 WL 9385 2-zd--tyaio6t-uyaiostizn Propachior 2 -chloro-N-isopropylacetanilide CP 50144 2-chloro-N-2 ,6-diethylphenyl-N- methoxymethylacetapmjde CP 31675 2-chloro-N-(2 methyl-6-t-butylpheny1)acetamide Cypromid 3 4 '-dichlorocyclopropane carboxanilide Fenuron NN-dimethyl-N-phenylurea Chlorbromuron N' 4 -bromo- 3 -chlorophenyl)..Nmethoxy-Nmethylurea Ametryne 2-ehlecpo4ehlmn-6iorplaiostizn Prometryne 2 -methylmercapto-4,6-bisisopropyl amnino-s-triazjne DCPA dimnethyl 2,3,5,6, tetrachloroterephthalate Benefin N-butyl-N.-ethyl-2 9 2 2 -trifluoro-2,6-dinitro-p-toluidine Nitralin 2 ,6-dinitro-4-methylsulfonyl.N, N-dipropyl-aniline PP 493 2 ,6-difluoro-3 ,5-dichloro-4-hydroxy pyridine CNP 2 4 6 -trichloropheny1-4'-nitrophenyI ether Pentachioro nitrobenzene 1-(butyl carbamoyl)-2-benzimidazole carbamaic acid, methyl ester (BENLATE19).

Carbaryl (methylnaphthyl carbamate) (active ingredient in Sevin).

The third group constitutes those compounds which are water-soluble, such as, salts, the isopropylamine salt of phosphonomethyl glycine, the sodium salt of 2,4-dichiorophenoxy acetic acid, the sodiumn salt of methoxy dichioro benzoic acid (dichioro anisic acid), and dicamba (dimethylaniine salt of methoxy dichioro- -16 benzoic acid), Assert bisulfate (American Cyanamid), the ammonium salt of imazaquin (American Cyanamid), and the like.

The following Examples illustrate the invention:

S

*5 The materials used in the Examples and designated by trademark or tradename are as follows: copolymer of vinyl pyrrolidone and C 6 a- olefin in 50:50 weight ratio with a number average molecular weight of about 9500; Agrimer AL30 graft copolymer containing 80% by weight of C2 a-olefin and 20% by weight of polymerized vinylpyrrolidone with a number average molecular weight of about 8600 available as a solid; Agrimer AL22 graft copolymer containing 80% by weight of C 16 a-olefin and by weight of polymerized vinylpyrrolidone with a number average molecular weight of about 7300 available as a liquid; Agrimer VA3 copolymer containing 30 mole vinylpyrrolidone units and mole vinylacetate unit with a number average molecular weight of 5700 and weight average molecular weight of 28,800 determined by the GPC method; 17 Acrylidone ACP- 1004 Rodeo Latron B1956 10 Prowl Roundup 15 Gramoxone a.

S.

5* a a *5 5*5* a a. S

S

a a.

copolymer containing 50:50 weight ratio of the monomer with number average molecular weight =30,000 60,000, 100,000 300,000.

a commercially available pesticide of an aqueous solution containing 53.8% of the isopropylamine salt of phosphonomethylglycine (Monsanto).

77 modified phthalic glycol alkyl resin, and 23 inert ingredients including organic solvent (Rohm Haas); an emulsion concentrate containing 42.0% by wt. pendiinethalin The balance constitutes surfactants and solvents.

a commercially available concentrate of glyphosate with suitable wetting agents. Glyphosate is the isopropylamine salt of phosphonomethylglycine.

a commercially available concentrate of Paraquat in suitable wetting agents. Paraquat is 1, l-dimrethyl-4,4'-bipyridinium dichloride (American Cyanamid).

a commercial form of calcium dodecyl benzene sulfonate produced by Rhone Poulenc containing an oil-soluble anionic surfactant (0.32 parts propylene glycol, 0.65 parts n-butanol, 3.90 parts calcium dodecyl benzene sulfonate and 1.62 parts of aromatic hydrocarbons).

1-ethylpropyl)-3 ,4-dirnethyl-2 ,6-d initrobenzenamine.

Alcasurf CA Pendiniethalin 18 Fusilade EC a commercial formulation of the active ingredient butyl trifluoromethyl-2-pyridyloxy)phenoxy] propionate (FUSILADE 2000) which is a selective systemic herbicide for control of grass weeds in broadleaved crops.

Thiadiazuron N-phenyl-N'-1,2,4-thiadiazol-5-yl urea.

The following examples (Examples 1 through 9) relate to the inventive composition as described above.

In accordance with this embodiment of the invention, emulsion concentrates (EC) may be prepared by mixing an active ingredient with a water-insoluble polymer in accordance with the invention and a solvent for the water-insoluble polymer. Such solvents can include aromatic diluents as well as long-chain alkyl pyrrolidones. These concentrates may then be diluted with water to provide *oo **so ooo [N:\LIBZZ]00008:RRB 19 stable emulsions. I have discovered that a stable emulsion can be prepared from such a concentrate without the presence of a water-soluble surfactant. Thus, in Example 1 comparison of a composition with an aromatic diluent and with and without a water-soluble surfactant is shown. In Example. 2 the use of N-octyl pyrrolidone as a solvent is shown with and without the presence of a water-soluble surfactant. In each case, a stable macroemulsion could be obtained by dilution of the compositions without the water-soluble surfactant. In addition, as is shown in Example 3 the inventive emulsion concentrates provide excellent rainfastness with respect to retention of the active ingredient.

Examples 1 and 2 illustrate the preparation of inventive compositions ~wherein a solvent, an aromatic diluent or long-chain alkyl pyrrolidone, are used.

Example 1 The compositions shown in Table 1 below were prepared by mixing the ingredients and shaking in an orbital shaker for 30 minutes to form homogeneous concentrates.

TABLE 1 Ingredients Weight (grams) IA IB Pendimethalin 21 21 Exxon Aromatic 150 74 74 Gafac RE 610 Agrimer AL 25* AL 25 is commercially available as a 50 percent solution in isopropyl alcohol (IPA). It is used in these examples as a solid obtained by stripping the IPA by evaporation under vacuum below 65 0

C.

The emulsifiable concentrates IA and IB were evaluated for cold stability and the quality of the emulsion obtained on dilution to two percent with water. It is noted that this is the conventional dilution rate for use in the field. The results are shown in Table 1A.

TABLE 1A FREEZE STABILITY OF Pendimethalin EC* Formula (EC) I'

I

Time 24 hrs no crystals no crystals 48 hrs no crystals no crystals measured at 2* The emulsions were evaluated to determine the amount of active ingredient which could be recovered. For this purpose, 50 g of the emulsions obtained on dilution of the compositions I^ and I, were introduced to a long Nessler tube. 1 g aliquots of samples were withdrawn from the middle of the tube periodically, diluted with ethanol 1/500 times and UV spectra were taken. The absorbance at 238.5 nm (X max. the wavelength corresponding to maximum absorbance) was measured and calibration data for absorbance versus concentrations was obtained using standard solutions. Using a least squares line (absorbance 0.08058 x concentration (ppm) 0.0008785), the amount of active ingredient present in the 10 sample taken from the Nessler tube was evaluated over a period of 24 hours. A constant recovery rate of 100% was obtained for each of compositions I, and IB.

The above diluted emulsion concentrate (Ec) A^ and IB were evaluated C: for emulsion stability on standing. Formation of foam, solid, cream, oil and crystal formation upon microscopic examination were observed. The emulsion was passed 15 through various mesh screens to separate any crystals formed which were observed under 250 x magnification. The results are shown in Table 1B hereinafter.

TABLE IlB EMULSION EVALUATION OF PENDIMETHALIN EC ON STANDING Formula I 'AI Dilution I 1 g EC/50 g hard water Pendimethalin 0..42% 0.4i o time After 20 Inversions Key: no emulsion oil stayed on top Ig EC/50 g hard water Top Bottom *6.

foam 0Ohr solid 1 hr cream* 2 hr oil* 4 hr 6 hr 24 hr 24 hr microscope 250X mesh 100 250 translucent macroemulsi( Top 0 f5 C6 C7 C7 C7 Bottom 0 0 0 0 0 0 C6 C7 C7

CIO

0 0 0 0 As used herein, the oil means a clear layer and cream means a cloudy layer of solid and oil.

Table IC shows the formation of crystals for compositions 'A and IB over a period of time.

23 TABLE I C CRYSTAL FORMATION OBSERVATIONS FOR PEND1METHJ&IIN

EC

MICROSCOPE 250X A

'B

Dilution lgl5Og hard water 1 .5g150g hard water 0-Time none observed 50 crystals per view I hr none observed none observed 2 hr none observed 4 hr none observed 10 crystals per view 6 hr none observed 1 crystal per 80 view 24 hr none observed 1 crystal per 30 view Average size crystal 3 x 7 micron Filtered 60eesh0* 100 mesh 0 0 250 mesh 0 0 L I 0- 1- Example 2 Compositions were prepared using the procedure of Example 1 and the following ingredients: TABLE 2 000000 II ~Ingredients -qL The emulsifiable concentrates were evaluated for quality of emulsion on dilution. These results obtained using the same procedure as. for Compositions

'A

and 'B are shown in Table .2A and 2B.

TABLE 2A EMULSION EVALUATION OF Thiadiazuron EC ON STANDING FFormula l *Dilution Ig/50mI lg/50m1 lg/50m] *.0Diluted with DI H 2 0 WHO DI H 2 0 WHO0 *00%Thiadiazuron 0.2% 0.2% 0.2% 0.2% After 20 emulsion emulsion emulsion emulsion Inversions Key T B T B T B T

B

foam 0Omin. 9 070 41 0 in.0 cream iour 6 2 0 0 0 6 s *oi 30r mi1 0 05 0 30 0 02 0 cemso I4hor 621 0 66 0 06 0 651 0 oi 82hr 63 1 0 66 S2 C1 0 65 0 24~4hr65 S 52 C7 0 6 E O fieraede emso 60h 6 0 660 C60 650 250 0hr6 1 2 0 +5 0 24 Top B5 1 65o2tCt0 65 TABLE .2B CRYSTAL FORMATION OBSERVATIONS FOR THIADIAZURON

EC

MICROSCOPE 250X Formula IIA

II

Dilution 2g/100g hard water 2 g/100g hard water 0-Time none observed none observed 1 hr none observed none observed 2 hr none observed none observed 4 hr none observed none observed 6 hr none observed none observed 24 hr none observed none observed Average Size crystal Stirred Emulsion As shown, a stable emulsion on dilution with water can be obtained with the inventive emulsion concentrate without the use of a water-soluble surfactant.

Example 3 Rainfastness evaluations were carried out for polymer films formed in accordance with the invention. These evaluations were carried out using compositions prepared from commercially available formulations. Such formulations conventionally are composed of an agriculturally active chemical (the active ingredient), surfactants and organic diluents as solvents. Consequently, with such commercial formulations, simply by adding the water insoluble polymer in accordance with the present invention, one can obtain the emulsion concentrate of the invention, the solvent and surfactant being present. It is noted that while the surfactant is already present in the commercial formulation as obtained and, consequently, cannot be removed, it is actually not necessary when used with the water-insoluble polymer according to the invention. However, its presence does not adversely affect the ability to produce a significant improvement in the rainfastness of the commercial formulation.

1.

The general procedure used was as follows: 1. A commercial formulation of a given agriculturally active ingredient was admixed with a film-forming water-insoluble polymer.

2. The liquid mixture was then diluted to end use concentrations.

3. An appropriate dose (0.1 g to 0.5 g) was uniformly applied to a 150mm x 0 150mm glass plate uniformly as a 25 -75mm square patch. The patch was dried in a hood under ambient conditions for 48 -72 hours. (3 samples were tested for each formulation.) 4. After a dry film was formed, a fine spray of water was applied to simulate 12 -50mm of rain wash-off. The washings were collected in a waste jar.

The remaining washed patch was extracted with a solvent (ethanol is preferred) quantitatively into a 100 ml volumetric flask. If desired, appropriate dilutions of the ethanol extract were made.

6. The ethanol extract was subjected to ultraviolet spectra examination and the absorbance at a X max. was determined (this value is designated Blank samples of compositions III, III,,, I D HIF, Ip,. and III, were obtained by diluting each in ethanol to yield a solution containing 8 ppm of the active ingredient. The UV absorption of each was measured. These values were utilized to prepare a calibration chart.

This value is designated

X,.

The percent retained was then determined by dividing X, by X, and multiplying by 100.

Blanks of the commercial formulations without polymer were run under identical conditions. The percentage was calculated.

For samples wherein the pesticide used is Pendimethalin, X max. is 239 nm. 0.3 g of diluted samples were used for patches (6.5-13 square centimetres). The amount of wash-off water used as 1.5 to 2.5 g.

9.

10.

In all examples using an aromatic oil in the formulations, samples of the alcohol extract from the dried spot after the rain wash were completely evaporated in a vacuum oven to remove any residual aromatic solvent so as to avoid interference therefrom in the absorbance analysis.

Using the above general procedure, rainfastness evaluations for commercial pendimethalin formulations using Prowl as a commercially available emulsifiable concentrate of this active ingredient. This commercial formulation contains 42.0% of the active ingredient with the balance being surfactants and organic solvents. The compositions used were as follows: Composition III Composition IIIs Composition IIIc Composition mD Composition IIIE 1 g of Prowl was diluted with 100 ml of D.I. water to provide an end use composition containing 0.42% active ingredient.

90 parts of Prowl were mixed with solid Agrimer AL 25 parts). 1 g of this mixture was diluted to 100 parts with D.I.

water.

The formulation of IA (1 g diluted to 50 g with D.I. water).

The formulation of Is (1 g diluted to 50 g with D.I. water).

This composition was the same as III, except that Agrimer VA3 was used in place of Agrimer AL 25. Agrimer VA 3 is commercially available as a 50% solution in ethanol. In these examples, it was used in solid form obtained by stripping the ethanol from the solution under vacuum at low temperature under 65 The resulting composition was obtained by diluting 1 g to 100 ml with D.I. water.

90 parts of Prowl were mixed with 10 parts of solvent-stripped Latron B1956. 1 g of this composition was diluted to 100 g with D.I. water.

The composition was the same as composition mI except that Agrimer AL 25 was replaced with Agrimer AL Composition III Composition IIIl The results of the rainfastness formulations are shown in Table 3.

TABLE 3 Comn- Spotted Contents Weight Appearance Rain Wash Vol. EtoH Absorbance Relative position Sample Sample g Water Used Rainfastness ___ml IIIA.I 1 commercial 0.3003 slightly 1.46 1/100 0.648 56.9 (blank) 2 pendimethalin 0.3021 beaded film 1.48 1/100 0.530 46.2 3 (Prowl) No 0.3008 (25mm dia. 1.50 1/100 0.654 57.3 _____Agrimer surface area) 53.5 6 ilia 1 commercial 0.3064 clear, even 1.48 1/100 0.993 95.6 2 pendimethalin 0.3018 film 1.66 1/100 0.986 96.5 3 (Prowl) 0.3020 (lO0mm dia.) 1.54 1/100 0.986 96.4 4 Agrimer 0.3039 1.55 1/100 0.990 96.4 25 (0.1 0.4 11D I pendimethalin 0.3028 clear beaded 1.47 1150 0.255 13.6 2 0.3065 film 1.44 1150 0.295 15.2 3 Gafac RE 610 0.3020 (1O0mm dia.) 1.51 1150 0.406 21.5 4 solvent 0.3021 1.52 1150 0.239 12.8 15.8 4 111C I pendimethalin 0.3008 clear even 1.50 1/100 79.0 2 0.2996 film 1.51 1/100 92.9 3 Agrimer AL25 0.3075 (lO0mnidia.) 1.51 1/100 92.9 4 solvent 0.3060 1.52 1/100 82.0 86.7 7 (no surfactant) 9 9. 9 9.

.9 9*9 9.

9 9 9 9* 9 9. 9 9 9 9.

999999 99 9 9 9 9 *9 9 999999 9 9999 9 9 9 9 Corn- Spotted Contents Weight Appearance Rain Wash Vol. EtoH Absorbance Relative position Sample Sample g Water Use Rainfastness 'lIE 1 Prowl 0.3062 uneven 1.57 1/100 0.919 85.5 VA 3 2 Agrimer VA 3 0.3028 dry 1.58 1/100 0.903 85.0 3 0.3030 film 1.56 1/100 0.986 92.7 IF I Prowl solvent 0.3516 beaded film 2.31 '1/100 0.612 53.6 2 stripped L-ation 0.3 169 2.36 1/100 0.487 47.3 3 B1956 0.3189 2.31 1/100 0.616 59.2 ±6 III(; I Prowl 0.3457 drug residue 2.36 1/100 0.796 70.6 2 Agrimer AL 30 0.3330 unevenly 2.29 1/100 0.738 67.9 3 (1 0.3309 spread 2.33 1/100 0.803 74.3 70.9 ±3 11A2 I Prowl 0.3287 beaded un- 2.30 1/100 0.320 25.3 (blank)* 2 (no agrimer) 0.322 even film 2.25 1/100 0.245 19.8 3 0.3074 2.28 1/100 0.299 25.3 L0.3167 2.31 1/100 0.256 21.0 3 For comparison with "'IF and 111G.

To test the validity of the procedure, compositions III,, III,, III, III, IIIE, III, and II' were diluted in ethanol to yield a solution containing 8 ppm of the active ingredient. The UV absorbance was measured at X max. and all values (concentration of active ingredient) were within 2 of the theoretical values.

0 0 Composition I Composition I Example 4 The following compositions were prepared: IVA identical to composition TA VB same as composition mII except that 2 parts of Agrimer AL were mixed with 98 parts of Prowl and 1 g of this mixture was diluted to 100 g with D.I. water.

Vc This was the same as composition mn except 5 parts of Agrimer AL 25 were mixed with 95 parts of Prowl.

Composition I The rainfastness was evaluated using the experimental procedure of Example 3. The percent of active ingredient recovered from the formulations is shown in Table 4.

Compositions TABLE 4 Agrimer AL 25 in the final dilution 0 0.02 0.05 a.i. recovered

IVA

IV

8 'Vc 54.7 6 77.2 2 80.1 7 The Composition VA

S..

S

EXAMPLE following formulations were prepared: 14.61 g of dried Agrimer AL 25 were dissolved in 64.29 g of Exxon Aromatic 150, 14.61 g N-octyl pyrrolidone were added, followed by the addition of 6.49 g of a surfactant, Alcasurf CA.

The mixture was stirred for 40 minutes in an orbital shaker to produce a clear solution. The composition can also be prepared by using 29.2 g of a 50% isopropyl alcohol solution of the polymer (Agrimer AL 25) and 14.61 g of N-octylpyrrolidone with 64.3 g of Exxon Aromatic 150 (or other higher boiling diluents). The isopropyl alcohol may be separated by evaporation under atmospheric or reduced pressure. 6.49 g Alcasurf CA, is then added to produce 100 g of the inventive composition.

14.6 g of Agrimer AL 30 were dissolved in 14.6 g of N-octyl pyrrolidone, 64.3 g of Exxon aromatic 150 and 6.5 g of Alcasurf CA. The mixture was stirred for 30 minutes to produce a clear solution.

15 g of Agrimer AL 25 (solvent-stripped) were dissolved in g of Exxon aromatic 150.

S

S

Composition

V

B

Composition Vc Composition VD This composition was the same as composition

V

c except that the Agrimer AL 25 was replaced by an equivalent amount of Agrimer AL 30 (solvent-stripped).

(The above-noted compositions are depicted in Table TABLE WEIGHT COMPOSITIONS OF SOLVENT

BASED

POLYMER COMPOSITIONS: f. Ingredients VA VB V c

VD

N-octylpyrrolidone 14.6 14.6 Exxon Aromatic 150 64.3 64.3 85 Ethanol Agrimer AL25 14.6 Agrimer AL 30 14.6 Alcasurf CA 6.5 6.5 Total 100.0 100.0 100 00 t •ft Compositions V^ and Va were diluted with D.I. water or 342 ppm hard water to produce stable emulsions at dilution rates of 1/10, 1/20, 1/50, 1/100 and 1/1000. The emulsions produced from composition V, were more stable than those from composition V8. Hard water produced more stable emulsions than D.I.

water. Formulation of stable emulsions in water makes it possible to use the above compositions in both oil based and water based active ingredient formulations. It is noted that compositions V^ and V, are particularly advantageous for use in oil base active ingredient concentrates in aqueous medium.

'0 o 0 00..

'00 -96 C. 0 .000.

0 0* 0 se e 0* EXAMPLE 6 Rainfast evaluations using the procedure of Example 3 hereinabove were carried out for compositions VB, Vc, and VD as well as at Latron B 1956 for comparison purposes. The compositions used were as follows: Composition VI blank This was essentially the same as composition 'rA* Composition VIA 1 g of Prowl was mixed with 0.67 g of composition V^ and then diluted to 100 g with D.I. water.

Composition VIB 1 g of Prowl was mixed with 0.67 g of composition VB and then diluted to 100 g with D.I. water.

Composition VI c 1 g of Prowl was mixed with 0.67 g of composition Vc and then diluted to 100 g with D.I. water.

Composition VID 1 g of Prowl was mixed with 0.67 g of composition VD and then diluted.to 100 g with D.I. water.

Formulations VI blank, VIA, VIB, VI c and VI D were evaluated for rainfastness of the pendimethalin using 0.32 0.34 g for spotting and 2.2 to 2.4 g of wash water to simulate rain. The evaluation showed that formulations VIA, VIE, VIc and VID exhibited increased retention of the active ingredient as compared to the blank. The effectiveness was in the following decreasing order: VI^ (38.7 6) ViE (30 1) VID (23 4) VIc (19.4 3) VI (12 1) The foregoing represent the averages of three runs for each composition.

In the above experiment, the pump spray equipment used, force of spray, to simulate rain was different from the procedure outlined in Example 3.

This could explain the lower retention.

The evaluation of Latron B1956 as a tank mix additive showed that the inventive formulations produced 60 to 80% higher retention at the same level of Z"application as the Latron B1956 containing composition.

EXAPLE -7 A series of formulations was prepared containing commercial carbaryl (Sevin) and evaluated for rainfastness. Sevin is a formulation containing 27% of carbaryl as an active ingredient. The compositions were as follows: Composition VII blank I g of commercial Sevin was diluted to 200 g with D.I.

'water to produce an emulsion of about 0. 14 active ingredient.

Composition VII^ Same composition as VII blank except that 0.27 g of composition V A was added prior to dilution.

Composition

VI

B Same composition as VII^except that 0.67 g of composition

V

A

were added.

Composition VIIc Same composition as VII^except that composition V

A

was replaced with composition

VI.

Composition VID ,Same as composition VIIBexcept that composition V^ was replaced by composition

V

B

Composition VIE Composition

VII,-

Same as composition VIIB except that composition VA was replaced by composition Vc.

Same as composition VII except that composition V, was replaced by composition

VD.

see* 0* S 96 S (S S 0.0; 'S 66

S.

'S

SSSS

(5 S 5 45.95 S6,, '6~ These formulations were evaluated using the same procedure as set for in Example 3 Specifically, 0.45 0.54 g of the sample were spotted onto glass plates and 1.5 1.7 g of water was used to simulate rain wash. The X max. used for the evaluation was 279 nm and the least square line was used according to the following formula: absorbance 0.03276 X concentration (ppm) 0.016416.

The results of the evaluations are shown in Table 6.

37 TABLE 6 SUMMARY RESULTS OF RAINFASTNESS FOR CARBAMYL ("SEVIN")

FORMULATIONS

COMPOSITION AGRIMERA..R

OVPD

VII (blank) 0 3.

VIIA Agrimer AL 25 (0.02%) :VLIB Agrimer AL 25 VILC Agrimer AL 30 6 (0.05%) VIID Agrimer AL 30 6 VIlIE Agrimer AL 25 56 6 VHF Agrimer AL 30 59.6 ±8 EXAMPLE 8 It is noted that formulation VA is particularly useful as an adjuvant for oil based concentrates. Such oil based concentrates (concentrates based on a nonaqueous hydrophobic solvent) normally are composed of: active ingredients 10 to 60 percent; surfactants (wetting agents and emulsifiers) 1 to 30 percent; hydrophobic non-aqueous solvents 10 to 80 percent; and optionally, defoamers, rheology modifiers and the like as needed 0 to 5 percent.

38 It exhibits enhanced efficacy with the active ingredient Fusilade

EC

when used at a 0.2 concentration in the final dilution. Also, increased biological activity with chloropyrifos, an insecticide, was observed when composition V, was used with an oil based concentrate for this active ingredient at a 0.2 concentration in the final dilution.

EXAMPLE 9 The compositions of the present invention, for example, Compositions VA and V, can be used as granulating fluids to incorporate the water-insoluble polymers in solid water-dispersible granular formulations. A typical formulation is as 10 follows: Active ingredient (Atrazine) 82.3 by weight Binder (polyvinyl pyrrolidone optional) Dispersant Wetting agent Defoamer 0.2 Composition V, or V B 10.0 Typical examples of the dispersants, wetting agents, and defoamers are: Morwet D-425, alkylated naphthalene sulfonate sodium salt, Morwet EFW which is a proprietary mixture of sulfated alkylcarboxylate and a sulfonated alkylnaphthalene sodium salt, and FOAMASTER soap L which is a proprietary soda soap.

In such a composition, the aromatic oil diluent can be dispensed with.

The water-dispersible granules are prepared by charging the weight ingredients (200 g) in a V-blender and mixing for 10 to 30 minutes. The charge is then loaded to a 61cm pan granulator set at an angle of 50 to 550. The pan is rotated at a speed of 15 rpm and granulation is accomplished by spraying the charge with water at an appropriate speed, typically, 20 to 30 ml of water is used over a period of 10 to minutes. After granulation, the wet granules are dried at 40 to 50°C to reduce the moisture level to about 1 to The dry granules can be sieved to segregate them into different size fractions as desired. Undersized granules can be reformulated by recycling to the process. The granules can also be prepared by using a conventional extrusion process with a suitable extruder.

o oo

Claims (14)

1. An emulsion concentrate comprising: a) an effective amount of an agriculturally active chemical; b) a solvent for the agriculturally active chemical; and c) a water-insoluble film forming polymer being a graft polymer of N-vinylpyrrolidone and an a-olefin wherein the a-olefin is present in an amount of at least 5 wt based on the weight of the graft polymer.

2. The emulsion concentrate of claim 1 wherein the solvent is a long-chain alkylpyrrolidone having the formula R2 N 0 R 3 wherein R 2 is hydrogen or alkyl having from 6 to 14 carbon atoms and R 3 is alkyl having from 6 to 14 carbon atoms with the proviso that at least one of R 2 or R 3 must contain at least 6 carbon atoms and the sum of the carbon atoms in R 2 and R 3 cannot exceed 14, or a synthetic or naturally occurring oil having a high hydrophobic character or having a fractional dispersive solubility parameter of greater e 1eq 5 than 70%

3. The emulsion concentrate of claim 2 wherein R 2 is hydrogen and R 3 is Cs or C12 alkyl.

4. The emulsion concentrate of claim 2 or 3 which further contains N-methylpyrrolidone.

5. The emulsion concentrate of claim 1 wherein the solvent is selected from the group consisting of soybean oil, rapeseed oil, long chain alcohols, long chain ketones, long chain esters, 20 ethers, aromatic petroleum oils composed of heavy aromatic solvent naphtha about 60%; middle distillate solvent extractant about 40%, and combinations thereof.

6. The emulsion concentrate of any one of claims 1 to 4 wherein the solvent is selected from the group consisting of N-octylpyrrolidone, N-methylpyrrolidone, a crude oil distillate having an average boiling point of at least 1200C, and mixtures thereof. 25 7. The emulsion concentrate of claim 1 comprising from about 2 to 90 weight percent of a solvent selected from the group consisting of N-octyl-pyrrolidone, a crude oil distillate having an average boiling point of at least 120°C and mixtures thereof, from about 1 to 60 weight percent of a copolymer of N-vinyl-pyrrolidone and a C 1 6 a-olefin in a 50:50 weight ratio and a number average weight of about 9500.

8. The emulsion concentrate of any one of claims 1 to 7 wherein the N-vinylpyrrolidone is present in at least 20 percent on a weight basis of the graft polymer

9. The emulsion concentrate of any one of claims 1 to 8 wherein the a-olefin contains up to 0 carbon atoms. [R:\LIBFF]O8778speci.doc: njc An emulsion concentrate comprising an agriculturally active chemical, a solvent for the agriculturally active chemical and a water-insoluble film-forming polymer, substantially as hereinbefore described with reference to any one of Examples 1, 2, compositions IlII, IIIc, IllD, llIE, IlIF, IlIG, IVB, IVc, VA, VB, Vc, VD, VIA, Via, Vic, VID, VIIA, Vilg, Vlec, VIID, VIlE, VIIF, Examples 8 or 9.

11. A method of preparing an emulsion concentrate comprising an agriculturally active chemical, a solvent for the agriculturally active chemical and a water-insoluble film-forming polymer which method is substantially as hereinbefore described with reference to any one of Examples 1, 2, compositions IIIB, Illc, IID, llIE, IIIF, IIIG, IVg, IVc, VA, VB, Vc, VD, VIA, VI, Vic, VID, VIIA, Vile, Vilc, Vllo, VIIE, VIIF, Examples 8 or9. o 12. An emulsion concentrate comprising: a) 2 to 90% by weight of a solvent selected from the group consisting of long-chain alkyl pyrrolidones, synthetic or naturally occurring hydrophobic oils, and mixtures thereof; b) 1 to 60% by weight of a water-insoluble graft polymer of N-vinyl-pyrrolidone and an a- olefin wherein the N-vinylpyrrolidone is present in at least 20% on a weight basis; and c) 1 to 85% by weight of an oil-soluble surfactant.

13. The concentrate of claim 12 wherein the solvent is selected from the group consisting of 10-20% by weight N-octylpyrrolidone, 50-70% by weight of the hydrophobic oil, or mixtures thereof, the water-insoluble polymer is present in an amount from 10 to 20% by weight and the oil-soluble surfactant is present in the amount from 5 to 10% by weight. 20 14. The concentrate of either of claims 12 or 13 wherein the solvent is a long-chain alkylpyrrolidone. The concentrate of any one of claims 12 to 14 wherein the polymer is a copolymer of N- .vinylpyrrolidone and a C16 a-olefin in a 50:50 weight ratio and having a number average weight of about 9500. 2i. 5 16. The concentrate of any one of claims 12 to 15 wherein the polymer is a copolymer of N- vinylpyrrolidone and a C20 a-olefin in a 20:80 weight ratio.

17. A composition for application to agricultural crops comprising an emulsion of the emulsion concentrate of any one of claims 1 to 10 or 12 to 16, diluted at least 2-fold with water.

18. A method for treating crops comprising applying the composition of claim 17 to the crops.

19. A method for producing a water-dispensible granule of an agriculturally active ingredient comprising charging the emulsion concentrate of any one of claims 1 to 10 or 12 to 16 to a granulator to form granules, and drying the granules. Granules obtained by the method claim 19. [R:\L1BFF]08778speci.doc:njc 42

21. A method for treating crops comprising mixing the granules of claim 20 with water to form an emulsion and applying the emulsion to the crops. Dated 14 June, 2000 ISP Investments Inc. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON [R\LI BF F1087 7 8speci. doc: n.1c