Patent Publication Number: US-5834006-A

Title: Latex-based agricultural compositions

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This is a continuation of application Ser. No., 07,469,427 filed Apr. 5, 1990 
    
    
     This invention relates to agricultural compositions, and in particular to herbicidal, fungicidal, and insecticidal compositions (hereinafter referred to as pesticidal compositions), for a variety of pre and post-emergence applications. 
     It is generally desired of such pesticidal compositions that they should be easy to handle, and to apply in any desired concentration. Pesticidal compositions are generally supplied in a variety of forms, for example, as wettable powders, emulsifiable concentrates, and suspension concentrates. Such types of formulation have application for a wide range of active ingredients. 
     It is often desirable to incorporate two active components into a single agricultural composition. Thus, for example, it will often be desirable to incorporate together two different types of insecticide, or two different types of herbicide, in order to obtain a broader spectrum of activity. Also, it is frequently desired to incorporate different types of pesticide within the same composition, for example, to formulate a fungicide with a herbicide, or a fungicide with an insecticide. Attempts to formulate such compositions containing two active ingredients can give rise to substantial difficulties because of various types of incompatibility between the active substances employed. Examples of different types of incompatibility are the following: 
     (a) physico-chemical incompatibility 
     (b) chemical incompatibility 
     (c) biological incompatibility (often evidenced as a phytotoxic response). 
     (a) Examples of physico-chemical incompatibility are the following: 
     1. From a biological standpoint, a mixture of fluroxypyr (as 1-methyl heptyl ester) with chlortoluron is attractive. Fluroxypyr 1-methyl heptyl ester is an organosoluble product with a melting point of about 56° C., usually formulated as an emulsifiable concentrate. Chlortoluron is a high melting point product normally formulated as an aqueous suspension concentrate. When attempts are made to produce a suspension concentrate of the mixture, by milling both components together in an aqueous medium, a melting point depression is observed rendering the formulation unstable. 
     2. Again, from a biological standpoint, it is often desirable to attempt to mix chemicals which are either oils or low melting point solids of appreciable organic solvent solubility with solids of high melting point and low organic solvent solubility. This technique of preparing suspension-emulsions is very difficult due mainly to the problem of preventing transfer of material between phases resulting in gross physical changes or chemical instability. Some advances have been made in this area, as exemplified by European Patent Application No. 0117999 which describes the use of phthalate esters as solvents to produce acceptable formulations. This disclosure is however restricted to a limited range of pesticides since the pesticide must be compatible with phthalate esters. 
     3. The problem of mixing a non-aqueous phase with an electrolyte solution is one often addressed by the pesticide formulator and although specific products can be produced to be compatible with electrolytes, these are often so finely balanced in terms of emulsion performance that the product does not perform well in dilution in the natural water of a spray-tank. This difficulty is especially true with liquid fertilizer applications but also in the case of mixing one pesticide active as a salt solution with an oil-solution of another pesticide and attempting to produce a stable mixture therefrom. 
     4. When chemicals interact to produce melting point depressions, if that melting point depression is large the resultant mixed melting point product can sometimes be formulated in the same way as a low melting point single component but there still remains the problem of formulating this new oil-phase with a solid phase. This cannot easily be achieved using conventional technology. 
     (b Examples of chemical incompatibility of components are very many but can be illustrated by the following: 
     Chlorpyrifos-methyl is an organo-phosphate pesticide which has shown an improved spectrum of activity when sprayed with another type of pesticide, the insect growth regulators, the acyl areas. One of this group,  1-3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenyl!-3-(2,6-difluorobenzoyl) urea, referred to herein as &#34;Active N&#34; is highly active in combination with chlorpyrifos-methyl. Active N is only poorly organo-soluble, necessitating the use of potent solvents, e.g., N-methyl pyrrolidone in order to achieve oil solution of both chlorpyrifos-methyl and Active N. In such solutions, however, there is a chemical incompatibility between chlorpyrifos-methyl and Active N resulting in the ester hydrolysis of chlorpyrifos-methyl. Other methods are therefore required to achieve such mixed products. 
     (c) Examples of biological incompatibility are usually those where mixtures of products demonstrate lack of efficacy (often traced back to a chemical or physico-chemical incompatibility) or where mixtures of products show increased unacceptable crop damage (phytotoxicity). An example of this is a mixture of bifenox with a non-aqueous solvent, when applied to cereals. Bifenox in combination with most non-aqueous solvents (sometimes just in combination with surfactant) is usually unacceptably phytotoxic. Therefore it is desirable to provide a method of lowered phytotoxicity when mixing a product such as bifenox with a herbicide soluble in non-aqueous solvents, designed to broaden its spectrum of activity. 
     Naturally, some pesticide mixtures will display more than one of the problems outlined above but these are all problems necessary to be overcome by the formulation chemist in order to prepare marketable pesticide formulations. 
     European Patent Specification No. 0080516, discloses insecticidal compositions in which the active substance is incorporated within particles of a latex and that thereby waterborne dispersions may be prepared. These prior art disclosures are, however, restricted to the use of specific insecticides, chlorpyrifos and chlorpyrifos-methyl, and the disclosure indicates that it is essential that the pesticide utilized is either a liquid or a low-melting solid at ambient temperatures, so that it can be solubilized into the polymer at temperatures less than 100° C. as a liquid. Furthermore the disclosure does not indicate that such use of latex-containing pesticidal formulations can eliminate incompatibilities between otherwise incompatible active ingredients. 
     Furthermore, although the method disclosed in EP 0080516 enables the preparation of latex-containing compositions of chlorpyrifos, its method requires that the active substance should be heated to 60° C. for 2 hours. This is both inconvenient to carry out industrially, and can give rise to thermal degradation of the chlorpyrifos. 
     In addition the method is very unsatisfactory with pesticides which have a somewhat higher melting point. 
     GB-A-2072506 (Desowag-Bayer) is concerned with a film-forming wood preservative concentrate substantially free of inorganic salts or pigments. The compositions disclosed therein comprise an insecticide or fungicide, a water insoluble solvent, and a water-dilutable aqueous plastics dispersion which may be a polymer or copolymer of a vinyl ester, an acrylic acid ester, or a methacrylic acid ester. The compositions also comprise from 0 to 2% of an emulsifier. Although the compositions are somewhat dilutable in water (up to 1:4), the compositions are not in the nature of suspension concentrates, i.e., ones which are essentially infinitely diluable (particularly dilutable up to at least 50:1) in water. This is not surprising when it is considered that the essential characteristic of the compositions of the reference is that they contain drying oils and/or an alkyd resin. They are thus in the nature of paints, for application to timber and the like and the purpose of the latex in the composition is to act as a film-former. 
     It is inconsistent with the latex acting as film-former that high levels of surfactant should be present, and in particular that a sufficient amount of surfactant should be present to enable the compositions to be essentially infinitely dilutable with water). It is well known that the presence of surfactants will interfere with the film forming properties of latex dispersions such as are described in GB-A-2072506, such that incomplete and non-adhesive deposits will be produced, and not the continuous adherent films which the Patentees seek to produce. 
     As in EP-A-0080516, GB-A-2072506 does not teach that the use of a latex in a pesticide composition is effective to improve compatibility of incompatible active materials. 
     GB-A-658222 (B.F. Goodrich) discloses pesticidal composition containing a latex of PVC or the like, to assist the active material to stick to the intended substrate. This patent is not however concerned with the preparation of stabilized concentrate solutions. 
     U.S. Pat. No. 3,400,093 (Feinberg) discloses insecticide-containing compositions including polymers and polymer latexes. The latexes are present in these compositions to improve their coating properties and the compositions are not like those of GB-A-207250 and GB-A-658222, and are not water-dilutable concentrates. 
     DE-A-3304457 (Toagosei Chem Ind (sic)) is concerned with the dispersion of solid pesticidal particles within a latex. 
     JP-A-8072-501 (Toa Gosei Chem Ind) is concerned with the preparation of what are effectively solutions of high molecular weight polymers, including pesticidal substances, which are obtained by the neutralization of an acid dispersion of a copolymer with an alkali. This reference is not concerned with the stabilization of pesticide-containing emulsions, using polymer latexes. 
     GB-A-2138291 (Tzang) is also concerned with the coating compositions in the nature of paints, containing insecticidally active ingredients. These compositions contain polymer latexes. 
     BE-A-708798 (Bayer) is similar in some ways in its disclosure to EP 0080516, in that it is concerned with insecticidal compositions, in which the insecticidal material can be directly imbibed into the particles of a latex for application purposes. 
     GB-A-1367137 (PVO International) is concerned with insecticidal compositions for mothproofing of wool. The aim of the invention is to improve the persistence of insecticides in a treated fabric, by holding the insecticidal material in place on the woollen subtrate, using a polymer, which has been polymerized in situ. This is achieved by applying the insecticidal material as a composition including a polymerizable resin. Such resins are, in some embodiments, used in the form of a latex. 
     None of these references address the problems of incompatibility between different active ingredients in pesticidal compositions. 
     We have now surprisingly discovered that incompatibility problems such as discussed above can largely be solved for many systems by formulating the composition in the form of a pesticide-containing aqueous latex dispersion wherein a first one of the active components is substantially wholly contained in a dispersed phase derived from a latex. The second different type of active component is not substantially wholly contained within this phase and is present as a dispersion and/or a solution in the continuous aqueous phase. 
     An agricultural composition, comprising at least a first active pesticidal component, and at least one other active component which is a second type of pesticidal component or a fertilizer, 
     wherein the said at least one other active component is physico-chemically, chemically or biologically incompatible with the first pesticidal component, the composition being in the form of an aqueous dispersion having a continuous aqueous phase, and at least a first dispersed phase, 
     wherein the composition comprises at least one emulsifying surfactant in an amount sufficient to render the composition water-dispersible, 
     characterized in that the first dispersed phase contains particles derived from a latex, the said first pesticidal component is present in the composition substantially wholly within the said first dispersed phase, and in that the said other at least one active ingredient is essentially all present either in the continuous aqueous phase, or in a second dispersed phase, whereby the said incompatibility is reduced or eliminated. 
     The pesticide-containing latex dispersion may be produced by, for example, the method disclosed in EP 0080516 when the active substance has a suitably low melting point, e.g., 40° C. or lower. Alternatively and preferably the active substances may be dissolved in an appropriate water-immiscible solvent, and thus an oil-in-water emulsion of the resulting solution is formed. The emulsion is combined with a latex and the second active substance. 
     The term &#34;particles&#34; as used herein is not meant to carry with it any implication as to the physical state (i.e. liquid or solid) of the dispersed phase, and specifically is intended to include within its scope droplets comprising the pesticidal substance. It should also be understood that the term &#34;water immiscible&#34; as used herein is not intended to signify that the solvent is totally water-immiscible but only that the solvent is not freely miscible with water. 
     The term &#34;latex&#34; as used herein is intended to include any polymeric product produced as an aqueous suspension by an emulsion polymerisation process and includes within its scope both synthetic latexes and natural latexes. 
     The preferred latexes comprise polymers and copolymers of styrene, alkyl styrenes, isoprene, butadiene, acrylonitrile, lower alkyl acrylates, vinyl chloride, vinylidene chloride, vinyl esters of lower carboxylic acids and alpha, beta-ethylenically unsaturated carboxylic acids, including polymers containing three or more different monomer species copolymerized therein, the size of the polymeric particles being in the range of from 0.03 to 20 microns, preferably from 0.1 to 10 microns. Small amounts, for example, 0-10% of bifunctional vinyl monomers may be employed to crosslink the polymers if desired. 
     Specifically, it has been discovered that particularly good results are obtained when the initial droplet size of the emulsion formed is from 1 to 100 microns, wherein the latex employed has a particle size of from 0.03 to 20 microns, and wherein the resulting dispersion formed has a particle size which lies between that of the initially-formed emulsion particles, and that of the latex particles. This can be determined by examining optically the average particle size of the dispersion formed, and noting optically the change of the particle size with time. 
     In general, it is found that an emulsion having a relatively large particle size (1 to 100 microns) is formed initially, but that the droplet size decreases with time. It is believed the latex combines with the emulsion droplets to produce a dispersion having a substantial number of particles with an intermediate particle size, for example, in the range of 0.03 to 20 microns, preferably from 0.1 to 10 microns, more preferably from 0.1 to 5 microns, more preferably still from 0.1 to 2 microns. Some individual droplets larger than these size ranges may also be present. 
     The first active pesticidal component may, preferably be dissolved in a water immiscible solvent prior to the initial emulsion formation, or if it has a sufficiently low melting point, it may be emulsified without the use of an organic solvent. 
     The latex may be present when the initial emulsion is formed, in which case the emulsion droplets will begin to combine with the latex immediately after they are formed. Alternatively, an emulsion may first be formed by combination of the solution of the pesticide with the emulsifier, in the presence of water, and the emulsion thus formed may thereafter be combined with the latex. 
     In order to form an initial aqueous dispersion of pesticide solution having the desired droplet size, it has been found necessary to employ an emulsifier (i.e. a surfactant). The emulsifier can be incorporated into the continuous (aqueous) phase, (in which case the surfactant preferably has a hydrophile-lipophile balance (HLB) number of 12 or more). Alternatively the surfactant may be incorporated into the dispersed phase (in which case the surfactant preferably has a HLB number of less than 12). 
     Surfactants which can be advantageously employed herein can be readily determined by those skilled in the art and include various nonionic, anionic, cationic or amphoteric emulsifiers, or a blend of two or more emulsifiers may be employed. The surfactant employed for the emulsification of the non-aqueous phase should be compatible with the latex and with any surfactants which may be present in the latex composition. 
     Examples of nonionic surfactants useful in preparing the oil-in-water emulsion include the polyalkylene glycol ethers and condensation products of alkyl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxide or mixtures of ethylene and propylene oxides such as the ethoxylated alkyl phenols or ethoxylated aryl or polyaryl phenols and carboxylic esters solubilized with a polyol or polyoxyethylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amines. Anionic emulsifiers include the oil-soluble (e.g. calcium, ammonium) salts of alkyl aryl sulphonic acids, oil soluble salts of sulphated polyglycol ethers, salts of the esters of sulphosuccinic acid, or half esters thereof with nonionic surfactants and appropriate salts of phosphated polyglycol ethers. Preferred emulsifiers are those which form and stabilize oil-in-water emulsions such as ethoxylated alcohols, alkoxylated alkyl phenols or polyalkylene oxide co-polymers. The surfactant is employed in an amount sufficient to ensure that the emulsion so formed prior to addition of a latex is easily formed and yet does not cause the latex to coagulate. This amount will be from 0.1 to 15.0% of the total composition, preferably 1.0% w/w to 10%. 
     The nature of the water-immiscible solvent, if present, used in the present invention will vary depending upon the pesticidal substance which it is desired to incorporate, and the latex type. Specific examples, however, are the aromatic liquids, particularly alkyl substituted benzenes such as xylene or propyl benzene fractions, and mixed naphthalene and alkyl naphthalene fractions; mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene, polybutenes; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty acids such as the dimethyl amide of caprylic acid; chlorinated aliphatic and aromatic hydrocarbons such as 1,1, 1-trichloroethane and chlorobenzene, esters of glycol derivatives, such as the acetate of the n-butyl, ethyl, or methyl ether of diethylene glycol, the acetate of the methyl ether of dipropylene glycol, ketones such as isophorone and trimethyl cyclo-hexanone (dihydroisophorone) and the acetate products such as hexyl, or heptyl acetate. The preferred organic liquids are xylene, propyl benzene fractions, dihydroisophorone, and alkyl acetates. 
     Pesticidal substances suitable for use as the first pesticidal component in the composition in accordance with the invention include the following insecticides: 
     
         ______________________________________                                    
allethrin           butocarboxim                                          
amitraz             carbophenothion                                       
azinphos-ethyl      carbosulfan                                           
azinphos-methyl     chlordimeform                                         
benfuracarb         chlorfenvinphos                                       
benzoximate         chlormephos                                           
bifenthrin          chlorobenzilate                                       
binapacryl          chloropropylate                                       
bioallethrin        chlorphoxim                                           
bioresmethrin       chlorpyrifos                                          
bromophos           chlorpyrifos-methyl                                   
bromophos ethyl     crotoxyphos                                           
bromopropylate      cyanophos                                             
butocarboxim        cyfluthrin                                            
cypermethrin        cyhalothrin                                           
deltamethrin        ethiofencarb                                          
demeton             ethion                                                
demeton-S-methyl    ethofumesate                                          
1,3-dichloropropene ethoprophos                                           
dichlorvos          etrimfos                                              
dicofol             fenamiphos                                            
dinobuton           fenitrothion                                          
dioxabenzofos       fenobcarb                                             
dioxacarb           fenpropathrin                                         
dioxathion          fenthion                                              
disulfoton          fenvalerate                                           
endosulfan          flucythrinate                                         
EPN                 fluvalinate                                           
pirimiphos-methyl   fonofos                                               
profenofos          furathiocarb                                          
promecarb heptenophos                                                     
propaphos           hydroprene                                            
propargite          isofenphos                                            
prothiofos          isoxathion                                            
quinalphos          malathion                                             
resmethrin          mecarbam                                              
sulprofos           mephospholan                                          
temephos            methacrifos                                           
tetradifon          methidathion                                          
tetramethrin        methoprene                                            
thiocyclam          mevinphos                                             
thiometon           naled                                                 
tralomethrin        parathion                                             
triazophos          parathion methyl                                      
xylylcarb           permethrin                                            
                    phenothrin                                            
                    phosalone                                             
                    phosfolan                                             
                    phosmet                                               
                    phoxim                                                
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     N-2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene-2,4-xylidine. 
     The following fungicides: 
     
         ______________________________________                                    
benalaxyl           dodemorph                                             
bis-(2,4-dichlorophenyl                                                   
                    tridemorph                                            
ethyl phosphate                                                           
bupirimate          fenpropidin                                           
buthiobate          fenpropimorph                                         
carboxin            and other morphine                                    
dodine              fungicides and                                        
                    ergosterol                                            
edifenphos          biosynthesis inhibitors                               
etridiazole         such as                                               
imazalil            bitertanol                                            
iprobenfos          fenarimol                                             
nuarimol            myclobutanil                                          
oxycarboxin         penconazole                                           
tolclofos-methyl    prochloraz                                            
                    triadimefon                                           
                    triadimenol                                           
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     The following herbicides: 
     
         ______________________________________                                    
acetochlor          2,4-D esters                                          
alachlor            2,4-DB esters                                         
anilophos           di-allate                                             
benfluralin         2,4-DP esters                                         
bensulide           diclofop-methyl                                       
benzoylprop-ethyl   diethatyl                                             
bifenox             dimethachlor                                          
bromoxynil octanoate                                                      
                    dinitramine                                           
butachlor           EPTC                                                  
butamifos           ethalfluralin                                         
butralin            ethofumesate                                          
butylate            fenoxaprop-ethyl                                      
fluorochloridone    flamprop-methyl                                       
chlorphropham       fluazifop butyl                                       
clopyralid          fluchloralin                                          
ethylhexyl ester                                                          
cycloate            flumentralin                                          
cycloxydim          fluorodifen                                           
fluroxypyr-1-methyl fluoroglycofen ethyl                                  
heptyl ester                                                              
fluroxypyr ester    flurecol-butyl                                        
haloxyfop ester     oxadiazon                                             
(methyl/ethbxyethyl)                                                      
ioxynil octanoate   oxyfluorfen                                           
isopropalin         pendimethalin                                         
MCPA esters         phenisopham                                           
MCPB esters         phenmedipham                                          
CMPP esters         picloram esters                                       
metolachlor         profluralin                                           
molinate            propachlor                                            
monalide            propanil                                              
napropamide         pyridate                                              
nitrofen            quizalafop-ethyl                                      
trifluralin         sethoxydim                                            
                    triallate                                             
                    triclopyr esters                                      
                    tridiphane                                            
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     2-(4-(2-fluoro-4-bromophenoxy)phenoxy propionic acid esters and the resolved isomers 2-(4-((3-fluoro-5-(trifluoromethyl)-2-pyridinyl)oxy)phenoxy propanoic acid esters and their resolved isomers. 
     The first active component may be an organosoluble derivative of a pesticidal compound which is itself poorly organosoluble or insoluble, such as cyhexatin dodecylbenzene sulphonate. 
     The first pesticidal component may also be a compatible mixture of two such pesticidal substances, for example, a solution of one such substance in another, or a eutectic mixture of two such substances (e.g. a eutectic mixture of fluroxypyr 1-methyl heptyl ester with bifenox). 
     The compositions of the invention may also include optional adjuvants such as freezing point depressants preferably in amounts of 0-15%, flow aids to prevent caking or aid in the redispersion of bottom sediment preferably in amounts of 0-5%, thickening agents preferably in amounts of 0-3% and defoamers preferably in amounts of 0-1% to improve the overall properties under field storage and use conditions. 
     Similarly conventional pesticide adjuvants such as solvents, surfactants for increasing penetration of the active substances or salts may be incorporated into the compositions to maintain or improve biological efficacy of the composition. These may be incorporated into the oil phase or aqueous phase as appropriate, typically in amounts of from 0 to 50% by weight. 
     The compositions of the invention may be prepared by first preparing an oil-in-water emulsion and subsequently adding a polymer latex dispersion, with stirring at a temperature from 0° C. to 100° C., preferably from 10° C. to 80° C., more preferably from 20° C. to 50° C. 
     The oil phase may contain from 10 to 80% w/v of the pesticide, preferably 10 to 60% and most preferably 20 to 50% w/v. The latex content of the composition will depend upon the latex type as well as the pesticide and surfactant type but may vary from 5 to 80% w/v, preferably 5 to 60% w/v and most preferably 10 to 50% w/v. 
     The emulsion may be prepared prior to addition of the polymer dispersion or by addition of the solution of the pesticide in the non-aqueous solvent to the polymer dispersion. A variety of stirring methods may be employed, from simple shaking, stirring through to sonication and high shear emulsification, including bead milling. The method employed, the temperature chosen and the time taken for equilibration will depend upon 
     a) the nature and amount of the pesticidal compound and solvent employed. 
     b) the nature and amount of latex employed. 
     c) the nature and amount of surfactant employed. 
     The second different type of active component may be, for example, a water soluble component which is present in the aqueous phase of the resulting composition. The second active component is preferably a pesticide, for example, a pesticide which is intrinsically water soluble, or a water-soluble salt derivative such as a salt of an otherwise water-insoluble pesticide. 
     Examples of such second different type of active pesticide components which are either water-soluble or have water soluble-salts include the insecticides: 
     
         ______________________________________                                    
             acephate                                                     
             cartap                                                       
             omethoate                                                    
             oxamyl                                                       
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     The fungicides: 
     
         ______________________________________                                    
        bronopol                                                          
        dichlorophen                                                      
        dimethirimol                                                      
        dodemorph                                                         
        dodine                                                            
        fenpropimorph                                                     
        quazatine                                                         
        tridemorph                                                        
        (±) 1-amino propyl phosphonic acid                             
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         ______________________________________                                    
           acifluorfen                                                    
           alloxydim                                                      
           amitrole                                                       
           ammonium sulphamate                                            
           asulam                                                         
           benazolin                                                      
           bentazone                                                      
           bromoxynil                                                     
           clopyralid                                                     
           2,4-D                                                          
           dalapon                                                        
           2,4-DB                                                         
           2,4-DES                                                        
           dicamba                                                        
           dich1orprop                                                    
           difenzoquat                                                    
           diquat                                                         
           endothal                                                       
           fenprop                                                        
           fomesafen                                                      
           glufosinate                                                    
           glyphosate                                                     
           imazapyr                                                       
           imazaquin                                                      
           ioxynil                                                        
           MCPA                                                           
           MCPB                                                           
           CMPP                                                           
           paraquat                                                       
           picloram                                                       
           triclopyr                                                      
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     The plant growth regulators: 
     
         ______________________________________                                    
chlormequat          ethophon                                             
chlorphonium         mepiquat                                             
daminozide           piproctanyl                                          
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     The second different type of active component may also be, for example, a water insoluble (or poorly water soluble) pesticide or mixture of pesticides present as a particulate dispersion in the aqueous phase. Examples of such second different type of active pesticide components include the insecticides: 
     
         ______________________________________                                    
            bendiocarb                                                    
            binapacryl                                                    
            carbaryl                                                      
            carbofuran                                                    
            chlormethiuron                                                
            clofentezine                                                  
            cyhexatin                                                     
            diflubenzuron                                                 
            gamma-HCH                                                     
            hexythiazox                                                   
            trichlorfon                                                   
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     teflubenzuron and other acylurea insecticides such as chorfluazuron, and &#34;Active N&#34; referred to above. 
     The fungicides: 
     
         ______________________________________                                    
anilazine           iprodione                                             
anthraquinone       3-isopropoxy-o-                                       
                    toluanilide                                           
captafol            mancozeb                                              
captan              ofurace                                               
carbendazim         copper oxinate                                        
chlorothalonil      pencycuron                                            
copper oxychloride  thiabendazole                                         
cyprofuram          thiophanate methyl                                    
dichlofluanid       thiram                                                
dichlobutrazol                                                            
dichloran                                                                 
dithianon                                                                 
ethirimol                                                                 
fentin                                                                    
flutriafol                                                                
hexaconazole                                                              
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     The herbicides: 
     
         ______________________________________                                    
           aclonifin                                                      
           ametryn                                                        
           atrazine                                                       
           aziprotryne                                                    
           bifenox                                                        
           chloridazon                                                    
           chlorotoluron                                                  
           chlorosulfuron                                                 
           cynazine                                                       
           difenoxuron                                                    
           diflufenican                                                   
           diuron                                                         
           fluometuron                                                    
           isoproturon                                                    
           isoxaben                                                       
           karbutilate                                                    
           lenacil                                                        
           metamitron                                                     
           metazachlor                                                    
           methabenzthiazuron                                             
           metoxuron                                                      
           metribuzin                                                     
           metsulfuron                                                    
           neburon                                                        
           proglinazine ethyl                                             
           promethryne                                                    
           propazine                                                      
           simazine                                                       
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     Certain active substances may be present either in the first dispersed phase, or in the continuous phase depending on the formulation type. For example, esters of 2,4-D are soluble in organic solvents, and thus suitable for incorporation into the first dispersed phase. Its sodium salt is water-soluble and suitable for incorporation as the second different type of active component dissolved in the aqueous continuous phase. 
     In certain circumstances, it is even possible for the same pesticidal substance to be contained within both the first and the second different type of active components. For example, fluroxypyr 1-methyl heptyl ester forms a eutectic mixture in a 3:1 ratio mixture with bifenox. It is however not normally possible to incorporate further bifenox to make a storage-stable preparation, without the use of substantial quantities of organic solvents, which give rise to phytotoxicity. 
     Thus, in one embodiment, the first pesticidal component is a eutectic mixture of first and second pesticidal substances (for example fluroxypyr 1-methyl heptyl ester and bifenox), and the second component is a solid phase of one of the said substances, dispersed in the aqueous phase (for example dispersed bifenox). 
     The compositions of the invention may be produced by the preparation of a latex dispersion containing the first active component by a variety of means as discussed earlier, followed by blending with an aqueous solution or dispersion of the second active component. The aqueous dispersions of this second active or mixture of components may be prepared by the many techniques known in the art such as sand milling, bead milling and dry milling followed by dispersion in water. Such aqueous dispersions generally contain a surfactant system composed of a wetting agent and a dispersing agent or a combined wetter/dispersing agent, a suspension/flow and optionally an antifreeze agent and an antifoam agent. The levels of all such additives may be adjusted dependent upon the ratio of latex containing first pesticide phase to second active. 
     The range and choice of adjuvants is well known to those skilled in the art but as general examples the wetting agents employed may be an alkali metal salt of a phosphate partial ester of a (C 6  -C 24 ) alkyl polyglycol ether (containing 2-20 EO units), an alkali metal salt of an alkyl naphthalene sulphonic acid or a nonionic polyglycol ether. The dispersing agents can be alkali metal or amine salts or sulfosuccinic acid half-esters, amine salts of phosphate partial esters of polyaryl phenol polyglycol ethers, alkali metal lignin sulfonates or condensation products of formaldehyde and cresols. Small quantities of an aluminium silicate having a lamellar structure of the bentonite type, such as, for example, Hectorite or montmorillonite may be added as a thickener with or without small quantities of a polysaccharide such as, for example, Rhodopol 23. Antifreeze agents may include ethylene glycol, propylene glycol or glycerol. The aqueous solutions may be prepared by simple dissolution of a water-soluble chemical in water or by neutralization of an acid with an appropriate base or by neutralization of a base with an appropriate acid. The aqueous continuous phase may contain active substances both dispersed in it and dissolved in it resulting in a three phase pesticide system for the product of the invention. 
     As discussed earlier the first and the second different type of pesticide components may be physico-chemically incompatible, chemically incompatible or biologically incompatible. 
     They also have the ability, since they contain film forming latexes in many cases, to be utilized in those areas where film forming is a desirable effect, such as in seed treatments and pest control usage in dwelling places. The invention is illustrated by the following examples which are not limiting but merely illustrative: 
     The following list identifies the various starting materials used in the Examples. 
     
         ______________________________________                                    
Common Name          Trade Mark                                           
______________________________________                                    
ACTIVES                                                                   
A     chlortoluron       DICURANE                                         
B     chlorpyrifos-methyl (technical)                                     
                         RELDAN                                           
C     myclobutanil       SYSTHANE                                         
D     prochloraz         SPORTAK                                          
E     fluoroxypyr 1-methyl heptyl ester                                   
                         STARANE                                          
F     isoproturon        ARELON                                           
G     bifenox            MODOWN                                           
H     fenpropimorph                                                       
I     ioxynil octanoacetate                                               
J     copper oxinate                                                      
K     anthraquinone                                                       
L     nuarimol                                                            
M     (±)-1-aminopropyl phosphonic acid                                
N     1- 3,5-dichloro-4-(1,1,2,2-                                         
      tetrafluoroethoxy)phenyl!-3-(2,6-                                   
      difluorobenzoyl)urea                                                
SURFACTANTS                                                               
A     ethoxylated alcohol                                                 
                         ATLOX 4991                                       
B     ethoxylated alcohol blend                                           
                         ATLOX 4896                                       
C     acrylic graft copolymer                                             
                         ATLOX 4913                                       
D     phosphate ester    AGRILAN TKA125                                   
E     block copolymer    AGRILAN F502                                     
F     anionic ether sulphate                                              
                         SOPROPHOR 4D384                                  
G     polyaryl phenol ethoxylate                                          
                         SOPROPHOR BSU                                    
H     half ester sulphosuccinate                                          
                         PESTILISER B                                     
I     ethoxylated tallow amine                                            
                         ETHOMEEN T25                                     
J     block copolymer    PLURIOL PE6100                                   
K     block copolymer    PLURIOL PE 6200                                  
L     phosphate ester    SOPROPHOR FL                                     
M     polycarboxylate    AGRILAN F460                                     
N     block copolymer    TENSIOFIX 35600DL                                
SOLVENT                                                                   
A     xylene                                                              
B     aromatic C9 benzenoid distillate                                    
                         SOLVESSO 100                                     
C     hexyl acetate      EXXATE 600                                       
D     mixed naphthalene fraction                                          
                         SOLVESSO 200                                     
E     fatty acid dimethylamide                                            
                         HALCOMID M-8-10                                  
______________________________________                                    
POLYMER LATEXES                                                           
TRADEMARK                                                                 
                                  Particle Size                           
      Type          Trade Mark    (Microns)                               
______________________________________                                    
A     terpolymer    VINAMUL 3452  0.1-0.3                                 
B     styrene butylacrylate                                               
                    DOW LATEX DL420                                       
                                  0.12-0.15                               
C     styrene butadiene                                                   
                    DOW LATEX DL893                                       
                                  0.14-0.2                                
______________________________________                                    
 
    
    
    
     EXAMPLE I 
     Preparation of a mixed formulation of fluroxypyr 
     1-methyl heptyl ester and chlorotoluron 
     Active E (142 g) was dissolved in xylene (150 g) to produce a 48.6% w/w ester solution. 300 g of polymer latex B was added to 10 g of surfactant I to produce a homogeneous dispersion. 292 g of the ester solution was added to the latex/surfactant dispersion with high shear stirring and stirred for 30 minutes. 121 g of this pesticide-containing latex dispersion was added to a previously prepared 600 g/L chlorotoluron (Active A) suspension concentrate (800 g) and homogenized with high shear mixing. The product was then diluted to 1 liter with water. On storage at 40° C., this product did not solidify but remained a stable mixed suspension concentrate. 
     EXAMPLE IA (COMPARATIVE) 
     Active E (330 g) was dispersed in water (500 g) containing surfactant E (14.0 g) and propylene glycol (25 g). This dispersion was bead milled until the particle size of the suspension was about 3,0 microns (vmd) by Coulter Counter TA II (Coulter Counter is a Trade Mark). The product was diluted to 1 liter with water. 100 g of this milled product was added to 960 g of a commercial suspension concentrate of Active A and the product homogenized with a high-shear mixer. This product on storage solidified at 40° C. owing to a melting-point endotherm between fluroxypyr 1-methyl heptyl ester and chlorotoluron and was thus unacceptable. 
     EXAMPLE II 
     Preparation of a mixed formulation of fluroxypyr 
     1-methyl heptyl ester, ioxynil octanoate and 
     isoproturon 
     Active E (45 g) and active I (84 g) were dissolved in solvent B (100 g) and mixed with 10 g surfactant F. This oil phase was added to a latex dispersion prepared by mixing a ternary latex (latex A) (230 g) and water (30 g) and stirred with high shear mixing for 30 minutes. This aqueous pesticide containing latex dispersion (500 g) was added to a commercial isoproturon aqueous suspension concentrate (active F) (580 g) and mixed for 5 minutes. This product on storage at both 40° C. and 54° C. showed no crystal growth or emulsion growth after a period of 3 months storage as evidenced by Coulter Counter examination and microscopic evaluation, indicating a physically stable product. 
     EXAMPLE IIA (COMPARATIVE) 
     Active E (45 g) and active I (84 g) were dissolved in solvent B (100 g) and mixed with surfactant F (10 g). This oil phase was then emulsified into water (240 g) and the prepared emulsion mixed under high shear mixing with a commercial isoproturon aqueous suspension concentrate (580 g) (active F). The product was then diluted with water to 1 liter (approx 25 g). This product on storage at 45° C. and 54° C. showed crystal growth and emulsion growth after 1 months storage as evidenced by Coulter Counter examination and microscopic evaluation indicating a physically unstable mixture. 
     EXAMPLE III 
     Preparation of a mixed formulation of fluroxypyr 
     1-methyl heptyl ester and bifenox 
     A solution was prepared of 300 g of active E a mixture of solvent D (240 g) and solvent E (60 g). This 50% w/w technical fluroxypyr ester solution (454.5 g) was stirred into a latex/surfactant dispersion prepared by mixing latex C (454.5 g) with 10 g of surfactant I and 122.6 g water. The mixture was stirred under high shear for 30 minutes. 260 g of this aqueous pesticide containing latex dispersion was added to 416 g of a commercial aqueous suspension of bifenox (active G) and diluted with water (104 g) to produce a stable mixed formulation containing 50 g/L fluroxypyr acid equivalent and 250 g/L bifenox. 
     EXAMPLE IIIA (COMPARATIVE) 
     A solution of 89 g fluroxypyr 1-methyl heptyl ester (active E) was prepared in a mixture of 120 g of solvent D with 27 g of solvent E. 
     This solution was emulsified into water (320 g) containing surfactant F (15 g) with a high shear mixer and the resultant emulsion mixed with a commercial bifenox aqueous suspension concentrate (493 g) (active G) and diluted with water to 1 liter. 
     Samples of Examples III and IIIa were applied to spring barley under glasshouse conditions. The compositions were applied at application rates of 3 L/ha and 2.5 L/ha respectively, so as to provide the same application rate of the active components. The dilution was in both cases such as to provide an application rate of 200 L/ha of the dilution. The spring barley was then grown in the glasshouse for 14 days and evaluated for phytotoxicity, expressed as percentage necrosis. The results are shown in the attached table. 
     
         ______________________________________                                    
            Rate of product                                               
                     necrosis after                                       
            (L/ha)   l4 days (%)                                          
______________________________________                                    
Formulation of                                                            
              3          3.5                                              
Example III                                                               
Formulation of                                                            
              2.5        12.5                                             
Example IIIA                                                              
Comparative                                                               
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     This illustrates the advantage of employing a pesticide containing latex formulation. 
     EXAMPLE IV 
     Preparation of a mixed formulation of fluroxypyr 
     1-methyl heptyl ester and bifenox 
     Although fluroxypyr 1-methyl heptyl ester has a melting point of about 56° C., a 3:1 ratio mix of fluroxypyr ester and bifenox has a melting point of 436° C. This was utilized to prepare a low solvent pesticide containing latex dispersion for subsequent admixture with an aqueous suspension concentrate of bifenox. 
     Fluroxypyr 1-methyl heptyl ester and bifenox (actives E and G) in a 3:1 ratio (24 g) were mixed with surfactants J (12 g) and K (4 g) and then mixed with high shear agitation into a styrene-butyl acrylate latex (latex B) (40 g) and the mixing continued for 30 minutes. Water (20 g) was added. This pesticide containing latex dispersion (42 g) was then added to a commercial bifenox aqueous suspension concentrate (55.4 g) (active G) and diluted with water to 100 ml to produce a formulation containing 50 g/l fluroxypyr acid equivalent and 250 g/L bifenox as a stable formulation. 
     Comparison of the phytotoxicity potential for 
     fluroxypyr/bifenox formulations 
     (EXAMPLES III AND IV) 
     Samples of Examples III and IV were applied to barley, cv. lgri, grown under glasshouse conditions, at rates of 200 L/ha. The barley was then grown in the glasshouse for 7 days and evaluated for phytotoxicity, scored according to the European Weed Research Council scoring recommendations for crop injury (listed below). 
     
         ______________________________________                                    
Crop Response                                                             
Rating  % Crop Injury  Verbal Description                                 
______________________________________                                    
1       0              No reduction or injury                             
2       1.0-3.5        Very slight discoloration                          
3       3.5-7.0        More severe but not lasting                        
4        7.0-12.5      Moderate and more lasting                          
5       12.5-20.0      Medium and lasting                                 
6       20.0-30.0      Heavy                                              
7       30.0-50.0      Very Heavy                                         
8       50.0-99.0      Nearly destroyed                                   
9       100            Completely destroyed                               
______________________________________                                    
 
    
     The results are as follows: 
     
         ______________________________________                                    
            Rate of product                                               
            (L/ha)   Crop Injury                                          
______________________________________                                    
Formulation of                                                            
              3          3.3                                              
Example III                                                               
Formulation of                                                            
              3          1.5                                              
Example IV                                                                
______________________________________                                    
 
    
     It can be seen that the omission of solvent from the composition, in Example IV, which is made possible by the melting point depression of the mixture, gives rise to even lower phytotoxicity than in Example III. 
     EXAMPLE V 
     Preparation of a seed treatment composition 
     containing fenpropimorph, thram and lindane 
     Fenpropimorph (38 g) was added with high shear stirring to a surfactant/latex dispersion produced by mixing 5 g of surfactant A with 38 g of a latex A and water (20 g). The stirring was continued for 15 minutes. This pesticide containing latex dispersion was added to a previously prepared 70% w/w lindane suspension concentrate (780 g). Air-jet milled thiram (75 g) added and Titanium dioxide (30 g) were added, and the mixture was homogenized. 160 g of a 1% xanthan gum concentrate was added and water to 1 liter to yield a stable, very fluid product. This product when applied directly to oil seed rape at a rate of 22 ml/kg seed, produced a much superior coating to the standard commercial product prepared by the use of fenpropimorph as its hydrochloride salt. 
     EXAMPLE VI 
     Preparation of a mixed formulation containing 
     myclobutanil, copper oxinate and anthraquinone 
     Myclobutanil (50 g) was dissolved in solvent C (150 g). Surfactant A (5 g) was added to a terpolymer latex (200 g) (latex A) and to this latex/surfactant dispersion was added the previously prepared solution with high shear agitation. The stirring was continued for 20 minutes to produce a stable myclobutanil containing latex. 
     A suspension concentrate of copper oxinate and anthraquinone was prepared by mixing together under high shear agitation, copper oxinate (67 g), anthraquinone (225 g), surfactant L (30 g), surfactant M (10 g), Ponceau Brilliant 4R (25 g), water (300 g) and xanthan gum (1.5 g). This mixture was then bead-milled to a particle size median of 2.0 microns and the previously prepared pesticide containing latex (400 g) added thereto. The product was diluted to 1 liter with water to produce a stable mixed dispersion. This dispersion was suitable for application to cereal seeds, giving excellent coverage on wheat and barley. A similar product prepared from an emulsion of myclobutanil in solvent C without added latex was physically unstable and did not coat seeds efficiently. 
     EXAMPLE VII 
     Preparation of a mixed formulation containing 
     prochloraz and nuarimol 
     Prochloraz (70 g) was dissolved in solvent C (25 g) and added with high shear agitation to a previously prepared surfactant/latex dispersion of surfactant A (9.0 g) and latex A (100 g). The stirring was continued for 15 minutes to produce a stable prochloraz containing latex. 
     A suspension concentrate of nuarimol was prepared by mixing together under high shear agitation, nuarimol (38 g), surfactant N (4.0 g), surfactant M (1.0 g), water (300 g) and Xanthan gum (2.0 g). This mixture was then bead-milled to a medium particle size of 2.5 microns and the previously prepared pesticide containing latex (204 g) added thereto. The product was diluted to 1 liter with water to produce a mixed dispersion which was stable on storage for at least 1 month. A similar preparation utilizing an emulsion of prochloraz in Exxate 600 without latex was physically unstable. 
     EXAMPLE VIII 
     Preparation of formulation continuing (±)-1-aminopropyl 
     phosphonic acid and prochloraz 
     Prochloraz (70 g) was dissolved in solvent C (25 g) and added with high shear agitation to a previously prepared dispersion of surfactant H (5.0 g) and latex A (100 g). The stirring was continued for 15 minutes to produce a stable prochloraz containing latex. This was added to a 42% w/w solution of Active M as the Potassium salt (55 g) to produce a stable dispersion in this elecrolyte solution. A similar preparation of the prochloraz/Exxate 600 emulsion in the (±)-1-aminopropyl phosphonic acid solution without use of a latex was physically unstable, resulting in gross creaming of the mixture. 
     EXAMPLE IX 
     Preparation of a formulation of 
     chlorpyrifos in liquid fertiliser 
     Chlorpyrifos was dissolved in xylene to produce a 70% w/w solution in xylene. Surfactant H (5 g) was added to 430 g of this 70% w/w chlorpyrifos solution and this oil-phase added to latex A (250 g) with high shear agitation and the stirring continued for 1 hour. The product was then diluted to 1 liter with water. This product was then diluted at 10% v/v into a 9:9:9 NPK solution fertilizer to produce a stable non-creaming product. A similar preparation utilizing an emulsion of chlorpyrifos in xylene without latex was physically unstable, creaming rapidly on being allowed to stand unagitated. 
     EXAMPLE X 
     Preparation of a mixed formulation containing 
     myclobutanil, anthraquinone and (±)-1-aminopropyl 
     phosphonic acid 
     Myclobutanil (25 g) was dissolved in Solvent C (50 g) and surfactant D (4.5 g) was added to the solution. This mixture was added with high shear agitation to a latex A (82 g) and water (18 g). The stirring was continued for 10 minutes. This pesticide containing latex dispersion was added to a previously prepared suspension concentrate of anthraquinone prepared by bead milling the following components together to an average particle size of 1.5 microns: 
     
         ______________________________________                                    
       anthraquinone                                                      
                 120 g                                                    
       Surfactant C                                                       
                  50 g                                                    
       Surfactant B                                                       
                  25 g                                                    
       Red pigment                                                        
                  75 g                                                    
       Silicone antifoam                                                  
                  5 g                                                     
       Water to  500 g                                                    
______________________________________                                    
 
    
     This mixture of myclobutanil and anthraquinone was finally added to a solution of (±)-1-aminopropyl phosphonic acid as the potassium salt (30 g) in water (200 g) and adjusted to one liter with water to produce a stable complex pesticide formulation containing myclobutanil as a latex-stabilised oil phase, anthraquinone as a particulate dispersion in water and (±)-1-amino propyl phosphonic acid (potassium salt) in aqueous solution. Attempts were made to formulate the same active components by conventional techniques, but no other formulation type was found to produce a stable product. 
     EXAMPLE XI 
     Preparation of a mixed formulation containing 
     chlorpyrifos-methyl and active N 
     Chlorpyrifos-methyl (active B) (240 g) was dissolved in solvent B (160 g) and added with high shear agitation to a previously prepared surfactant/latex dispersion of surfactant A (48 g), latex A (240 g) and water (200 g). The stirring was continued for 30 minutes to produce a stable chlorpyrifos-methyl containing latex. To this was added 200 g of a 300 g/L aqueous suspension concentrate of active N prepared by mixing active N (300 g), surfactant E, (25 g), Xanthan gum (1.0 g) and water (approx. 700 g) and bead-milling this mixture to a particle size median of about 1 micron. The product was diluted to 1 liter with water and stirred to homogenize the components, yielding a product containing 240 g/L chlorpyrifos-methyl and 60 g/L of active N. This product was stable on storage, especially showing no physical changes. A similar preparation utilizing an emulsion of active B in solvent B without latex was physically unstable showing gross separation of the phases on storage for one month.