Compositions of insoluble film-forming polymers and uses therefor

Emulsion concentrates of water-insoluble film-forming polymers are disclosed which can be utilized to form water-resistant films of active ingredients, such as, agriculturally active chemicals. Methods for preparation and use of the emulsion concentrates are disclosed.

BACKGROUND OF THE INVENTION 
Certain types of polymers exhibit film-forming properties and when 
dissolved in an organic solvent, can be applied for the purpose of 
providing a water-resistant coating on a substrate. Usually, the 
film-forming polymer in the solvent is applied to the particular substrate 
to be coated, and the solvent is allowed to evaporate or removed leaving a 
film of the polymer. 
Generally, however, such water-resistant, film-forming polymers are soluble 
only in organic solvents, i.e., 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. 
Typical of such polymers are copolymers of N-vinylpyrrolidone with 
.alpha.-olefins, vinyl acetate, styrene, acrylates, acrylic acids, amides, 
maleic acid, mono and diesters of maleic acids, and the like. 
In parent application Ser. No. 07/975,811, a method is disclosed 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 active ingredients, e.g., fungicides, preservatives, insecticides, 
insect repellents, pheromones, radiation absorbents, dyes, and the like, 
can be included in the composition. 
The compositions disclosed therein are composed of the water-insoluble 
polymer, a surfactant, and a long-chain alkylpyrrolidone. The amounts of 
the polymer surfactant and long-chain alkylpyrrolidone can vary within a 
broad range. However, the relative compositional ranges of each must be 
such that a clear, stable microemulsion or solution of the insoluble 
polymer is obtained on the addition of water. 
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 efficiency of the chemicals, since the longer the 
chemical remains in contact with the plant or soil surface, the more 
effective it is. 
SUMMARY OF THE INVENTION 
I have discovered a new class of emulsion concentrates of such 
water-insoluble film-forming polymers which comprise a water-insoluble 
polymer, an agriculturally active chemical, and an organic solvent for the 
agriculturally active chemical. The water-insoluble polymers used in the 
present invention are graft polymers of vinylpyrrolidone and 
.alpha.-olefin wherein the N-vinylpyrrolidone is present in more than 
about 5 percent on a weight basis. Preferably, the weight percent of 
N-vinyl pyrrolidone is at least about 10 percent. The .alpha.-olefin 
should contain from 8 to 30, and preferably, from 16 to 20 carbon atoms. 
The inventive compositions are particularly convenient for use with 
oil-based concentrates, e.g., 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). 
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 agriculturally active 
chemical or ingredient (hereinafter, sometimes referred to as a.i.). 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 active 
ingredient forms a film on the particular substrate, e.g., the plant or 
soil, which results in improved retention and enhanced bioactivity of the 
agriculturally active ingredient and also provides superior rainfastness 
for such ingredients on leaf and substrate surfaces.

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 1 micron, and usually greater than about 10 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. 
"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 a.i.) 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, i.e., 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. 
Long-chain N-alkylpyrrolidones suitable for use as a solvent in the present 
invention have the formula 
##STR1## 
wherein R.sub.2 is hydrogen or allcyl having from 6 to 14 carbon atoms and 
R.sub.3 is alkyl having from 6 to 14 carbon atoms with the proviso that at 
least one of R.sub.2 or R.sub.3 must contain at least 6 carbon atoms and 
the sum of the carbon atoms in R.sub.2 and R.sub.3 cannot exceed 14. 
Preferably, R.sub.2 is hydrogen and R.sub.3 is C.sub.8 or C.sub.12. 
Mixtures of two long-chain 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 also be an organic diluent which is a synthetic or 
naturally occurring oil having a high hydrophobic character or having a 
fractional dispersive solubility parameter of greater than 70% and 
preferably greater than 85% and a molar volume of greater than 90 cm.sup.3 
/mole. These properties are defined in the C.R.C. Handbook. 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.degree. 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 60%; 
Middle distillate solvent extractant--about 40%; 
Normally, these oils contain predominantly the C.sub.9 .multidot.C.sub.15 
aromatic hydrocarbons and primarily the C.sub.10 -C.sub.12 hydrocarbons 
having a flash point of about 203.degree. F. 
When a surfactant is used, e.g., 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, 
e.g., 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, 
e.g., 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 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, 
N.J.) 
Polymers particularly suitable for use in the present invention include 
copolymers of vinyl pyrrolidone and .alpha.-olefins. Typically, such 
.alpha.-olefins contain up to 20, and preferably 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 AL25 (International Specialty Products (ISP) Corporation), which 
is a copolymer of an .alpha.-olefin having the formula C.sub.14 H.sub.29 
CH.dbd.CH.sub.2 (50%) and N-vinylpyrrolidone (50%), and Agrimer AL30 (ISP 
Corporation), which is a copolymer of an .alpha.-olefin having 20 carbon 
atoms (80%), and N-vinylpyrrolidone (20%). Copolymers of 
N-vinylpyrrolidone and vinyl acetate should contain at least about 10% 
N-vinylpyrrolidone and have a weight average molecular weight of at least 
about 10,000. 
Typically, the inventive concentrate comprises from about 2 to 90 percent, 
preferably from 5 to 85, and most preferably, from about 30 to 80 percent 
by weight solvent, e.g., N-alkyl pyrrolidone, organic diluent or both and 
from about 1 to 60, and 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, the amount is 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, 
and lubricating, purposes and to impart hydrophobicity or hydrophilicity. 
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 water-insoluble 
film-forming polymers in an aqueous based vehicle, i.e., solution, 
emulsion 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 film-forming 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. 
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 herein, 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 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, i.e., between 40.degree. F. and 
90.degree. F. and their solubility or miscibility with water or other 
common organic solvents, e.g., aromatics, such as, toluene, xylene, 
methylated and polyalkylated naphthalenes, and aliphatic solvents. 
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 acid, 
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-dichlorobenzoic acid, 
Common esters of 2-methyl-4-chlorophenoxyacetic acid, 
Piperonyl butoxide 3,4-methylenedioxy-6-propyl benzyl n-butyl diethylene 
glycol ether, 
Bromophos ethyl: 0,0-diethyl-0-2,5-dichloro-4-bromophenyl thionophosphate, 
N-(2-mercaptoethyl) benzene-sulfonamide (BETASAN.RTM.), 
Isobomyl Thiocyanoacetate (THANITE.RTM.), 
Ioxynil ester of octanoic acid, 
Molinate S-ethyl hexahydro-1H-azepine-1-carbothioate, 
PP 511 0,0-dimethyl-(2-diethylamine 4-methyl-6-pyrimidinyl) carbamate, 
PP 211 0,0-diethyl 0-(2-diethylamine-4-methyl-6-pyrimidinyl) 
phosphorocarbamate, 
5-Ethoxy-3-(trichlorometyl)-1,2,4-thiadiazole (TERRAZALE.RTM.), 
Ethyl-s-s-dipropyl-phosphodithioate (MOCAP.RTM.), 
S-Ethyl dipropylthiocarbamate (EPTAM.RTM.), 
S-Ethyl diisobutylthiocarbamate (SUTAN.RTM.), 
S-n. propyl-di-n-propylthiocarbamate (VERNAM.RTM.), 
S-propyl butylethylthiocarbamatae (TILLAM.RTM.), 
S-ethyl ethylcyclohexylthiocarbamate (RO-NEET.RTM.), 
Malathion (S-(1,2-dicarboxyethyl)-0,0-dimethyl phosphorodithioate), 
Diazinon (0,0-diethyl,0-(2-isopropyl-4-methyl-6-pyrimidinyl) 
phosphorothioate, 
-Ethyl-S-phenyl-ethylphosphonodithioate (DYFONATE.RTM.), 
Toxaphene (Octachlorocamphene), 
Bromoxynil (3,5-dibromo-4-hydroxy benzonitrile ester of n. octanoic acid, 
2-chloro-N-2,6-diethylphenyl-N-methoxymethylacetamide (LASSO.RTM.), 
Diallate S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate, 
Triallate S-2,33-trichloroallyl 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 (2,4,5-trichlorophenoxy acetic acid) 
Monuron (3-(p-chlorophenyl)-1,1-dimethyl urea) 
Diuron (3-(3,4-dichlorophenyl)-1,1-dimethyl urea) 
Bromacil (5-bromo-3-sec. butyl-6-methyl uracil) 
Isocil (5-bromo-3-isopropyl-6-methyl uracil) 
Linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methyl urea 
Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) Simazine 
(2-chloro-4,6,-bis(ethylamino)-s -triazine 
Dodine (n-dodecylguanidine acetate) 
Thiram (tetramethylthiuram disulfide) 
N-(mercaptomethyl)phthalimide s-(o,o dimethylphosphorodithioate) 
(IMIDAN.RTM.) 
Lindane (gamma 1,2,3,4,5,6 hexachlorocyclohexane) 
Folpet (N-trichloromethylphthalimide) 
Manazon (s-(4,6-diamino- 1,3,5-triazin-2-yl methyl)dimethyl 
phosphorothiolthionate) 
Barban (4-chloro-2 butynyl m-chlorocarbanilate) 
Tricumba 2-methoxy-3,5,6-trichlorobenzoic acid 
Trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) 
(2,3dihydro-5-carboxanilido-6-methyl-1,4-oxathiin) (VITAVAX.RTM.) 
2,4-dichlorophenoxyacetic acid 
-(4-chloro-2-methylphenoxy) butyric acid 
2-(2,4-dichlorophenoxy) propionic acid 
Ioxynil: 3,5 diiodo-4-hydroxybenzonitrile 
Bromoxynil: 3,5 dibromo-4-hydroxybenzonitrile 
Methoxychlor: 2,2,-Bis(p-methoxyphenyl)- 1,1-trichloroethane 
PP 781: 4(2-chloro phenylhydrazono)-3-methyl-5-isoxazolone* 
PP 675: 5-butyl-2-dimethylamino-4-hydroxy-6-methyl pyrimidine* 
PP 062:5,6-dimethyl-2-dimethylamino-4 pyrimidinyl dimethylcarbamate* 
PP 149:5-n-butyl-2 ethylamino-4-hydroxy-6 methylpyrimidine* 
C 6313 N'-(4-bromo-3-chlorophenyl)-N-methoxy-N-methylurea 
C 6989 2,4'dinitro-4-trifluoromethyl-diphenylether 
Chloroxuron N'-4-(chlorophenoxy) phenyl-NN-dimethylurea 
Dichlobenil 2,6-dichlorobenzonitrile 
FNT * Manufactured by Imperial Chemical Industries Limited 
Diphenamid NN-dimethyl-2,2-diphenylacetamide 
Fenac 2,3,6-trichlorophenylacetic acid 
Fluomemron N'-(3-trifluoromethylphenyl)-NN-dimethylurea 
GS 14260 4-ethylamino-2-methylthio-6-t-butyl-amino- 1,3,5-triazine 
PCP Pentachlorophenol 
Lenacil 3-cyclohexyl-6,7-dihydro-1H-cyclo-pentapyrimidine-2,4-(3 
H,5H)-dione 
Pyrazon 5-amino-4-chloro-2-phenyl-3-pyridazone 
Metrobromuron N'-(4-bromophenyl)-N-methoxy-N-methylurea 
Metoxymarc N-(4-methoxybenzoyl)-N-(3,4-dichlorophenyl)-N',N '-dimethylurea 
Neburon N-butyl-N'-(3,4-dichlorophenyl-N-methylurea 
NIA 11092 1,1-dimethyl-3-[3-(n-t-butyl carbamyloxy)phenyl]urea 
Mecoprop 2-(4-chloro-2 methylphenoxy)propionic acid 
Monolinuron N'-(4-chlorophenyl)-N-methoxy-N-methylurea 
Nitrofen 2,4-dichlorophenyl 4-nitrophenylether 
Propanil N-(3,4-dichlororphenyl)propionamide 
Pyriclor 2,3,5-trichloro-4-pyridinol 
Solan 3'-chloro-2-methyl-p-valerotoluidide 
Terbacil 5-chloro-3-t-butyl-6-methyluracil 
UC 22463 (SIRMATE)-3,4-dichlorobenzyl N-methylcarbamate 
WL 9385 2-Azido-4-ethylamino-6-t-butylamino-s-triazine 
Propachlor 2-chloro-N-isopropylacetanilide 
CP 50144 2-chloro-N-2,6-diethylphenyl-N-methoxymethylacetamide 
CP 31675 2-chloro-N-(2 methyl-6-t-butylphenyl)acetamide 
Cypromid 3',4'-dichlorocyclopropane carboxanilide 
Fenuron NN-dimethyl-N-phenylurea 
Chlorbromuron N'-(4-bromo-3-chlorophenyl)-N-methoxy-N-methylurea 
Ametryne 2-methy lmercapto-4-ethy lamino-6-isopropyl-amino-s-triazine 
Prometryne 2-methylmercapto-4,6-bisisopropyl amino-s-triazine 
DCPA dimethyl 2,3,5,6, tetrachloroterephthalate 
Benerin N-buty 1-N-ethyl-2,2,2, trifluoro-2,6-dinitro-p-to luidine 
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-trichlorophenyl-4'-nitrophenyl ether 
Pentachloro nitrobenzene 
1-(butyl carbamoyl)-2-benzimidazole carbamic acid, methyl ester 
(BENLATE.RTM.). 
Carbaryl (methylnaphthyl carbamate) (active ingredient in Sevin). 
The third group constitutes those compounds which are water-soluble, such 
as, salts, e.g., the isopropylamine salt of phosphonomethyl glycine, the 
sodium salt of 2,4-dichlorophenoxy acetic acid, the sodium salt of methoxy 
dichloro benzoic acid (dichloro anisic acid), and dicamba (dimethylamine 
salt of methoxy dichlorobenzoic acid), Assert bisulfate (American 
Cyanamid), the ammonium salt of imazaquin (American Cyanamid), and the 
like. 
The following Examples illustrate the invention: 
The materials used in the Examples and designated by trademark or tradename 
are as follows: 
__________________________________________________________________________ 
Agrimer AL25 
copolymer of vinyl pyrrolidone and C.sub.16 .alpha.-olefin in 
50:50 
weight ratio with a number average molecular weight of about 
9500; 
Agrimer AL30 
graft copolymer containing 80% by weight of C.sub.20 
.alpha.-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.sub.16 
.alpha.-olefin and 
20% 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 70 
mole % vinylacetate unit with a number average molecular 
weight of 5700 and weight average molecular weight of 28,800 
determined by the GPC method; 
ACP-1004 
copolymer containing 50:50 weight ratio of the monomer with 
number average molecular weight = 30,000-60,000, 100,000- 
300,000. 
Rodeo a commercially available pesticide of an aqueous solution con- 
taining 53.8% of the isopropylamine salt of phosphonomethyl- 
glycine (a.i.-1) (Monsanto). 
Latron B1956 
77% modified phthalic glycol alkyl resin, and 23% inert 
ingredients including organic solvent (Rohm & Haas); 
Prowl an emulsion concentrate containing 42.0% by wt. pendimethalin 
(a.i.-2). The balance constitutes surfactants and solvents. 
Roundup a commercially available concentrate of glyphosate with suitable 
welling agents. Glyphosate is the isopropylamine salt of 
phosphonomethylglycine. 
Gramoxone 
a commercially available concentrate of Paraquat in suitable 
wetting agents. Paraquat is 1,1-dimethyl-4,4'-bipyridinium 
dichloride (American Cyanamid). 
Alcasurf CA 
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). 
Pendimethalin 
N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine. 
Fusilade EC 
a commercial formulation of the active ingredient butyl 2-[4-(5- 
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. 
__________________________________________________________________________ 
In accordance with the present 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 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, e.g., 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 
______________________________________ 
Weight (grams) 
Ingredients I.sub.A 
I.sub.B 
______________________________________ 
Pendimethalin 21 21 
Exxon Aromatic 150 74 74 
Gafac RE 610 -- 5 
AgriLiner AL 25* 5 -- 
______________________________________ 
*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.degree. C. 
The emulsifiable concentrates I.sub.A and I.sub.B 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.sub.A I.sub.B 
______________________________________ 
Time 24 hrs no crystals 
no crystals 
48 hrs no crystals 
no crystals 
______________________________________ 
*measured at 2.degree. .+-. 1.degree. C. 
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.sub.A and I.sub.B 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 (.lambda. max. i.e., 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.times.concentration 
(ppm)+0.0008785), the amount of active ingredient present in the 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.sub.A and I.sub.B. 
The above diluted emulsion concentrate (Ec) I.sub.A and I.sub.B were 
evaluated for emulsion stability on standing. Formation of foam, solid, 
cream, oil and crystal formation upon microscopic examination were 
observed. The emulsion was passed through various mesh screens to separate 
any crystals formed which were observed under 250.times. magnification. 
The results are shown in Table lB hereinafter. 
TABLE 1B 
______________________________________ 
EMULSION EVALUATION OF PENDIMETHALIN 
EC ON STANDING 
Formula I.sub.A I.sub.B 
______________________________________ 
Dilution 1 g EC/50 g hard water 
1 g EC/50 g hard water 
% Pendi- 0.42% 0.42% 
methalin 
0 time no emulsion partial emulsion 
oil stayed on top 
half way down the tube 
After 20 translucent macroemulsion 
Inversions 
macroemulsion 
Key: Top Bottom Top Bottom 
foam 0 hr 
0 O f10 0 
solid 1 hr 
f5 0 C5 0 
cream* 2 hr 
C6 0 C6 0 
oil* 4 hr 
C7 0 C7 0 
6 hr C7 0 C7 0 
24 hr C7 0 C10 0 
24 hr 
microscope 
250X mesh 
60 0 0 
100 0 0 
250 0 + 
______________________________________ 
*As used herein, the oil means a clear layer and cream means a cloudy 
layer of solid and oil. 
Table 1C shows the formation of crystals for compositions I.sub.A and 
I.sub.B over a period of time. 
TABLE 1C 
______________________________________ 
CRYSTAL FORMATION OBSERVATIONS FOR 
PENDIMETHALIN EC MICROSCOPE 250X 
I.sub.A I.sub.B 
______________________________________ 
Dilution 1 g/50 g hard water 
1.5 g/50 g hard water 
0-Tiine none observed 50 crystals per view 
1 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 .times. 7 micron 
Filtered 
60 mesh 0 0 
100 mesh 0 0 
250 mesh 0 0 
______________________________________ 
EXAMPLE 2 
Compositions were prepared using the procedure of Example 1 and the 
following ingredients: 
TABLE 2 
______________________________________ 
Weight (grams) 
Ingredients II.sub.A 
II.sub.B 
______________________________________ 
Thiadiazuron 10 10 
Agsol Ex 8 (N-octylpyrrolidone) 
80 80 
Agrimer AL 35 5 -- 
Gafac RE 610 -- 5 
______________________________________ 
The emulsifiable concentrates were evaluated for quality of emulsion on 
dilution. These results obtained using the same procedure as for 
compositions I.sub.A and I.sub.B are shown in Table 2A and 2B. 
TABLE 2A 
______________________________________ 
EMULSION EVALUATION OF Thiadiazuron 
EC ON STANDING 
Formula # II.sub.A II.sub.B 
______________________________________ 
Dilution 1 g/50 ml 
1 g/50 ml 1 g/50 ml 
1 g/50 ml 
Diluted with 
DI H.sub.2 O 
WHO DI H.sub.2 O 
WHO 
% 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 0 min. 
9 0 7 0 41 0 38 0 
solid 30 min. 
0 0 0 0 30 0 0 0 
cream 1 hour 
o 1 0 o 2 0 0 0 o 1 0 
oil 2 hr o 1 0 o 5 0 C1 0 o 2 0 
E = separated 
emulsion 
#: mm 
4 hr o 2 0 o 6 0 C6 0 o 5 0 
6 hr o 3 S1 o 6 S2 C6 0 o 5 0 
8 hr o 3 S1 o 6 S2 C6 0 o 5 0 
24 hr o 5 S1 o 5 S2 C7 0 o 5 E 50 
filtered 
mesh 
60 0 0 0 0 
100 0 0 0 + 
250 0 0 + + 
______________________________________ 
T = Top; B = Bottom 
TABLE 2B 
______________________________________ 
CRYSTAL FORMATION OBSERVATIONS FOR 
THIADIAZURON EC MICROSCOPE 250X 
Formula # II.sub.A II.sub.B 
______________________________________ 
Dilution 2 g/100 g hard water 
2 g/100 g 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. 
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. An 
appropriate dose (0.1 g to 0.5 g) was uniformly applied to a 6".times.6" 
glass plate uniformly as a 1-3" 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 0.5-2 inches of rain wash-off. The washings were collected in a 
waste jar. 
5. 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 .lambda. max was determined (this value is designated 
X.sub.1). 
7. Blank samples of compositions III.sub.A, III.sub.B, III.sub.C, 
III.sub.D, III.sub.E, III.sub.F, and III.sub.G 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.sub.2. 
8. The percent retained was then determined by dividing X.sub.1 by X.sub.2 
and multiplying by 100. 
9. Blanks of the commercial formulations without polymer were run under 
identical conditions. The percentage was calculated. 
10. For samples wherein the pesticide used is Pendimethalin, .lambda. max. 
is 239 nm. 0.3 g of diluted samples were used for patches (1-2 square 
inches). The amount of wash-off water used was 1.5 to 2.5 g. 
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.sub.A --1 g of Prowl was diluted with 100 ml of D.I. water 
to provide an end use composition containing 0.42% active ingredient. 
Composition III.sub.B --90 parts of Prowl were mixed with solid Agrimer AL 
25 (10 parts). 1 g of this mixture was diluted to 100 parts with D.I. 
water. 
Composition III.sub.C --The formulation of I.sub.A (1 g diluted to 50 g 
with D.I. water). 
Composition III.sub.D --The formulation of I.sub.B (1 g diluted to 50 g 
with D.I. water). 
Composition III.sub.E --This composition was the same as III.sub.B 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.degree. C.). The resulting 
composition was obtained by diluting 1 g to 100 ml with D.I. water. 
Composition III.sub.F --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. 
Composition III.sub.G --The composition was the same as composition 
III.sub.B except that Agrimer AL 25 was replaced with Agrimer AL 30. 
The results of the rainfastness formulations are shown in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Vol. EtoH 
Com- Spotted Weight Rain Wash 
Used % Relative 
position 
Sample 
Contents Sample g 
Appearance 
Water (g) 
ml Absorbance 
Rainfastness 
__________________________________________________________________________ 
II.sub.A-1 
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 
(1" dia. 
1.50 1/100 0.654 57.3 
Agrimer surface area) 53.5 .+-. 6 
III.sub.B 
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 
(4" dia.) 
1.54 1/100 0.986 96.4 
4 Agrimer 0.3039 1.55 1/100 0.990 96.4 
AL 25 (0.1%) 96.2 .+-. 0.4 
III.sub.D 
1 pendimethalin 
0.3028 
clear beaded 
1.47 1/50 0.255 13.6 
2 (a.i) 0.3065 
film 1.44 1/50 0.295 15.2 
3 Gafac RE 610 + 
0.3020 
(4" diameter) 
1.51 1/50 0.406 21.5 
4 solvent 0.3021 1.52 1/50 0.239 12.8 
15.8 .+-. 4 
III.sub.C 
1 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 
(4" diameter) 
1.51 1/100 92.9 
4 solvent 0.3060 1.52 1/100 82.0 86.7 .+-. 7 
(no surfactant) 
III.sub.E 
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 (0.1%) 0.3030 
film 1.56 1/100 0.986 92.7 
87.7 .+-. 
III.sub.F 
1 Prowl + solvent 
0.3516 
beaded film 
2.31 1/100 0.612 53.6 
2 stripped Lation 
0.3169 2.36 1/100 0.487 47.3 
3 B1956 0.3189 2.31 1/100 0.616 59.2 
(0.1%) 53.4 .+-. 6 
III.sub.G 
1 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 
III.sub.A-2 
1 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 
0.3167 2.31 1/100 0.256 21.0 
22.9 .+-. 3 
__________________________________________________________________________ 
*For comparison with Ill.sub.F and III.sub.G. 
To test the validity of the procedure, compositions III.sub.A, III.sub.B, 
III.sub.C, III.sub.D, III.sub.E, III.sub.F, and III.sub.G were diluted in 
ethanol to yield a solution containing 8 ppm of the active ingredient. The 
UV absorbance was measured at .lambda. max. and all values (concentration 
of active ingredient) were within .+-.2% of the theoretical values. 
EXAMPLE 4 
The following compositions were prepared: 
Composition IV.sub.A --identical to composition III.sub.A 
Composition IV.sub.B --same as composition III.sub.B except that 2 pans of 
Agrimer AL 25 were mixed with 98 pans of Prowl and 1 g of this mixture was 
diluted to 100 g with D.I. water. 
Composition IV.sub.C --This was the same as composition III.sub.B except 5 
pans of Agrimer AL 25 were mixed with 95 parts of Prowl. 
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. 
TABLE 4 
______________________________________ 
% Agrimer AL 25 
Compositions 
in the final dilution 
% a.i. recovered 
______________________________________ 
IV.sub.A 0 54.7 .+-. 6 
IV.sub.B 0.02 77.2 .+-. 2 
IV.sub.C 0.05 80.1 .+-. 7 
______________________________________ 
EXAMPLE 5 
The following formulations were prepared: 
Composition V.sub.A --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. 
Composition V.sub.B --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. 
Composition V.sub.C --15 g of Agrimer AL 25 (solvent-stripped) were 
dissolved in 85 g of Exxon aromatic 150. 
Composition V.sub.D --This composition was the same as composition V.sub.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 5) 
TABLE 5 
______________________________________ 
% WEIGHT COMPOSITIONS OF SOLVENT BASED 
POLYMER COMPOSITIONS: 
Ingredients V.sub.A V.sub.B V.sub.C 
V.sub.D 
______________________________________ 
N-octylpyrrolidone 
14.6 14.6 -- -- 
Exxon Aromatic 150 
64.3 64.3 85 85 
Ethanol -- -- -- -- 
Agnmer AL25 14.6 -- 15 -- 
Agriiner AL 30 -- 14.6 -- 15 
Alcasurf CA 6.5 6.5 -- -- 
Total 100.0 100.0 100 100 
______________________________________ 
Compositions V.sub.A and V.sub.B 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.sub.A 
were more stable than those from composition V.sub.B. 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.sub.A and V.sub.B are particularly advantageous for use in 
oil base active ingredient concentrates in aqueous medium. 
EXAMPLE 6 
Rainfast evaluations using the procedure of Example 3 hereinabove were 
carried out for compositions V.sub.A, V.sub.B, V.sub.C, and V.sub.D 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 
III.sub.A. 
Composition VI.sub.A --1 g of Prowl was mixed with 0.67 g of composition 
V.sub.A and then diluted to 100 g with D.I. water. 
Composition VI.sub.B --1 g of Prowl was mixed with 0.67 g of composition 
V.sub.B and then diluted to 100 g with D.I. water. 
Composition VI.sub.C --1 g of Prowl was mixed with 0.67 g of composition 
V.sub.C and then diluted to 100 g with D.I. water. 
Composition VI.sub.D --1 g of Prowl was mixed with 0.67 g of composition 
V.sub.D and then diluted to 100 g with D.I. water. 
Formulations VI blank, VI.sub.A, VI.sub.B, VI.sub.C and VI.sub.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 VI.sub.A, VI.sub.B, VI.sub.C and VI.sub.D 
exhibited increased retention of the active ingredient as compared to the 
blank. The effectiveness was in the following decreasing order: 
EQU VI.sub.A (38.7.+-.6)&gt;VI.sub.B (30.+-.1)&gt;VI.sub.D (23.+-.4)&gt;VI.sub.C 
(19.4.+-.3)&gt;VI(12.+-.1) 
The foregoing represent the averages of three runs for each composition. 
In the above experiment, the pump spray equipment used, i.e., 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 application as the Latron B1956 containing composition. 
EXAMPLE 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 1 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.sub.A --Same composition as VII blank except that 0.27 g of 
composition V.sub.A was added prior to dilution. 
Composition VII.sub.B --Same composition as VII.sub.A except that 0.67 g of 
composition V.sub.A were added. 
Composition VII.sub.C --Same composition as VII.sub.A except that 
composition V.sub.A was replaced with composition V.sub.B. 
Composition VII.sub.D --Same as composition VII.sub.B except that 
composition V.sub.A was replaced by composition V.sub.B. 
Composition VII.sub.E --Same as composition VII.sub.B except that 
composition V.sub.A was replaced by composition V.sub.C. 
Composition VII.sub.F --Same as composition VII.sub.B except that 
composition V.sub.A was replaced by composition V.sub.D. 
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 .lambda. 
max. used for the evaluation was 279 nm and the least square line was used 
according to the following formula: 
EQU absorbance=0.03276.times.concentration (ppm)-0.016416. 
The results of the evaluations are shown in Table 6. 
TABLE 6 
______________________________________ 
SUMMARY RESULTS OF RAINFASTNESS 
FOR CARBAMYL ("SEVIN") FORMULATIONS 
COMPOSITION % AGRIMER % A.I. RECOVERED 
______________________________________ 
VII (blank) 0 39.2 .+-. 4 
VI.sub.A Agrimer AL 25 
55.4 .+-. 7 
(0.02%) 
VII.sub.B Agrimer AL 25 
59 .+-. 8 
(0.05%) 
VII.sub.C Agrimer AL 30 
63 .+-. 7 
(0.05%) 
VII.sub.D Agrimer AL 30 
62 .+-. 9 
(0.05%) 
VII.sub.E Agrimer AL 25 
56 .+-. 6 
(0.05%) 
VII.sub.F Agrimer AL 30 
59.6 .+-. 8 
(0.05%) 
______________________________________ 
EXAMPLE 8 
It is noted that formulation V.sub.A 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. 
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.sub.A 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 
V.sub.A and V.sub.B can be used as granulating fluids to incorporate the 
water-insoluble polymers in solid water-dispersible granular formulations. 
A typical formulation is as follows: 
______________________________________ 
Active ingredient (Atrazine) 
82.3% by weight 
Binder (polyvinyl pyrrolidone - optional) 
3.0 
Dispersant 3.0 
Wetting agent 1.5 
Defoamer 0.2 
Composition V.sub.A or V.sub.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 24 inch pan granulator set at an angle of 50.degree. to 
55.degree.. 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 30 minutes. 
After granulation, the wet granules are dried at 40.degree. to 50.degree. 
C. to reduce the moisture level to about 1 to 2%. 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.