Delivery system for agricultural chemicals
CROSS-REFERENCE TO OTHER APPLICATIONS 
     This application is a continuation-in-part of application Ser. No. 505,030, filed Apr. 5, 1990, which, in turn, is a continuation-in-part of application Ser. No. 07/448,707, filed Dec. 11, 1989, now U.S. Pat. No. 5,071,463, (hereinafter, the Parent Applications) the contents of all of which are incorporated herein by reference. 
    
    
     BACKGROUND OF THE INVENTION 
     I. Field of the Invention 
     The invention relates to a delivery system for agriculturally active chemicals. More particularly, the invention relates to an emulsifiable concentrate of difficult to dissolve agricultural chemicals making use of biodegradeable solvents. 
     II. Description of the Prior Art 
     Agricultural chemicals are most preferably applied in the form of aqueous emulsions, solutions, or suspensions. Occasionally, they may also be applied in the form of a dust wherein the active ingredient is adsorbed onto or mixed with a finely divided inert carrier material, such as, china clay, or the like. With such powdered or dust compositions, drift due to wind is a problem and consequently, liquid formulations are preferred. 
     One of the problems with such liquid formulations is the fact that chemicals having agricultural activity often exhibit extreme insolubility in water. This results in their having to be dissolved either in organic solvents or utilized in the form of emulsions or suspensions. With respect to the use of organic solvents, these are generally disadvantageous from an environmental and cost viewpoint. Particularly, such organic chemicals may exhibit toxicity or side-effects which may be adverse to the effect of the agricultural chemical itself or to the subsequent fruit or vegetable produced in the particular agricultural use. This toxicity may also be disadvantageous with respect to handling. 
     When attempts are made to provide emulsified or suspension formulations, difficulties are encountered with respect to providing a desirably high concentration of the agriculturally active ingredient. Thus, when such agriculturally active chemicals are formulated into an emulsion, it is difficult to maintain the emulsified state. This makes it difficult to maintain a uniform formulation, particularly, when the formulation is diluted with water for application to the plants. 
     Typically, for example, the agriculturally active ingredient is mixed with one or more of a variety of conventional solvents and an emulsifying agent to form a concentrate. This concentrate may be an emulsion, suspension, or solution. The concentrate is then stored until it is transported to the site of use or may simply be transported and stored at the site of use. In any event, the concentrate normally will undergo some period of storage until it is ready for use. Understandably, it is most desirable to be able to transport the agriculturally active ingredient at the highest concentration possible so as to minimize the volume of material which need be transported. By the same token, however, at the use site, it is normally not feasible to admix ingredients together or to process them other than to dilute the concentrate with water. Accordingly, it is important that the concentrate emulsify easily, i.e., exhibit good &#34;bloom&#34;, upon the addition of water. In addition, at the use site, it is often necessary to store the diluted concentrate for extended time periods until the actual application to the plants. Consequently, it is important that the diluted form of the concentrate exhibit good stability with respect to the uniformity of the emulsion and to avoid precipitation of the active ingredients. If non-uniformity or precipitation occurs in the diluted form, then non-uniformity will result in the application of the diluted formulation to the plants. 
     An attempt to provide concentrates of agriculturally useful chemicals is disclosed in South African Patent Application No. 695,393, filed Jul. 25, 1969. This application is directed to the formulation of a concentrate substantially water-insoluble pesticides for agricultural use. The pesticides, either in oil or solid form, are mixed with pyrrolidones having a hydrogen or a lower alkyl group containing from 1 to 4 carbon atoms attached to the nitrogen atom of the pyrrolidone ring. The application discloses that concentrated solutions of difficult to dissolve pesticides could be formulated and that such concentrates exhibited good stability. The concentrates utilized are those containing the pesticidal active ingredient, the particular lower alkyl pyrrolidone, a co-solvent which is usually a common organic solvent, such as, an aromatic including xylene, methylated and polyalkylated naphthalenes and aliphatic solvents, and a dispersing or emulsifying agent, such as, a surfactant, including polyoxyethylene alkylphenols, polyoxyethylene fatty esters, polyoxyethylene sorbitan fatty esters which may be blended with oil-soluble sulfonates, calcium and aminosulfonate salts, and the like. 
     This prior art does not offer a solution to the problem arising from the difficulty in maintaining the stability of the emulsion after the concentrate is diluted with water. Consequently, unless the diluted form of the concentrate is used immediately after emulsification, it is difficult to provide a stable diluted formulation for application to the plants. 
     In addition, for such agricultural uses, it is desirable to avoid the use of toxic solvents, including those of Lists 1 and 2 of 40 C.F.R. 154.7 dated Apr. 22, 1987, which includes inerts of toxicological concern and solvents having high flash points, as well as to increase the amount of the agriculturally active material in the concentrate. Moreover, many organic solvents which have been used in the past, even those exhibiting relatively low toxicities, are not biodegradeable and thus remain as a pollutant. 
     SUMMARY OF THE INVENTION 
     We have discovered a novel emulsifiable concentrate of an agriculturally active chemical, which concentrate provides, upon dilution, a highly stable emulsion and avoids precipitation of the active ingredient on extended storage. In addition, the inventive emulsifiable concentrates may contain relatively high concentrations of the agriculturally active ingredient, sometimes referred to as a &#34;loading&#34;, making it advantageous from both economic and handling viewpoints. Also, the concentrates of the present invention utilize organic materials which do not pose environmental problems either in use or handling, and are biodegradeable. 
     More particularly, the emulsifiable concentrate of the present invention is composed of an agriculturally active chemical, a surfactant, and a hydrophobic solvent having the following Hansens&#39; solubility parameters: 
     Dispersive component from about 56 to 75%; 
     Polar component from about 8 to 24%; and 
     H-bonding component of from about 10 to 30%. 
     This solvent should also have surfactant properties and act as a non-ionic surfactant with an HLB value ranging from about 2 to 8. 
     For a discussion of the solubility parameters, see C.R.C. Handbook of Solubility Parameters and Other Cohesion Parameters, Allan F. M. Barton, 1983, Table 9, p, 167-170. 
     In another embodiment, the inventive emulsifiable concentrate is composed of an agriculturally active chemical, a surfactant, and a solvent having a first component, a second component (the hydrophobic solvent), or combinations thereof. In the inventive compositions, no diluent, as defined in the Parent Applications, is used. 
     The first component of the solvent is selected from those compounds which have a sufficiently high hydrophilic property to solubilize the agriculturally active chemical. Preferably, the first component will have the following Hansens&#39; solvent parameters: 
     Dispersable component from about 40 to 50%; 
     Polar components of from about 25 to 40%; and 
     H-bonding component of 10 to 30%. 
     The second component is a hydrophobic solvent having the following Hansens&#39; solubility parameters: 
     Dispersable component from about 56 to 75%; 
     Polar component from about 8 to 24%; and 
     H-bonding component of from about 10 to 30%. 
     An important advantage of these embodiments is that the solvent used is completely biodegradeable. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     As used herein, the term &#34;agriculturally active chemical&#34; includes 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, 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. Particularly, such chemicals would normally take the form of water-immiscible or oily liquids and/or solids which is substantially insoluble in water. By the term &#34;substantially insoluble&#34;, it is meant 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&#39;s bioavailability or avoid the use of excessively large volumes of solvent. 
     Suitable agriculturally active chemicals which can be used with the present invention include insecticides, such as, cyclocompounds, carbamates, animal and plant derivatives, synthetic pyrethroids, diphenyl compounds, non-phosphates, organic phosphates, thiophosphates, and dithiophosphates. (See Agricultural Chemicals, Book I, Insecticides, 1989 Revision by W. T. Thomson, Thomson Publications.) Typical of the insecticides are: 
     
         ______________________________________                                    
cyclocompounds:                                                           
               6,7,8,9,10,10-hexachloro-                                  
               1,5,5a,6,9,9a-hexahydro-6,9-                               
               methano-2,4,3-benzodioxathiepin-3-                         
               oxide                                                      
carbamates:    2-isopropyl phenyl-N-methyl                                
               carbamate;                                                 
               2-(1,3-dioxolan-2yl) phenylmethyl                          
               carbamate;                                                 
               2,3-isopropylidine dioxyphenyl                             
               methyl carbamate;                                          
animal and plant                                                          
               chlorinated hydrocarbons derived                           
derivatives:   from Southern pine; naturally                              
               occurring lactone glycoside;                               
synthetic      (±) α-cyano-3-phenoxybenzyl (±)                
pyrethroids:   cis,trans 3-(2,2-dichlorovinyl)-                           
               2,2-dimethyl cyclopropane carbox-                          
               ylate;                                                     
               (±) cyano (3-phenoxyphenyl methyl                       
               (±)-4-(difluoromethyoxy) α-(1-                    
               methylethyl) benzene acetate;                              
phenoxy compounds                                                         
               2,2-bis(p-methoxy phenyl)-                                 
and non-phosphate:                                                        
               1,1,1,trichloroethane;                                     
               1,3,5,tri-n-propyl-1,3,5-triazine-                         
               2,4,6 (1H,3H,5H) trione;                                   
               ethyl (2E,4E)-3,7,11-trimethyl-                            
               2,4-dodeca dienoate;                                       
               1-decycloxy 4-[(7-oxa-oct-4-                               
               ynyl)]-oxybenzene;                                         
organic phosphates:                                                       
               dimethyl phophate ester of 3-hy-                           
               droxy-N,N-dimethyl-cis-                                    
               crotonamide;                                               
               2-chloro-1-(2,4-dichloro phenyl)                           
               vinyl diethylphosphate;                                    
               4-(methyl thio) phenyl dipropyl                            
               phosphate;                                                 
thiophosphates:                                                           
               0,0-diethyl-0-4-nitrophenyl phos-                          
               phorothioate;                                              
               0,0-diethyl-0-(2,isopropyl-6-                              
               methyl-5-pyrimidinyl) phosphoro-                           
               thioate;                                                   
               2-diethylamino-6-methyl pyrimi-                            
               dine-4-yl dimethyl phosphoro-                              
               thioate;                                                   
dithiophosphates:                                                         
               0,0-dimethyl phosphorodithioate                            
               ester of diethylmercapto succi-                            
               nate;                                                      
               0-ethyl-S-phenyl ethyl phosphoro-                          
               dithioate.                                                 
______________________________________                                    
 
    
     Typical herbicides include phenoxy compounds, benzoic, acetic, and phthalic acids, aniline derivatives, nitriles, amides, acetamides, anilides, carbamates, thiocarbamates, and heterocyclic nitrogen derivatives, e.g., triazines, pyridines, pyridazones, picolinic acid, and urea derivates and phosphates. (See Agricultural Chemicals, Book II, Herbicides, 1986-87 Edition, W. T. Thomson, Thomson Publications, Fresno, Calif. 93791.) Exemplary of the above compounds are: 
     
         ______________________________________                                    
phenoxy compounds:                                                        
              2,4-Dichlorophenoxy acetic acid                             
              2,4,5-trichloro phenoxyacetic                               
              acid;                                                       
              4-(2,4-dichlorophenoxy) butyric                             
              acid;                                                       
              S-ethyl 2 methyl-4-chlorophenoxy-                           
              thioacetate;                                                
              2-methyl-4-chloro-phenoxy acetic                            
              acid;                                                       
              methyl 5-(2,4-dichloro-phenoxy)-2-                          
              nitrobenzoate;                                              
benzoic and acetic                                                        
              3,6-dichloro-o-anisic acid                                  
acids of phthalic                                                         
              4-chloro-2-oxo benzothiazolin-3-yl                          
compounds:    acetic acid;                                                
              N-1-Naphthyl-phthalamic acid                                
nitriles and aniline                                                      
              3-5-dibromo-4-hydroxybenzo-ni-                              
derivatives:  trile;                                                      
              α,α,α,trifluoro-2,6-dinitro-N,            
              N-dipropyl-p-tolinidine;                                    
              N-(1-ethylpropyl)-2,6-dinitro-3,4-                          
              xylidine;                                                   
amides, acetamides,                                                       
              N,N-diethyl-2-(1-naphthalenyl                               
anilides:     oxy)-propionamide;                                          
              2,6-dimethyl-N-2&#39; methoxy-ethyl-                            
              chloro-acetanilide;                                         
              3&#39;,4&#39;-dichloro-propionanilide;                              
              α-chloracetic-N-(3,5,5-trimethyl-                     
              cyclohexen-1-yl)-N-isopropylamide;                          
              4-benzyl-N-isopropyl trimethyl                              
              acetamide;                                                  
thiocarbamates:                                                           
              S-ethyl dipropyl thiocarbamate;                             
urea derivatives:                                                         
              3-(5-tert-butyl-3-isoxazoyl)-1,1-                           
              dimethyl urea;                                              
              N-(2,6-trifluoro-benzoyl)-N&#39;-[2,5-                          
              dichloro-4-(1,1,2,3,3,3-hexa-                               
              fluoropropyloxy) phenyl] urea;                              
pyrrolidone   1-(m-trifluoro methyl phenyl)-3-                            
derivatives:  chloro-4-chloromethyl-2-pyrroli-                            
              done;                                                       
amino acid    methyl N-benzoyl-N-(3-chloro-4-                             
derivatives:  fluorophenyl)-DL alarinate;                                 
              N-chloroacetyl-N-(2,6-diethyl phe-                          
              nyl)-glycine ethyl ester;                                   
carbamates:   isopropyl-m-chlorocarbanilate;                              
              3-ethoxy (carbonyl aminophenyl)-N-                          
              phenyl carbamate;                                           
heterocyclics:                                                            
              4-amino-3,5-dichloro-6-fluoro-2-                            
              pyridyloxy acetic acid;                                     
              4-(1,2-Dimethyl-N-propyl amino)-2-                          
              ethyl amino-6-methyl thio-S-                                
              triazine;                                                   
              2-[4,5-dihydro 4-methyl-4-(1-meth-                          
              yl ethyl)-5-oxo-1 H-imidazoyl-2yl-                          
              3-byridinecarboxylic acid;                                  
              2-[3,5-dichlorophenyl)-2-(2,2,2-                            
              trichloroethyl) oxinane;                                    
              butyl-9-hydro-fluorene-(9)-                                 
              carboxylate;                                                
              2-[1-(ethoxy imino) butyl]-3-                               
              hydroxy-5-(2H-tetra hydro thiopy-                           
              ran-3-yl)-2-cyclohexene-ione;                               
              2-(2 chlorophenyl) methyl-4,4-di-                           
              methyl-3-iso oxazolidinone;                                 
phosphates:   0-ethyl-0-(3-methyl-6-nitro phen-                           
              yl) N-sec-butyl phosphoro thio                              
              amidate.                                                    
______________________________________                                    
 
    
     Typical fungicides include (See Agricultural Chemicals, Book IV, Fungicides, 1989 Revision, W. T. Thomson, Thomson Publications, Fresno, Calif. 93791): 
     
         ______________________________________                                    
organic compounds:                                                        
               2,5-dimethyl-N-Cyclohexyl-N-meth-                          
               oxy-3-furan carboxamide;                                   
               5-Ethyoxy-3-trichloromethyl-1,2,4-                         
               thiadiazole;                                               
               3-(2-methyl piperidino) propyl                             
               3,4-dichlorobenzoate;                                      
               N,N&#39;-(1, 4-piperazinediyl bis                              
               (2,2,2-trichloro) ethylidene) bis                          
               formamide;                                                 
               Tetramethyl thiuram disulfide;                             
               0-Ethyl-S,S,diphenyl-dithiophos-                           
               phate;                                                     
               5,10-dihydro-5, 10-dioxo naphtho                           
               (2,3,9)-p-dithiin-2,3-dicarbo-ni-                          
               trile;                                                     
               2-(Thiocyano methyl thio) benzo-                           
               thiazole;                                                  
               α-2-(4-chlorophenyl) ethyl]-α-                 
               (1,1-dimethyl ethyl)-1 H-1,2,4-                            
               triazole-1-ethanol;                                        
morpholines:   N-trideoyl-2,6-dimethyl morpho-                            
               line:                                                      
               4-N-dodecyl-2,6-dimethyl morpho-                           
               line.                                                      
______________________________________                                    
 
    
     Typical fumigants, growth regulators, repellants, and rodenticides include (See Agricultural Chemicals, Book III, Fumigants, 1988-1989 Revision, W. T. Thomson, Thomson Publications, Fresno, Calif. 93791): 
     
         ______________________________________                                    
growth regulants:                                                         
               1,2 Dihydro-6-ethyoxy-2,2,4-tri-                           
               methylquinoline;                                           
               (2-chloroethyl) phosphoric acid;                           
               4-[acetamino) methyl]-2-chloro-N                           
               (2,6-diethyl phenyl acetamide;                             
               Benzoic acid,3,6 dichloro-2-                               
               methoxy,2-ethoxy-1-methyl-2-oxo                            
               ethyl ester;                                               
repellants:    0,0-dimethyl-0-[(4-methyl thio)-m-                         
               tolyl] phosphorothioate;                                   
               Tetriary butyl-sulfenyl dimethyl                           
               dithio carbamate;                                          
seed softener: 2-chloro-6-(trichlomethyl) pyri-                           
               dine;                                                      
               5-ethoxy-3-trichloromethyl-1,2,4-                          
               thiadiazole;                                               
               N-phenyl-N&#39;-1,2,3-thiadiazol-5-yl                          
               urea.                                                      
______________________________________                                    
 
    
     Pesticides may be characterized by their physical properties, depending on their physical state at normal or ambient conditions, i.e., between 40° F. and 90° 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 two 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-trichlorophenozy) 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: O,O-diethyl-O-2,5-dichloro-4-bromophenyl thionophosphate, 
     N-(2-mercaptoethyl) benzene-sulfenamide (BETASAN®), 
     Isobornyl Thiocyanoacetate (Thanite®), 
     Ioxynil ester of octanoic acid, 
     Molinate S-ethyl hexahydro-1H-azepine-1-carbothioate, 
     PP 511 O,O-dimethyl-(2-diethylamine 4-methyl-6-pyrimidinyl) carbamate, 
     PP 211 O,O-diethyl O-(2-diethylamine-4-methyl-6-pyrimidinyl) phosphorocarbamate, 
     Chlordane, 
     5-Ethoxy-3-(trichlorometyl)-1,2,4-thiadiazole (TERRAZALE®), 
     Ethyl-s-s-dipropyl-phosphodithioate (MOCAP®), 
     S-Ethyl dipropylthiocarbamate (EPTAM®), 
     S-Ethyl diisobutylthiocarbamate (SUTAN®), 
     S-n. propyl-di-n-propylthiocarbamate (VERNAM®), 
     S-propyl butylethylthiocarbamatae (TILLAM®), 
     S-ethyl ethylcyclohexylthiocarbamate (RO-NEET®), 
     Malathion (S-(1,2-dicarboxyethyl)-O,O-dimethyl phosphorodithioate), 
     Diazinon (O,O-diethyl,O-(2-isopropyl-4-methyl-6-pyrimidinyl) phosphorothioate, 
     O-Ethyl-S-phenyl-ethylphosphonodithioate (DYFONATE®), 
     Toxaphene (Octachlorocamphene), 
     Bromoxynil (3,5-dibromo-4-hydroxy benzonitrile ester of n.octanoic acid, 
     2-chloro-N-2,6-diethylphenyl-N-methoxymethylacetamide (LASSO®), 
     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®) 
     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-trifluoromethylamiline) (2,3 dihydro-5-carboxanilido-6-methyl-1,4-oxathiin) (VITAVAX®) 
     2,4-dichlorophenoxyacetic acid 
     4-(4-chloro-2 methylphenoxy) butyric acid 
     2-(2,4-dichlorophenoxy) propionic acid 
     Ioxynil: 3,5 diiodo-4-hydroxybenzonitrile 
     Bromoxynil: 3,5 dibromo-4-hydroxybenzonitrile 
     Carbaryl: 1-naphthyl-N-methylcarbamate 
     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&#39;-(4-bromo-3-chlorophenyl)-N-methoxy-N-methylurea 
     C 6989 2,4&#39;dinitro-4-trifluoromethyl-diphenylether 
     Chloroxuron N&#39;-4-(chlorophenoxy) phenyl-NN-dimethylurea 
     Dichlobenil 2,6-dichlorobenzonitrile 
     Diphenamid NN-dimethyl-2,2-diphenylacetamide 
     Fenac 2,3,6-trichlorophenylacetic acid 
     Fluometuron N&#39;-(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-(3H,5H)-dione 
     Pyrazon 5-amino-4-chloro-2-phenyl-3-pyridazone 
     Metrobromuron N&#39;-(4-bromophenyl)-N-methoxy-N-methylurea 
     Metoxymarc N-(4-methoxybenzoyl)-N-(3,4-dichlorophenyl)-N&#39;,N&#39;-dimethylurea 
     Neburon N-butyl-N&#39;-(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&#39;-(4-chlorophenyl)-N-methoxy-N-methylurea 
     Nitrofen 2,4-dichlorphenyl 4-nitrophenylether 
     Propanil N-(3,4-dichlororphenyl)propionamide 
     Pyriclor 2,3,5-trichloro-4-pyridinol 
     Solan 3&#39;-chloro-2-methyl-p-volerotoluidide 
     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&#39;,4&#39;-dichlorocyclopropane carboxanilide 
     Fenuron NN-dimethyl-N&#39;phenylurea 
     Chlorbromuron N&#39;-(4-bromo-3-chlorophenyl)-N-methoxy-N-methylurea 
     Ametryne 2-methylmercapto-4-ethylamino-6-isopropyl-amino-s-triazine 
     Prometryne 2-methylmercapto-4,6-bisisopropyl amino-s-triazine 
     DCPA dimethyl 2,3,5,6, tetrachloroterephthalate 
     Benefin N-butyl-N-ethyl-2,2,2-trifluoro-2,6-dinitro-p-toluidine 
     Nitralin 2,6-dinitro-4-methylsulfonyl-NN-dipropyl-aniline 
     PP 493 2,6-difluoro-3,5-dichloro-4-hydroxy pyridine 
     CNP 2,4,6-trichlorophenyl-4&#39;-nitrophenyl ether 
     Pentachloro nitrobenzine 
     1-(butile carbamoyl)-2-benzimidazol carbamic acid, methyl ester (BENLATE®) 
     Typical examples of first components suitable for use in the solvent are alkylpyrrolidones having from 1 to 4 carbon atoms in the alkyl group, cyclic lactones, e.g., gamma-butyrolactones, lower alkyl cyclic carbonates, i.e., ethylene carbonate, propylene carbonate, butylene carbonate, lower akylimidazolone, e.g., N-N,dimethylimidazolone, lower alkylamides of formic acid and acetic acid, e.g., dimethyl formamide and dimethylacetamide, and lower alkyl sulfoxides, e.g., dimethylsulfoxide. (The term &#34;lower alkyl&#34; in these examples means one or two carbons.) Mixtures of these may also be used as the first component. 
     Examples of appropriate second components or hydrophobic solvents include alkylpyrrolidones having an alkyl portion containing from 6 to 14 carbon atoms, e.g., octylpyrrolidone, dodecylpyrrolidone, or N-(2&#39;-ethylhexylpyrrolidone), alkyl gamma-butyrolactones, alkyl cyclic carbonates and combinations thereof, wherein the alkyl chains contain from 6 to 14 carbon atoms. The alkyl portion may be distributed at one or more sites on the ring so long as one portion contains at least 6 carbon atoms and the total number of alkyl carbon atoms does not exceed 14. Preferred 6 to 14 carbon alkyl portions are composed of straight chains. Branched or cyclic alkyl portions may also be used. 
     Preferably, the first component is selected from the group consisting of pyrolidones having the formula ##STR1## wherein R is hydrogen or lower alkyl having from 1 to 4 carbon atoms and R 1  is lower alkyl having from 1 to 4 carbon atoms. 
     The hydrophobic solvent or second component is preferably selected from pyrrolidones having the formula ##STR2## 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. 
     In the inventive composition, the amount of solvent is in the range from about 40 to 90%. 
     The inventive composition also contains one or more additional emulsifier(s) or surfactant(s) which is generally selected on a case by case basis in order to optimize the solubility and stability of the emulsion. Typically, such emulsifiers include ethoxylated alkyl phenols, linear aliphatic polyesters, linear aromatic polyesters, polyethoxylated alcohols, linear aliphatic ethoxylates, polyethoxylated castor oil, polyethoxylated carboxylates, and polyethoxylated alkylamines. Anionic surfactants may be used as the emulsifier and include phosphate esters and their salts, alkyl sulfonamides, salts of sulfated nonylphenoxypoly(ethyleneoxy) ethanol, salts of alkylbenzene sulfonates, 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&#39;s, Emulsifiers and Detergents (1989), published by McCutcheon&#39;s Division of M. C. Publishing Co., Glen Rock, N.J.) Generally, the amount of emulsifier (surfactant) is from about 1 to 25% based on the total weight of the composition. 
     The agriculturally active chemical (sometimes referred to herein as AAC) concentration should be as high as possible so long as it does not precipitate out upon dilution of the concentrate with water for a reasonable period of time and achieves the desired effect. Precipitation (crystal formation) on standing not only depletes the solution of AAC, it can also lead to fouling of application equipment, i.e., sprayers, etc. With the present invention, it is possible to obtain concentrates with agriculturally active chemical concentrations in excess of 5  weight percent which form a stable emulsion upon being diluted with water. Depending on the particular agriculturally active chemical, the concentration of the AAC is from about 5 to 25% based on the total weight of the composition before dilution. 
     The final use concentration values depend on the AAC. However, it is important that upon dilution, the diluted form remain stable for a time sufficient to allow it to be applied. This, of course, will vary with the schedule for the application in the field. Normally, the diluted concentrate is applied within four hours of dilution. It is possible, however, due to equipment and personnel delays, that a standing period of up to 24 hours may be encountered. With the present invention, prolonged stability of the emulsified concentrate, as is, as well as in the diluted form is obtained. In particular, the emulsified concentrate in accordance with the present invention can be diluted to final use concentrations in the range from about 10 ppm to 2 percent, depending on the specific AAC, without any adverse effects, and specifically, precipitation of the AAC from the solution. 
     The following examples illustrate the present invention*: 
    
     A series of experiments was carried out wherein the type and amount of agriculturally active chemical, hydrophobic solvent, and other components were varied. The samples were evaluated for ease of emulsion and emulsion stability by measuring the amount of separation before and after mixing. The compositions used and results obtained are set forth in the tables that follow. 
     EXPERIMENTAL PROCEDURE 
     Formulations 
     Formulations were prepared by weighing the exact proportion of ingredients and mixing them together in a bottle. The solvents were weighed in first. The AAC was dissolved completely in the solvent system followed by addition of the wetting agent or emulsifying agent. Typically, about 10g of each of the formulations was prepared. 
     The contents were stirred well in an automatic rocking shaker for about 30 minutes when the AAC dissolved completely. The samples thus prepared were evaluated for freeze-thaw stability on storage and ease of emulsification and emulsion stability on dilution. For dilution, 2 grams of concentrate were diluted to 50 grams using World Health Organization (WHO) standard (6 g of CaCl 2  and 2.78 g of MgCl 2  6H 2  O dissolved in 20 L) hard water having a hardness of 342 ppm expressed as CaCO 3  equivalent. 
     Freeze-Thaw Stability 
     The concentrates were stored for a period of 24 hours in the cold (temperature 5° C.) in a refrigerator and taken out and thawed to room temperature and then stored at 55° C. in an oven for a period of 24 hours. The alternate storage in the cold (5° C.) and warm condition at 55° C. was repeated for three cycles. Any separation during the storage was recorded. A concentrate is &#34;stable&#34; if there is no substantial separation after the 24 hour cycles at each temperature. All of the solutions exemplified hereinafter exhibited stability according to this test between the temperatures of 5° C. and 55° C. Some of the solutions were even stable at a lower range of -5° C. 
     Evaluation of Emulsion Stability and Ease of Emulsification 
     A Nessler tube (1.8 cm diameter; 28 cm long) was filled with an appropriate quantity (47-48 g) of WHO water. Using a serological pipette, 0.5-2.5 g of emulsion concentrate was dropped into the Nessler tube containing 47.5-49.5 g water. The initial bloom was observed at zero time without stirring and the quality of the bloom was graded by visual appearance as shown below. The Nessler tube was stopped and inverted 20 times; the bloom was again recorded and so also stability as judged by volume or height of the sedimentation (cream/ppt/oil) followed at different intervals of time: 0, 1 hour, 2 hours, up to 24 hours. 
     Stability of Diluted Concentrate 
     The composition of the concentrate (EC) diluted with water was considered &#34;stable&#34; if at EC concentrations of from 0.2 to 1%, the composition after mixing (twenty inversions) exhibited two mm or less cream and no oil in one hour. Both top and bottom should be checked. 
     
         ______________________________________                                    
Bloom: Excellent Thick emulsion cloud with no separation                  
       Good      Emulsion cloud may be thin, or may ex-                   
                 hibit trailing, small number of oil                      
                 droplets within cloud                                    
       Poor      Many oil droplets within cloud, some                     
                 droplets separate from cloud                             
______________________________________                                    
 
    
     Each of the emulsifiable concentrates thus prepared were analyzed for ease of emulsification (bloom) upon addition of water and after twenty inversion of the sample as well as emulsion stability upon dilution with water. The composition of the samples and the results of the analysis are set forth in the following tables. 
     Crystal Formation Studies 
     A number of the samples were evaluated for precipitation of AAC, i.e., crystal growth over varying time periods. This was done using the following techniques: 
     1. The diluted sample was placed in a 100 ml beaker and stirred continuously. Aliquots were removed at 1, 4, 7, and/or 24 hour intervals and examined under 250 x magnification, using a 2×2 mm slide, which provided 1500 separate viewing areas. The number of crystals, if any, in ten different viewing areas were counted and averaged. If no crystals were found, second and third aliquots were examined. 
     2. The remaining portion of the diluted sample was passed through U.S. Standard screens (60, 100 and 250 mesh) and sediment retained is reported. 
     3. The diluted sample was allowed to stand without stirring for 24 hours and inverted twenty times. An aliquot of the inverted sample was examined under 250× and the results reported as above. The reamining portion was passed through screens and retained sediment reported. 
     The results for the crystal growth studies are reported as follows: 
     0 means no crystals 
     * means &lt;10 crystals/view area 
     ** means 10-100 crystals/view area 
     *** means 100-1000 crystals/view area 
     **** means &gt;1000 crystals/view area 
     The components set forth in the Tables are referred to by their commercial names for purposes of brevity. The chemical nomenclature of the materials is as follows: 
     
         ______________________________________                                    
LP-100     N-octylpyrrolidone                                             
LP-300     N-dodecylpyrrolidone (C.sub.12 chain)                          
LP-940     N-octadecylpyrrolidone (C.sub.18 chain)                        
Gafac RM 710                                                              
           Poly(oxy-1,2-ethanediyl)α-(dinonylphenyl)-               
           omega-hydroxy-phosphate.                                       
Igepal CO-630                                                             
           Ethoxylated nonyl phenol containing 9 EO                       
           units                                                          
Thidiazuron                                                               
           1-phenyl-3-(1,2,3-thiadiazol-5-yl)urea                         
Gafac RE-610                                                              
           Poly(oxy-1,2-ethanediyl)α-(nonylphenyl)-                 
           omega-hydroxy-phosphate.                                       
Silwet L-77                                                               
           (Silwet copolymer L-77) nonionic organo                        
           silicone (Union Carbide)                                       
Silwet L-7607                                                             
           (Silwet copolymer L-7607) nonionic organo                      
           silicone (Union Carbide)                                       
Pegol L-31 Ethoxylated polyoxy propylene                                  
______________________________________                                    
 
    
     In the tables, SUPER refers to the upper layer on separation and PCPT refers to the bottom layer. 
     
                                           TABLE 1                                 
__________________________________________________________________________
Run No.                                                                   
       1      2      3      4      5      6      7      8                 
__________________________________________________________________________
Composition                                                               
wt. %                                                                     
N-methyl-                                                                 
       0      0      75      0     0       0      0      0                
pyrrolidone                                                               
(M-Pyrol)                                                                 
N-octyl-                                                                  
       75     0       0      0     67.5   60     45     30                
pyrrolidone                                                               
(LP-100)                                                                  
N-dodceyl-                                                                
       0      75      0      0     7.5    15     30     45                
pyrrolidone                                                               
(LP-300)                                                                  
Aromatic oil                                                              
       0      0       0     75     0       0      0      0                
(Exxon 200)                                                               
Cocoyl-                                                                   
       0      0       0      0     0       0      0      0                
pyrrolidone                                                               
Gafac  10     10     10     10     10     10     10     10                
RE-610                                                                    
AAC:   15     15     15     15     15     15     15     15                
thidiazuron                                                               
Solubility at                                                             
       S      PS     IS     IS     S      S      S      S                 
23°C.                                                              
Results:**                                                                
Bloom:                                                                    
0 time poor   NA     NA     NA     poor   poor   poor   poor              
after 20 turns                                                            
       excellent                                                          
              NA     NA     NA     excellent                              
                                          excellent                       
                                                 excellent                
                                                        excellent         
Solids,                                                                   
       SU-                                                                
          PCPT                                                            
              SU-                                                         
                 PCPT                                                     
                     SU-                                                  
                        PCPT                                              
                            SU-                                           
                               PCPT                                       
                                   SU-                                    
                                      PCPT                                
                                          SU-                             
                                             PCPT                         
                                                 SU-                      
                                                    PCPT                  
                                                        SU-               
                                                           PCPT           
creams,                                                                   
       PER    PER    PER    PER    PER    PER    PER    PER               
or oil, mm:                                                               
 0 time                                                                   
       0  0   NA NA  NA NA  NA NA  0  0   0  0   0  0   0  0              
 1 hour                                                                   
       0  0   NA NA  NA NA  NA NA  0  0   0  0   0  0   0  0              
 2 hours                                                                  
       0  0   NA NA  NA NA  NA NA  0  0   0  0   0  0   0  0              
 4 hours                                                                  
       0  0   NA NA  NA NA  NA NA  0  0   0  0   0  0   0  0              
24 hours                                                                  
       0  6                        12 0   12 0   8  0   8  0              
After 24 hour                                                             
standing fil-                                                             
tered through                                                             
screen                                                                    
 60 mesh                                                                  
       -      NA     NA     NA     -      -      -      -                 
100 mesh                                                                  
       -      NA     NA     NA     -      -      -      -                 
250 mesh                                                                  
       -      NA     NA     NA     -      -      -      -                 
__________________________________________________________________________
Run No.                                                                   
       9      10     11     12     13     14     15     16                
__________________________________________________________________________
Composition                                                               
wt. %                                                                     
N-methyl-                                                                 
        0     0      15     22.5   30     15     15     22.5              
pyrrolidone                                                               
(M-Pyrol)                                                                 
N-octyl-                                                                  
       15     37.5   45     45     45     60     45     52.5              
pyrrolidone                                                               
(LP-100)                                                                  
N-dodceyl-                                                                
       60     37.5    0     0       0      0     15     0                 
pyrrolidone                                                               
(LP-300)                                                                  
Aromatic oil                                                              
        0     0      15     7.5     0      0      0     0                 
(Exxon 200)                                                               
Cocoyl-                                                                   
        0     0       0     0       0      0      0     0                 
pyrrolidone                                                               
Gafac  10     10     10     10     10     10     10     10                
RE-610                                                                    
AAC:   15     15     15     15     15     15     15     15                
thidiazuron                                                               
Solubility at                                                             
       S      S      IS     IS     IS     IS     IS     IS                
23°C.                                                              
Results:*                                                                 
Bloom:                                                                    
0 time poor   poor   NA     NA     NA     NA     NA     NA                
after 20 turns                                                            
       excellent                                                          
              excellent                                                   
                     NA     NA     NA     NA     NA     NA                
Solids,                                                                   
       SU-                                                                
          PCPT                                                            
              SU-                                                         
                 PCPT                                                     
                     SU-                                                  
                        PCPT                                              
                            SU-                                           
                               PCPT                                       
                                   SU-                                    
                                      PCPT                                
                                          SU-                             
                                             PCPT                         
                                                 SU-                      
                                                    PCPT                  
                                                        SU-               
                                                           PCPT           
creams,                                                                   
       PER    PER    PER    PER    PER    PER    PER    PER               
or oil, mm:                                                               
 0 time                                                                   
       0  0   0  0   NA NA  NA NA  NA NA  NA NA  NA NA  NA NA             
 1 hour                                                                   
       0  0   0  0   NA NA  NA NA  NA NA  NA NA  NA NA  NA NA             
 2 hours                                                                  
       0  0   0  0   NA NA  NA NA  NA NA  NA NA  NA NA  NA NA             
 4 hours                                                                  
       0  0   0  0   NA NA  NA NA  NA NA  NA NA  NA NA  NA NA             
24 hours                                                                  
       7  0   8  0                                                        
After 24 hour                                                             
standing fil-                                                             
tered through                                                             
screen                                                                    
 60 mesh                                                                  
       -      -      NA     NA     NA     NA     NA     NA                
100 mesh                                                                  
       -      -      NA     NA     NA     NA     NA     NA                
250 mesh                                                                  
       -      -      NA     NA     NA     NA     NA     NA                
__________________________________________________________________________
 S = soluble;                                                             
 IS = insoluble;                                                          
 PS = hazy, mostly soluble                                                
 - means no sediment;                                                     
 + means trace;                                                           
 ++ means more than trace &lt; 1%;                                           
 +++means 1-5%                                                            
 **2.5 g of concentrate were diluted with standard H.sub.2 O to 50 g.     
 
    
     
                                           TABLE 2                                 
__________________________________________________________________________
Run No.  17       18       19       20       21       22                  
__________________________________________________________________________
Composition                                                               
wt. %                                                                     
N-methyl-                                                                 
         75        0        0       37.5     0        37.5                
pyrrolidone                                                               
(M-Pyrol)                                                                 
N-octyl-  0       75        0       0        37.5     37.5                
pyrrolidone                                                               
(LP-100)                                                                  
N-dodceyl-                                                                
          0        0       75       37.5     37.5     0                   
pyrrolidone                                                               
(LP-300)                                                                  
Gafac RE-610                                                              
         10       10       10       10       10       10                  
AAC:     15       15       15       15       15       15                  
Triazol derivative                                                        
Results:**                                                                
Bloom:                                                                    
0 time   fair     poor     fair     fair     poor     fair                
after 20 turns                                                            
         excellent                                                        
                  excellent                                               
                           excellent                                      
                                    excellent                             
                                             excellent                    
                                                      excellent           
Solids, creams or                                                         
         SUPER                                                            
              PCPT                                                        
                  SUPER                                                   
                       PCPT                                               
                           SUPER                                          
                                PCPT                                      
                                    SUPER                                 
                                         PCPT                             
                                             SUPER                        
                                                  PCPT                    
                                                      SUPER               
                                                           PCPT           
oil, mm:                                                                  
 0 time  0    16   0   0   35   2   0    2   4    0   0    1              
 4 hours 0    19  10   0   42   0   0    3   9    0   0    5              
24 hours 0    14  14   10  35   0   7    3   35   0   4    5              
Crystal  **        0        0        *       0        *                   
Growth***                                                                 
After 24 hour                                                             
standing filtered                                                         
through screen                                                            
 60 mesh ++       -        -        +        -        +                   
100 mesh ++++     -        -        -        -        -                   
250 mesh ++++     -        -        -        -        -                   
__________________________________________________________________________
 - means no sediment;                                                     
 + means trace;                                                           
 ++ means more than trace &lt; 1%;                                           
 +++ means 1-5%;                                                          
 ++++ means &gt;5%                                                           
 **2.5 g of concentrate were diluted with standard H.sub.2 O to 50 g.     
 ***Crystal growth observed under 250× after 24 hours standing and 2
 inversions.                                                              
 
    
     
                       TABLE 2A                                                    
______________________________________                                    
MICROSCOPIC CRYSTAL GROWTH                                                
OBSERVATION FOR SELECTED FORMULATIONS                                     
Run No.       17     18     19   20    21   22                            
______________________________________                                    
Microscopic observation                                                   
under stirring for                                                        
crystal growth, 250×                                                
Time:                                                                     
 0 hour          0             0                                          
 1 hour          0             **                                         
 4 hours         0             **                                         
24 hours         0             ***                                        
After 24 hour stirring                                                    
filtered through screen                                                   
 60 mesh         -             -                                          
100 mesh         -             -                                          
250 mesh         -             +                                          
______________________________________                                    
 
    
     
                       TABLE 3                                                     
______________________________________                                    
Run No.     23         24         25                                      
______________________________________                                    
Composition wt. %                                                         
N-methyl-    0          0         0                                       
pyrrolidone                                                               
(M-Pyrol)                                                                 
N-octylpyrrolidone                                                        
            65          0         32.5                                    
(LP-100)                                                                  
N-dodecyl-   0         65         32.5                                    
pyrrolidone                                                               
(LP-300)                                                                  
Gafac RE-610                                                              
            15         15         15                                      
AAC:        20         20         20                                      
Triazine derivative                                                       
Solubility at 23° C.                                               
            S          IS         S                                       
Results:**                                                                
Bloom:                                                                    
0 time      fair       NA         fair                                    
after 20 turns                                                            
            excellent  NA         excellent                               
Solids, creams or                                                         
            SU-    PCPT    SU-  PCPT  SU-  PCPT                           
oil, mm:    PER            PER        PER                                 
 0 time      0     0       NA   NA    0    0                              
 1 hour      0     8       NA   NA    0    trace                          
 4 hours    35     9       NA   NA    1    2                              
24 hours    40     10      NA   NA    trace                               
                                           1                              
After 26 hour                                                             
standing filtered                                                         
through screen                                                            
 60 mesh    +          NA         +                                       
100 mesh    trace      NA         trace                                   
250 mesh    +          NA         trace                                   
______________________________________                                    
 S = soluble;                                                             
 IS = insoluble                                                           
 - means no sediment;                                                     
 + means trace;                                                           
 ++ means more than trace &lt; 1%;                                           
 +++ means 1-5%;                                                          
 ++++ means &gt;5%                                                           
 When observed under the microscpoe, after standing 24 hours and 20       
 inversions, no crystals were seen at 250×. The diluted samples were
 stirred and periodic observation under the microscope showed absence of  
 crystals up to 5 hours from Run Number 23 and 10-100 crystals per view   
 area from Run Number 25.                                                 
 **2.5 g of concentrate were diluted with standard H.sub.2 O to 50 g.     
 
    
     
                                           TABLE 4                                 
__________________________________________________________________________
Run No.                                                                   
       26     27     28     29     30     31     32     33                
__________________________________________________________________________
Composition                                                               
wt. %                                                                     
N-methyl-                                                                 
       80     -      16     16     -      80     -      16                
pyrrolidone                                                               
(M-Pyrol)                                                                 
N-octyl-                                                                  
       -      80     64     48     48     -      80     64                
pyrrolidone                                                               
(LP-100)                                                                  
N-dodceyl-                                                                
       -      -      -      16     -      -      -      -                 
pyrrolidone                                                               
(LP-300)                                                                  
Butane diol                                                               
       -      -      -      -      32     -      -      -                 
Gafac   5      5      5      5      5      5      5      5                
RE-610                                                                    
Igepal  5      5      5      5      5     -      -      -                 
(CO-630)                                                                  
Silwet (L-77)                                                             
       -      -      -      -      -       5      5      5                
Silwet -      -      -      -      -      -      -      -                 
(L-7607)                                                                  
AAC:   10     10     10     10     10     10     10     10                
triforine                                                                 
Solubility at                                                             
       S      S      S      S      IS     S      S      S                 
23°C.                                                              
Results:**                                                                
Bloom:                                                                    
0 time excellent                                                          
              no emulsion                                                 
                     poor   poor   NA     excellent                       
                                                 no emulsion              
                                                        no emulsion       
after 20 turns                                                            
       excellent                                                          
              excellent                                                   
                     excellent                                            
                            excellent                                     
                                   NA     excellent                       
                                                 excellent                
                                                        excellent         
Solids,                                                                   
       SU-                                                                
          PCPT                                                            
              SU-                                                         
                 PCPT                                                     
                     SU-                                                  
                        PCPT                                              
                            SU-                                           
                               PCPT                                       
                                   SU-                                    
                                      PCPT                                
                                          SU-                             
                                             PCPT                         
                                                 SU-                      
                                                    PCPT                  
                                                        SU-               
                                                           PCPT           
creams,                                                                   
       PER    PER    PER    PER    PER    PER    PER    PER               
or oil, mm:                                                               
 0 time                                                                   
        0 2   trace                                                       
                 0   0   0  trace                                         
                               0   NA NA  0  3   trace                    
                                                    0   0  0              
 1 hour                                                                   
       15 2   11 0   0   6   8 0   NA NA  4  3   10 0   5  0              
 2 hours                                                                  
       38 3   13 0   0  13  50 0   NA NA  5  4   13 0   8  0              
 4 hours                                                                  
       40 4   16 0   0  16  54 0   NA NA  6  4   16 0   10 0              
24 hours                                                                  
       40 6   16 0   0  26  55 0   NA NA  11 7   16 0   14 0              
After 24 hour                                                             
standing fil-                                                             
tered through                                                             
screen                                                                    
 60 mesh                                                                  
       ++     -      ++     +++    NA     ++ +   -      -                 
100 mesh                                                                  
       ++     -      ++     ++     NA     ++     -      -                 
250 mesh                                                                  
       +++    ++     ++     ++     NA     +++    ++     ++                
__________________________________________________________________________
Run No.                                                                   
       34     35     36     37     38     39     40     41                
__________________________________________________________________________
Composition                                                               
wt. %                                                                     
N-methyl-                                                                 
       16     -      80     -      16     16     -      80                
pyrrolidone                                                               
(M-Pyrol)                                                                 
N-octyl-                                                                  
       48     48     -      80     64     48     48     -                 
pyrrolidone                                                               
(LP-100)                                                                  
N-dodceyl-                                                                
       16     -      -      -      -      16     -      -                 
pyrrolidone                                                               
(LP-300)                                                                  
Butane diol                                                               
       -      32     -      -      -      -      32     -                 
Gafac   5      5      5      5      5      5      5      5                
RE-610                                                                    
Igepal -      -      -      -      -      -      -      -                 
(CO-630)                                                                  
Silwet (L-77)                                                             
        5      5     -      -      -      -      -      -                 
Silwet -      -       5      5      5      5      5     -                 
(L-7607)                                                                  
Pegol (L-31)                                                              
       -      -      -      -      -      -      -       5                
AAC:   10     10     10     10     10     10     10     10                
triforine                                                                 
Solubility at                                                             
       S      IS     S      S      S      S      IS     S                 
23°C.                                                              
Results:*                                                                 
Bloom:                                                                    
0 time poor   NA     excellent                                            
                            no emulsion                                   
                                   poor   poor   NA     excellent         
after 20 turns                                                            
       excellent                                                          
              NA     excellent                                            
                            excellent                                     
                                   excellent                              
                                          excellent                       
                                                 NA     excellent         
Solids,                                                                   
       SU-                                                                
          PCPT                                                            
              SU-                                                         
                 PCPT                                                     
                     SU-                                                  
                        PCPT                                              
                            SU-                                           
                               PCPT                                       
                                   SU-                                    
                                      PCPT                                
                                          SU-                             
                                             PCPT                         
                                                 SU-                      
                                                    PCPT                  
                                                        SU-               
                                                           PCPT           
creams,                                                                   
       PER    PER    PER    PER    PER    PER    PER    PER               
or oil, mm:                                                               
 0 time                                                                   
       trace                                                              
          0   NA NA   0 3   trace                                         
                               0    0 0   trace                           
                                             0   NA NA   0 1              
 1 hour                                                                   
        9 0   NA NA  23 3    6 0    3 0    9 0   NA NA   0 5              
 4 hours                                                                  
       34 0   NA NA  64 9   15 0   11 0   11 0   NA NA  15 7              
24 hours                                                                  
       37 0   NA NA  60 10  16 0   15 0   48 0   NA NA  50 11             
After 24 hour                                                             
standing fil-                                                             
tered through                                                             
screen                                                                    
 60 mesh                                                                  
       +++    NA     -      -      -      +++    NA     ++                
100 mesh                                                                  
       ++     NA     ++     -      ++     -      NA     ++                
250 mesh                                                                  
       ++     NA     +++    -      ++     -      NA     +++               
__________________________________________________________________________
Run No.                                                                   
       42     43     44     45     46     47     48     49                
__________________________________________________________________________
Composition                                                               
wt. %                                                                     
N-methyl-                                                                 
       -      16     16     -      80     -      16     16                
pyrrolidone                                                               
(M-Pyrol)                                                                 
N-octyl-                                                                  
       80     64     48     48     -      80     64     48                
pyrrolidone                                                               
(LP-100)                                                                  
N-dodceyl-                                                                
       -      -      16     -      -      -      -      16                
pyrrolidone                                                               
(LP-300)                                                                  
Butane diol                                                               
       -      -      -      32     -      -      -      -                 
Gafac   5      5      5      5     10     10     10     10                
RE-610                                                                    
Igepal -      -      -      -      -      -      -      -                 
(CO-630)                                                                  
Silwet (L-77)                                                             
       -      -      -      -      -      -      -      -                 
Silwet -      -      -      -      -      -      -      -                 
(L-7607)                                                                  
Pegol (L-31)                                                              
        5      5      5      5     -      -      -      -                 
AAC:   10     10     10     10     10     10     10     10                
triforine                                                                 
Solubility at                                                             
       S      S      S      IS     S      S      S      S                 
23°C.                                                              
Results:*                                                                 
Bloom:                                                                    
0 time none   poor   poor   NA     excellent                              
                                          no emulsion                     
                                                 poor   poor              
after 20 turns                                                            
       excellent                                                          
              excellent                                                   
                     excellent                                            
                            NA     excellent                              
                                          excellent                       
                                                 excellent                
                                                        excellent         
Solids,                                                                   
       SU-                                                                
          PCPT                                                            
              SU-                                                         
                 PCPT                                                     
                     SU-                                                  
                        PCPT                                              
                            SU-                                           
                               PCPT                                       
                                   SU-                                    
                                      PCPT                                
                                          SU-                             
                                             PCPT                         
                                                 SU-                      
                                                    PCPT                  
                                                        SU-               
                                                           PCPT           
creams,                                                                   
       PER    PER    PER    PER    PER    PER    PER    PER               
or oil, mm:                                                               
 0 time                                                                   
       trace                                                              
          0    0 0    0 0   NA NA  0  0   2  0   0  trace                 
                                                        0  0              
 1 hour                                                                   
       10 0    3 0    7 0   NA NA  0  1   8  0   0    5 5  0              
 4 hours                                                                  
       13 0   10 0   11 0   NA NA  No readings taken                      
24 hours                                                                  
       16 0   11 0   42 0   NA NA  0  15  15 0   0  14  11 0              
After 24 hour                                                             
standing fil-                                                             
tered through                                                             
screen                                                                    
 60 mesh                                                                  
       -      -      ++     NA     ++     -      -      +++               
100 mesh                                                                  
       -      -      -      NA     ++     -      ++     ++                
250 mesh                                                                  
       -      -      -      NA     +++    ++     -      ++                
__________________________________________________________________________
 S = soluble;                                                             
 IS = insoluble;                                                          
 - means no sediment;                                                     
 + means trace;                                                           
 ++ means more than trace &lt; 1%;                                           
 +++ means 1-5%                                                           
 **2.5 g of concentrate were diluted with standard H.sub.2 O to 50 g.     
 
    
     
                       TABLE 4A                                                    
______________________________________                                    
MICROSCOPIC CRYSTAL GROWTH                                                
OBSERVATION FOR SELECTED FORMULATIONS                                     
______________________________________                                    
Run No.     27      32     33    36    37  38                             
______________________________________                                    
Microscopic obser-                                                        
vation under stirring                                                     
for crystal growth,                                                       
250×                                                                
Time:                                                                     
 0 hour     0       0      0     **    0   0                              
 1 hour     0       0      0     **    0   0                              
 4 hours    0       0      0     **    0   ***                            
20 hours    ***     **     ***   ***   *   ***                            
25 hours    ***     **     ***   ***   *   ***                            
After 25 hour stir-                                                       
ring filtered through                                                     
screen                                                                    
 60 mesh    -       -      -     -     -   -                              
100 mesh    -       +      -     +     -   -                              
250 mesh    -       -      -     -     -   -                              
______________________________________                                    
Run No.  39      42      43    44    47    48                             
______________________________________                                    
Microscopic                                                               
ovservation                                                               
under stirring                                                            
for crystal                                                               
growth, 250×                                                        
Time:                                                                     
 0 hour  0       0       0     0     0     0                              
 1 hour  0       0       0     0     0     0                              
 4 hours ***     ***     0     **    ***   ***                            
20 hours ***     ***     ***   ***   ***   **                             
25 hours ***     ***     ***   ***   ***   **                             
After 25 hour                                                             
stirring fil-                                                             
tered through                                                             
screen                                                                    
 60 mesh -       -       -     -     -     -                              
100 mesh -       -       +     -     +     -                              
250 mesh +       +       -     +     +     -                              
______________________________________                                    
 
    
     
                                           TABLE 5                                 
__________________________________________________________________________
Run No.                                                                   
       50     51     52     53     54     55     56      57               
__________________________________________________________________________
Composition                                                               
wt. %                                                                     
N-methyl-                                                                 
       0      0      0      0      0      80     80      80               
pyrrolidone                                                               
(M-Pyrol)                                                                 
N-octyl-                                                                  
       80     80     80     80     80     0      0       0                
pyrrolidone                                                               
(LP-100)                                                                  
N-dodceyl-                                                                
       0      0      0      0      0      0      0       0                
pyrrolidone                                                               
(LP-300)                                                                  
Gafac  5      5      5      5      10     5      5       5                
RE-610                                                                    
Igepal 5      0      0      0      0      5      0       0                
(CO-630)                                                                  
Silwet (L-77)                                                             
       0      5      0      0      0      0      5       0                
Silwet 0      0      5      0      0      0      0       5                
(L-7607)                                                                  
Pegol (L-31)                                                              
       0      0      0      5      0      0      0       0                
AAC: Sevin                                                                
       10     10     10     10     10     10     10      10               
Results:**                                                                
Bloom:                                                                    
0 time none   none   none   none   none   good   excellent                
                                                         excellent        
after 20 turns                                                            
       excellent                                                          
              excellent                                                   
                     excellent                                            
                            excellent                                     
                                   excellent                              
                                          excellent                       
                                                 excellent                
                                                         excellent        
Solids,                                                                   
       SU-                                                                
          PCPT                                                            
              SU-                                                         
                 PCPT                                                     
                     SU-                                                  
                        PCPT                                              
                            SU-                                           
                               PCPT                                       
                                   SU-                                    
                                      PCPT                                
                                          SU-                             
                                             PCPT                         
                                                 SU-                      
                                                    PCPT                  
                                                        SU-               
                                                           PCPT           
creams,                                                                   
       PER    PER    PER    PER    PER    PER    PER    PER               
or oil, mm:                                                               
 0 time                                                                   
        0 0    0 0    0 0    0 0   0  0   0  0   0  0   0  0              
 1 hour                                                                   
       11 0   11 0   11 0    9 0   4  0   0  5   0  5   0  5              
 2 hours                                                                  
       12 0   12 0   13 0   11 0   6  0   0  5   0  5   0  5              
 4 hours                                                                  
       13 0   14 0   13 0   13 0   8  0   0  5   0  5   0  5              
24 hours                                                                  
       15 0   14 0   13 0   13 0   13 0   0  5   0  5   0  5              
After 24 hour                                                             
standing fil-                                                             
tered through                                                             
screen                                                                    
 60 mesh                                                                  
       -      -      -      -      -      -      -      -                 
100 mesh                                                                  
       -      -      -      -      -      +      ++     ++                
250 mesh                                                                  
       -      -      -      -      -      +++    ++     ++                
__________________________________________________________________________
Run No.                                                                   
       58     59     60     61     62     63     64     65                
__________________________________________________________________________
Composition                                                               
wt. %                                                                     
N-methyl-                                                                 
       80     80     32     32     32     32     32     16                
pyrrolidone                                                               
(M-Pyrol)                                                                 
N-octyl-                                                                  
       0      0      48     48     48     48     48     64                
pyrrolidone                                                               
(LP-100)                                                                  
N-dodceyl-                                                                
       0      0      0      0      0      0      0      0                 
pyrrolidone                                                               
(LP-300)                                                                  
Gafac  5      10     5      5      5      5      10     5                 
RE-610                                                                    
Igepal 0      0      5      0      0      0      0      5                 
(CO-630)                                                                  
Silwet (L-77)                                                             
       0      0      0      5      0      0      0      0                 
Silwet 0      0      0      0      5      0      0      0                 
(L-7607)                                                                  
Pegol (L-31)                                                              
       5      0      0      0      0      5      0      0                 
AAC: Sevin                                                                
       10     10     10     10     0      10     10     10                
Results:**                                                                
Bloom:                                                                    
0 time excellent                                                          
              excellent                                                   
                     poor   poor   poor   poor   poor   poor              
after 20 turns                                                            
       excellent                                                          
              excellent                                                   
                     excellent                                            
                            excellent                                     
                                   excellent                              
                                          excellent                       
                                                 excellent                
                                                        excellent         
Solids,                                                                   
       SU-                                                                
          PCPT                                                            
              SU-                                                         
                 PCPT                                                     
                     SU-                                                  
                        PCPT                                              
                            SU-                                           
                               PCPT                                       
                                   SU-                                    
                                      PCPT                                
                                          SU-                             
                                             PCPT                         
                                                 SU-                      
                                                    PCPT                  
                                                        SU-               
                                                           PCPT           
creams,                                                                   
       PER    PER    PER    PER    PER    PER    PER    PER               
or oil, mm:                                                               
 0 time                                                                   
       0  0   0  0   0  0   0  0   0  0   0  0   0  0    0 0              
 1 hour                                                                   
       0  5   0  4   6  0   3  0   3  0   1  0   0  0    9 0              
 2 hours                                                                  
       0  5   0  5   7  0   6  0   5  0   3  0   0  0   10 0              
 4 hours                                                                  
       0  5   0  5   7  0   7  0   7  0   4  0   trace                    
                                                    0   12 0              
24 hours                                                                  
       0  5   0  5   7  0   10 0   9  0   8  0   8  0   12 0              
After 24 hour                                                             
standing fil-                                                             
tered through                                                             
screen                                                                    
 60 mesh                                                                  
       -      -      -      -      -      -      -      -                 
100 mesh                                                                  
       +      ++     -      -      -      -      -      -                 
250 mesh                                                                  
       +++    ++     -      -      -      -      -      -                 
__________________________________________________________________________
Run No.      66        67        68        69        70                   
__________________________________________________________________________
Composition wt. %                                                         
N-methylpyrrlidone                                                        
             16        16        16        16        16                   
(M-Pyrol)                                                                 
N-octylpyrrolidone                                                        
             64        64        64        64        48                   
(LP-100)                                                                  
N-dodceylpyrrolidone                                                      
             0         0         0         0         16                   
(LP-300)                                                                  
Gafac RE-610 5         5         5         10        5                    
Igepal (CO-630)                                                           
             0         0         0         0         5                    
Silwet (L-77)                                                             
             5         0         0         0         0                    
Silwet (L-7607)                                                           
             0         5         0         0         0                    
Pegol (L-31) 0         0         5         0         0                    
AAC: Sevin   10        10        0         10        10                   
Results:**                                                                
Bloom:                                                                    
0 time       none      none      none      none      none                 
after 20 turns                                                            
             excellent excellent excellent excellent excellent            
Solids, creams or oil, mm:                                                
             SUPER                                                        
                  PCPT SUPER                                              
                            PCPT SUPER                                    
                                      PCPT SUPER                          
                                                PCPT SUPER                
                                                          PCPT            
 0 time      0    0    0    0    0    0    0    0    0    0               
 1 hour      4    0    7    0    5    0    3    0    9    0               
 2 hours     5    0    8    0    6    0    6    0    9    0               
 4 hours     6    0    9    0    8    0    10   0    9    0               
24 hours     11   0    11   0    10   0    11   0    10   0               
After 24 hour standing                                                    
filtered through screen                                                   
 60 mesh     -         -         -         -         -                    
100 mesh     -         -         -         -         -                    
250 mesh     -         -         -         -         -                    
__________________________________________________________________________
              Run No.      71       72       73       74                  
__________________________________________________________________________
              Composition wt. %                                           
              N-methylpyrrlidone                                          
                           16       16       16       16                  
              (M-Pyrol)                                                   
              N-octylpyrrolidone                                          
                           48       48       48       48                  
              (LP-100)                                                    
              N-dodceylpyrrolidone                                        
                           16       16       16       16                  
              (LP-300)                                                    
              Gafac RE-610 5        5        5        10                  
              Igepal (CO-630)                                             
                           0        0        0         0                  
              Silwet (L-77)                                               
                           5        0        0         0                  
              Silwet (L-7607)                                             
                           0        5        0         0                  
              Pegol (L-31) 0        0        5         0                  
              AAC: Sevin   10       10       10       10                  
              Results:**                                                  
              Bloom:                                                      
              0 time       none     none     none     none                
              after 20 turns                                              
                           excellent                                      
                                    excellent                             
                                             excellent                    
                                                      excellent           
              Solids, creams or oil, mm:                                  
                           SUPER                                          
                                PCPT                                      
                                    SUPER                                 
                                         PCPT                             
                                             SUPER                        
                                                  PCPT                    
                                                      SUPER               
                                                           PCPT           
               0 time      0    0    0   0   0    0   0    0              
               1 hour      7    0   11   0   5    0   3    0              
               2 hours     7    0   11   0   6    0   5    0              
               4 hours     9    0   11   0   7    0   8    0              
              24 hours     10   0   11   0   10   0   10   0              
              After 24 hour standing                                      
              filtered through screen                                     
               60 mesh     -        -        -        -                   
              100 mesh     -        -        -        -                   
              250 mesh     -        -        -        -                   
__________________________________________________________________________
 - means no sediment;                                                     
 + means trace;                                                           
 ++ means more than trace &lt; 1%;                                           
 +++ means 1-5%                                                           
 **2.5 g of concentrate were diluted with standard H.sub.2 O to 50 g.     
 
    
     
                       TABLE 5A                                                    
______________________________________                                    
MICROSCOPIC CRYSTAL GROWTH                                                
OBSERVATION FOR SELECTED FORMULATIONS                                     
______________________________________                                    
Run No.       50    51    52  53  54  55   56   57                        
______________________________________                                    
Microscopic observa-                                                      
tion under stirring for                                                   
crystal growth, 250×                                                
Time:                                                                     
 0 hour       0     0     0   0   0   *    *    *                         
 1 hour       0     0     0   0   0   *    *    *                         
 2 hours      0     0     0   0   0   *    *    *                         
 4 hours      0     0     0   0   0   *    *    *                         
24 hours      0     0     0   0   0   *    *    *                         
After 25 hour stirring                                                    
filtered through screen                                                   
 60 mesh      -     -     -   -   -   -    -    -                         
100 mesh      -     -     -   -   -   -    ++   ++                        
250 mesh      -     -     -   -   -   ++   ++   ++                        
______________________________________                                    
Run No.       58     59      60  61  62  63  64  65                       
______________________________________                                    
Microscopic observa-                                                      
tion under stirring for                                                   
crystal growth, 250×                                                
Time:                                                                     
  0 hour      *      *       0   0   0   0   0   0                        
 1 hour       *      *       0   0   0   0   0   0                        
 2 hours      *      *       0   0   0   0   0   0                        
 4 hours      *      *       0   0   0   0   0   0                        
24 hours      *      *       0   *   *   0   *   *                        
After 25 hour stirring                                                    
filtered through screen                                                   
 60 mesh      -      -       -   -   -   -   -   -                        
100 mesh      ++     +       -   -   -   -   -   -                        
250 mesh      ++     +++     -   -   -   -   -   -                        
______________________________________                                    
Run No.        66    67    68  69  70  71  72  73  74                     
______________________________________                                    
Microscopic observation                                                   
under stirring for                                                        
crystal growth, 250×                                                
Time:                                                                     
 0 hour        0     0     0   0   0   0   0   0   0                      
 1 hour        0     0     0   0   0   0   0   0   0                      
 2 hours       0     0     0   0   0   0   0   0   0                      
 4 hours       0     0     0   0   0   0   0   0   0                      
24 hours       *     0     0   0   0   0   0   0   **                     
After 24 hour stirring                                                    
filtered through screen                                                   
 60 mesh       -     -     -   -   -   -   -   -   -                      
100 mesh       -     -     -   -   -   -   -   -   -                      
250 mesh       -     -     -   -   +   -   -   -   -                      
______________________________________