JP2000514819A - Method for producing storage-stable pesticide dispersion - Google Patents

Abstract

  (57) [Summary] Ensure that aqueous dispersions of microcapsules containing high levels of pesticides in the form of supercooled melts or supersaturated solutions maintain the median volume particle size of the microcapsules below 6 μm. And by using a surfactant that does not form micelles under storage conditions, thereby inhibiting the transport of the pesticide through the aqueous phase, thereby reducing the crystallization of the pesticide. Be stabilized.

Description

The present invention relates to a method for producing an aqueous dispersion of polymer microcapsules containing a supersaturated solution or supercooled melt of a water-insoluble substance. . In particular, it relates to providing an aqueous dispersion of a pesticide which does not crystallize, so that a product with a high content of active ingredient which is storage-stable can be provided. A storage-stable, transportable aqueous dispersion of a pesticide that can be applied to crops and the like by conventional spraying techniques is provided. It is known to encapsulate highly water-insoluble pesticides in polymeric microcapsules so that the pesticides can be applied to crops and the like. Such microcapsule formulations are commonly provided in the form of spray-dried powders, which are rewetted prior to application. For example, US-A-516 0530 (Griffin) is a pesticide by melting the active ingredient and combining the melted material with a film-forming polymer such as polyvinyl alcohol (PVA). A method for encapsulating is disclosed. The substances are then emulsified together and lyophilized. A similar method is disclosed in U.S. Pat. No. 4,244,836 (Hoechst). For some applications, however, liquid concentrates, especially aqueous concentrates, have substantial advantages over dry formulations. Aqueous concentrates are generally easier to formulate for upland applications, and also result in a reduced likelihood of inhalation by the user. It is known to produce encapsulated pesticides as wet formulations, ie, aqueous dispersions of microcapsules. However, such aqueous concentrates tend to have lower loadings of active ingredient, and therefore tend to be more expensive to store and transport than the corresponding dry formulation. For example, US Pat. No. 4,938,797 includes an example of a wet formulation of microcapsules in which the suspension has an active ingredient content of 46% by weight. Pest control using very small amounts of solvent (so that the pesticide is encapsulated in the form of a supersaturated solution when the dispersion cools) or resulting in microcapsules containing a supercooled melt It is known to produce dried microcapsules containing a pesticide by performing the encapsulation process at an elevated temperature, either by encapsulating the melt of the agent. We have found, however, that concentrated aqueous formulations of microcapsules containing supercooled melts or supersaturated solutions are not storage stable. This is because crystallization of the pesticide occurs upon storage at ambient temperature. This makes the formulation unstable. Surprisingly, storage-stable aqueous dispersions of microcapsules containing a high loading of the active ingredient in the form of supercooled melts or supersaturated solutions have microcapsules not exceeding 6 μm, preferably not exceeding 5 μm It has been discovered that it can be stabilized against crystallization by providing a volume median particle size, more preferably not exceeding 2 μm. Crystallization of the active ingredient from such dispersions avoids the use of surfactants that form micelles under storage conditions (and thereby facilitate the transport of water-insoluble substances through the aqueous phase and cause crystallization). It has been further discovered that it can be reduced by WO 95/07614 relates to the use of polymeric stabilizers that alter the chemical potential of emulsion particles in oil-in-water emulsions and thereby inhibit Ostwald ripening. The use of such stabilizers in suspension-emulsions is also disclosed, which is a number of aqueous dispersing aids for such dispersions, including polyvinyl alcohol / polyvinyl acetate copolymers. This reference also discloses certain microcapsule suspensions. However, WO 95/07614 discloses the desirability of selecting a non-misellising surfactant to stabilize the particulate dispersion and the need to avoid surfactants that form micelles. not exist. In fact, the surfactant used to stabilize the dispersion of microcapsules disclosed in WO 95/07614 is the micellarized surfactant ethoxylated alcohol, Atrox [ATL0X] 4991 ™. . PCT / US95 / 15534 discloses the production of dry microcapsules by spray drying aqueous solutions of microcapsules containing PVA surfactant. However, there is indication in PCT / US95 / 15534 that the use of such surfactants (or the use of any non-micellarized surfactant) can improve the long-term stability of aqueous formulations. do not do. Accordingly, in a first aspect of the present invention, there is provided a method for producing a storage-stable aqueous dispersion of a water-insoluble substance, the method comprising the steps of producing emulsion particles having a median volume particle size not exceeding 6 μm. Emulsifying a non-aqueous phase containing a solution or melt of a water-insoluble substance in water to form, and performing a polymerization process to form an aqueous dispersion of microcapsules from the emulsion particles. The microcapsules having the water-insoluble substance contained therein in the form of a supersaturated solution or a supercooled melt, and comprising stabilizing the dispersion with a non-micellarized surfactant, The dispersed dispersion is essentially free of a micellizing surfactant. The amount and / or nature of the non-micellarized surfactant may be such that the solubility of the water-insoluble substance in the aqueous phase does not exceed 100 ppm, preferably does not exceed 50 ppm, more preferably does not exceed 5 ppm. As used herein, the term "non-micellarized" refers to micelles (facilitating the transport of water-insoluble substances through the aqueous phase under the conditions used to store the stabilized dispersion. Is intended to mean a surfactant that does not form The method of the invention generally involves storing the stabilized dispersion, for example after packaging in a closed container. The conditions for storage can be any conditions appropriate for the particular dispersion and water-insoluble material, but can generally be ambient. The tendency of surfactants to form micelles increases with surfactant concentration. The point at which micelles are formed is known as the critical micelle concentration (CMC). To find the CMC for a particular surfactant, the surface tension of the surfactant is plotted against the log of its concentration. Surfactants that readily form micelles, such as monomeric anionic and non-ionic surfactants, typically have a specific concentration (CMC) of that surfactant at which surface tension is reduced. Up to a very rapid decrease in surface tension with concentration. Such a plot is shown in FIG. 1, which is a plot of surface tension versus log concentration of ethoxylated alcohol surfactant (indicated as “◆”) and polyvinyl alcohol (indicated as “■”). 10 ethoxylated alcohols ^-2.5 It can be seen that micelles are formed at concentrations of w / w% and above. In contrast, the curve for PVA shows a gradually decreasing surface tension with concentration without a clear change in behavior, indicating that no micelles are formed. A simple plot of surface tension versus concentration can therefore be performed to determine if a surfactant forms micelles under the concentrations and conditions used in the formulation. Most surfactants appear to be "micellar" under essentially all practical conditions of use, and are therefore unsuitable. Examples of such surfactants are fatty alcohol ethoxylates (alkoxylates), fatty acid esters (and alkoxylates of fatty acid esters), alkoxylated amines, ethylene oxide-propylene oxide copolymers, fatty acid alkoxy as used in WO 95/07614. Nonionic surfactants such as acrylates (PAG esters, especially PEG esters), tall oil and rosin ester alkoxylates, alkylphenol alkoxylates, substituted phenolalkoxylates; dodebenzenesulfonic acid and its salts, alkyl sulfates, phosphorus Anionic surfactants such as nonionic alkoxylates that are oxidized or sulfated to yield the corresponding phosphate esters or ether sulfates, respectively. Beauty including cationic surfactants such as cetyltrimethylammonium chloride. Other micellizing surfactants can be found in the work of references such as "McCutcheons Emulsifiers &Detergents". Clearly, a balance exists between the emulsifying effect and the tendency to form micelles, both of which increase with surfactant concentration. It can be recognized that there is a group of surfactants that have some stabilizing effect but are not preferred between the preferred and unsuitable surfactants. Surfactants that form micelles under process conditions may be used, provided that they do not form micelles under storage conditions. This is because crystallization generally occurs during storage. As indicated above, "non-micellarized surfactants" are those capable of stabilizing the dispersed microcapsules so that they remain in the dispersion upon extended storage. Without wishing to be bound by theory, the surfactant in question impedes the transport of water-insoluble substances through the aqueous phase, thereby reducing the likelihood of nucleation and subsequent crystallization of said substances. Can be considered. In contrast, surfactants that have the unwavering ability to form micelles are believed to enhance transport of water-insoluble materials through the aqueous phase, resulting in crystallization. In principle, any surfactant which has a sufficient emulsifying effect when used at a concentration below its critical micelle concentration can be used. In practice, suitable surfactants tend to be polymeric surfactants having a relatively high molecular weight, for example, a weight average molecular weight of at least 10,000. Lignosulfates having a weight average molecular weight of at least 2,000 are also suitable. Preferred stabilizing surfactants are poly (vinyl pyrrolidone), copoly (vinyl alcohol / acetate) PVA, copoly (vinyl pyrrolidone / acetate), copoly (vinyl pyrrolidone / acetate / alcohol), copoly (acrylic acid / grafted polyethylene oxide) ), Copoly (alkyl (meth) acrylate), lignosulfonate, copoly (maleic anhydride / methyl vinyl ether), copoly (maleic anhydride / diisobutylene), carboxylated PVA, poly (styrenesulfonate), poly (alkylcellulose) or Poly (carboxyalkylcellulose). A particularly preferred surfactant is polyvinyl alcohol (PVA). The aqueous dispersion of the present invention can be packaged in a closed container for shipping and transportation purposes. In a preferred embodiment, the stabilizing surfactant is added prior to the polymerization step, and more preferably, prior to the emulsification step. Particle size (vmd) can be measured, for example, using a laser diffraction instrument, such as a Malvern Mastersizer ™. The term "water-insoluble substance" as used herein means a substance having a solubility in water not exceeding 100 ppm, more preferably not exceeding 50 ppm, more preferably still not exceeding 5 ppm. . The polymerizable substance is preferably polymerized by an interfacial reaction, and most preferably an interfacial condensation reaction. In a preferred embodiment, the polymerizable substance is a polyisocyanate that is polymerized by a condensation reaction with a polyamine. Alternatively, the polymerizable substance may be a crosslinkable substance that is used to coat the emulsion particles by a coacervation method and is subsequently crosslinked to form microcapsules. Both interfacial and coacervation methods involve either the production of an oil-in-water emulsion, followed by a condensation reaction at the oil / water interface that results in a polymer film or the production of a coacervate that can then be deposited on the oil interface, and then a variety With the formation and curing of the thin film, which can occur by various methods. The condensation reaction can be, for example, a multi-component reaction between, for example, an acid chloride and a polyamine isocyanate and a polyamine, an isocyanate and a polyhydric alcohol, or a mixture thereof. Coacervates can be formed by any of the methods taught in the art, for example, using gelatin / gum arabic. The microcapsules according to the invention are solutions or melts containing water-insoluble substances (eg pesticides), preferably PVA (as an aqueous solution) which enhances the formation of microcapsules, and one of the substances for forming microcapsules. It can be made by high shear mixing of a species (eg, a polymerizable material, such as an isocyanate or a crosslinkable material). PVA acts as an emulsifier, and in some systems no additional emulsifier may be required. However, in order to produce the desired emulsion of small particle size, it is desirable to add an additional emulsifier, which may be of a generally known type, provided that the emulsifier is defined herein. Does not form micelles). If the size of the emulsion is as desired, other polymeric crosslinkers are added to complete the interfacial polycondensation (eg, polyamines). As indicated above, the preferred reactant for polycondensation is a polyamine, which is typically a water-soluble reactive polyamine such as diethylenetriamine or tetraethylenepentamine. These amines begin to react with the isocyanate at the interface as soon as they are added to the emulsion. More complete control can sometimes be achieved by using either a water-soluble or a fat-soluble amine salt dissolved in the aqueous or oil phase, respectively, at an early stage of the process (eg, prior to emulsification). Due to the fact that they are salts, they do not react immediately with isocyanates, but do so immediately if the pH is adjusted to release the free amine, whereby crosslinking takes place. High shear mixing may be performed on a batch of material or may be performed continuously (in-line). In the former case, the time of addition or release of the reactive amine is determined by the processing time required to form an emulsion with the correct particle size distribution (clearly dependent on batch size). While in the latter case the interfacial reaction can be better controlled. The amine can be added / released at any desired time simply by choosing the injection point in the process stream, thus giving essentially complete control over the urea / urethane ratio. In a preferred embodiment, an additional non-micellarized surfactant is provided in the aqueous dispersion. The dispersion may also preferably contain an antifreeze, for example ethylene glycol or propylene glycol. The water-insoluble substance is preferably a pesticidal substance. The term "pesticides" includes but is not limited to insecticides, miticides, herbicides and fungicides. Suitable insecticides are: acrinatrine alletrin α-cypermethrin amitraz azinphosethyl azinphosmethylbenfracarb benzoximate β-cypermethrin β-cyfluthrin bifenthrin binapacrylbioarethrin bioallethrin S bioresmethrin bioresmethrin bromophos bromobutyprobutyrate Carboxin camda cyhalothrin chlordimeformol chlorofenvin phosfluflurazuron chlormefos chlorobenzylate chlorofoxime chloropropylischlorpyrifos methyl cyanophos cycloprotrin cyfurthrin cyhalothrin cypermethrin cyphenothrin deltamethrin dimethone dimethone-S-methyldicroton Benzafos dioxacarb disulfoton edifenphos empentrine endosulfan EPN ethiofencarb esfenvalerate etoprofosetofenprox ethrimphos fenamiphosfenazaquine fenitrothion fenobcarbbufenpropatrin fenthiocarb fenthionfenvalerate flucitrinate flufenoxuron-H Muron hydroprene isofenphos isoprocarbisoxathione malathion mephosphoranemethidathion methoprene methoxychlormevinphos N-2,3-dihydro-parathionmethyl 3-methyl-1,3-thiazol-2-ylidene-2,4-xylidenepermethrin Phenothrin Fentate Phosphorone Phosphorane Phosmet Mifosethyl pirimiphosmethyl profenphospromecarb propaphos propargite propetanfos pyraclophos quinalphosmethrin τ-fulvalinate tefluthrin tefluthrin temephos telbu hostel bufos tetrachlorinphos tetrachlorinphostetradione tetramethrin tralomethrin tralomethrin tralomethrin tralomethrin Liazophos xylylcarb. Suitable fungicides are azaconazole benalaxyl vitellanol bupyrimate carboxin cyproconazole diphenoconazole dimethomorph diniconazole jitarine phos dodemorph dodine epoxyconazole ethoxyquin etodiazole fenarimol fenpropidine fenpropimorph fluchloraline flucilazole imibenazole Microbutanil Microbutanyl nuarimol oxycarboxin penconazole prochlorazpropiconazole pyrifenox tebuconazole tetraconazole tolclofosmethyl triadimefon triadimenol tridemorph triflumizole. Suitable herbicides are 2,4-D esters 2,4-DB esters acetochloraclonifene alachlor anilofosbenfluralin benfresate venslide benzoylpropethyl biphenox bromoxynil bromoxynil esters butachlor butamifosbutralin Butyrate Carbetamido Chloronitrofen Chlorprofam Synmethylinthretodim Cromazone Clopyralid Esters CMPP Esters Cycloate Cycloxydimesmedipham Dichlorprop Esters Dichlop Methyl Diethathyl Dimetachlor Dinitramine Etalfluralin Ethofumesate Fenobucapfeno Ethyl fluazifop fluazifop-P fluchloralin flufenoxime flumetralin flumetrali Fluorodiphene Fluoroglycol Fluoroxypyrphenethyl Ester Esters Fluecol Butyl Fluorochlorin Halooxyfop Ethoxyethyl Haloxopmethyl Ioxynil Esters Isopropalin MCPA Esters Mecoprop-P Esters Metrachlormonalide Napropamide Nitrophenoxadiazon Oxyfluorfen Pendi Metallin phenissofam phenmedifam picloram esters pretilachlor profluralin propachlorpropanyl propaxafopyridate quizalofop-P triclopyr esters tridifen trifluralin. Particularly suitable pesticides are chlorpyrifos and trifluralin. Aqueous dispersions may include additional pesticides for those contained in the microcapsules. This additional pesticide may be present in the solution in the form of emulsion particles as a solid dispersion or may be contained within microcapsules. In a second aspect of the present invention there is provided a storage-stable aqueous dispersion of a water-insoluble substance, wherein the water-insoluble substance has a volumetric particle size not exceeding 6 μm, preferably not exceeding 5 μm, more preferably not exceeding 2 μm. Contained in the form of a supersaturated solution or supercooled melt in microcapsules having an average value of the diameter, the aqueous dispersion additionally comprising a non-micellarized surfactant for stabilizing the dispersion; Also, the stabilized dispersion is essentially free of a micellizing surfactant. Preferred non-micellarized surfactants are described above. The water-insoluble material (preferably a pesticide as described above) preferably comprises at least 50%, and most preferably at least 70%, by weight of the aqueous dispersion. When in a supersaturated solution (such as in xylene or any other suitable solvent known in the art), the amount of the substance is preferably at least 70% by weight of the solution, most preferably at least 80% by weight of the solution. %. The aqueous dispersion may include additional pesticides and / or additional surfactants as described above. The aqueous dispersion can be provided in a closed container. In a third aspect of the present invention there is provided the use of a non-micellarized surfactant (as described above) for inhibiting the crystallization of an aqueous dispersion containing a water-insoluble substance, comprising The insoluble substances are present in the dispersion in the form of microcapsules containing said substances as supersaturated solutions or supercooled melts. In a further aspect of the invention there is provided a method of controlling or eradicating a disease, comprising diluting an aqueous dispersion as described above to a pesticidally effective concentration, and dispersing the resulting dispersion. Comprising applying the body without any intervening spray-drying steps to the site where the disease or condition is to be specifically controlled. As indicated above, the method of the invention is particularly advantageous for the production of microcapsules having a small particle size, for example a VMD of 6 μm or smaller, preferably 2 μm or smaller. The main advantage of such small capsules is that as VMD is reduced, it is possible to retain most of the supercooled / supersaturated active ingredient in liquid form. Thus, it is possible to produce liquid core capsules in a reliable manner with minimal use of solvents, which in turn gives environmental benefits as well as higher active ingredient loading in the final product. In addition, such small capsules provide a larger surface area to mass ratio than larger particles, and thus provide an enhanced release rate and better blow. Yet another advantage of such small capsules is that they can penetrate the soil or surface grass humus layer better than the larger capsules, and thus, in certain applications where mobility of such soil or humus layer is required. Is more efficient. The presence of a liquid nucleus in a capsule made with the supercooled molten active ingredient has several advantages, the most important of which in the context of the present invention is that the nucleus does not crystallize and therefore the capsule Which can lead to both premature release and formulation instability on storage. A second advantage is that liquid nuclei can generally release their active ingredients more quickly than solids can. This, combined with the small particle size, gives a significant increase in the release rate of the active ingredient. A third advantage of keeping the active ingredient in a liquid state is the possibility of producing biologically smaller active polymorphs during crystallization, i.e. another US Pat. No. 5,160,530 (Griffin). There is no problem dealt with by the method. Any water-insoluble solvent can be used to dissolve the water-insoluble material in the manufacture of microcapsules, if a solvent is deemed desirable. The use of such solvents reduces the tendency of the material to crystallize. Examples of typical solvents are aromatic solvents, especially alkyl-substituted benzenes, such as the xylene or propylbenzene fraction, and mixed naphthalene and alkylnaphthalene fractions; mineral oils; kerosene, dialkylamides of fatty acids, especially caprylic acid. Dimethyl amides of fatty acids such as dimethyl amide; chlorinated aliphatic and aromatic hydrocarbons such as 1,1,1-trichloroethane and chlorobenzene; n-butyl, ethyl or methyl ether acetate of diethylene glycol; Esters of glycol derivatives such as methyl ether acetate, ketones such as isophorone and trimethylcyclohexanone (dihydroisophorone), and acetates such as hexyl or heptyl acetate. It is the product. Preferred organic liquids are the xylene, propylbenzene fraction, the alkyl acetate and the alkyl naphthalene fraction. Materials that are usually solid at ambient temperature but are capable of forming a eutectic with water-insoluble materials may be used. The use of such materials can generally reduce the tendency of water-insoluble materials to crystallize. A further advantage of the encapsulation method according to the invention is that it allows the production of an aqueous composition containing two or more active ingredients, wherein the substance is prepared by direct formulation of the substance. (I.e., without encapsulation of one or both of them) appears to lead to products that are chemically or physically unstable. In one aspect, the active ingredients can be separately encapsulated, however, in an alternative and preferred embodiment, one or more active ingredients (or some portion of a single active ingredient) are in accordance with the invention. The equilibrium can be encapsulated by the method described above, and the balance is not encapsulated, for example, merely dispersed in the aqueous phase. Thus, the unencapsulated active ingredient is immediately bioavailable upon application, while the encapsulated substance is released more slowly. The amount of each substance used in these different forms can vary depending on the particular application, but in general circumstances, each such substance will contain a total of 0. 1 to 99. Can constitute up to 9% by weight. The compositions of the present invention may also include stabilizers of the type disclosed in WO 95/07614. Other conventional additives such as emulsifiers, dispersants, and film-forming polymers can also be incorporated into the formulation (although such additives do not form micelles under storage conditions). A number of preferred embodiments of the present invention are described in the following examples. The following materials were used in the examples. Trade name Material properties Atlox 4913 Nonionic surfactant Solvesso 200 Aromatic solvent Sopropan T-36 Anionic copolymer Voranate M-220 Isocyanate boranate M -229 Isocyanate PAPI 135 Isocyanate Hivis 30 Poly (isobutylene) Hyvis04 Poly (isobutylene) Goherseran L-3266 Anionically modified PVA Morwet EFW Anionic surfactant Ingredient blend Gohsenol GH20 88% hydrated PVA, high molecular weight Gohsenol GL05 88% hydrated PVA, medium molecular weight Gohsenol GL03 88% hydrated PVA, low molecular weight Example 1: 50 ° C. The molten chlorpyrifos (615 g) was added to PAPI 135 (30 g). Mixed and was emulsified at 50 ° C. in water 4 60 g containing 10g of Gohsenol (Gohsenol) GH20 (aqueous PVA solution) and 10g of Gohsenol (Gohsenol) GL05 (aqueous PVA solution). This gave a vmd emulsion of about 2 μm. To this was added a solution of diethylenetriamine (10 g), Atlox 4913 (20 g) in water (70 g) to produce an encapsulated product containing about 600 g / l chlorpyrifos. The product did not show significant crystallization after two weeks of storage. Comparative examples made by emulsification of the same amount of chlorpyrifos in the same surfactant solution but without encapsulation crystallized on standing at laboratory temperature. Example 2 Trifluralin (615 g) melted at 50 ° C. is mixed with PAPI 135 (30 g), and then mixed with 50 g of 365 g water containing 10 g of Gohsenol GH20 and 10 g of Gohsenol GL05. And emulsified. An emulsion of about 3 μm v md was obtained. To this was added a solution of diethylenetriamine (10 g), Atlox 4913 (20 g) in water (70 g) to produce an encapsulated product containing about 600 g / l of trifluralin. The product did not show significant crystallization after two weeks of storage. Comparative examples made by emulsification of the same amount of trifluralin into the same surfactant solution crystallized on standing overnight at laboratory temperature. Example 3 The composition of Example 2 was repeated, but with about 1. Emulsified at 5 μm and diluted to 500 g / l. This product also did not show significant crystallization after two weeks of storage. Example 4 Chlorpyrifos (615 g) melted at 50 ° C. is mixed with PAPI 135 (30 g) and placed at 50 ° C. in 440 g of water containing 10 g of Gohsenol GH20 and 10 g of Gohsenol GL05. And emulsified. About 2. A 5 μm vmd emulsion resulted. To this was added a solution of diethylene triamine (10 g) and Atlox 4913 (20 g) in water (70 g) to give about 1. An encapsulated product containing about 600 g / l chlorpyrifos having a particle size of 29 μm was prepared. The product did not show significant crystallization after two weeks of storage. Example 5: Chlorpyrifos (615 g) melted at 50 ° C. is mixed with PAPI 135 (30 g) and dioctyl phthalate (50 g) and contains 10 g of Gohsenol GH20 and 10 g of Gohsenol GL05 Emulsified at 50 ° C. in 380 g of water. About 1. A 4 μm vmd emulsion resulted. To this was added a solution of diethylene triamine (10 g) and Atlox 4913 (20 g) in water (70 g) to give about 1. An encapsulated product containing about 600 g / l chlorpyrifos having a particle size of 38 μm was prepared. The product did not show significant crystallization after two weeks of storage. Example 6: Chlorpyrifos (462 g) melted at 55 ° C. is mixed with Voronate M-220 (32 g) and 40 g of Poval 203 (88% supplied by Kura ray) Emulsified at 50 ° C. in 400 g water containing hydrated PVA). About 1. An 84 μm vmd emulsion resulted. To this was added a solution of diethylenetriamine (8 g) in water (98 g) to produce an encapsulated product containing about 46% w / w chlorpyrifos. The product did not show significant crystallization after two weeks of storage. Example 7: Chlorpyrifos (615 g) melted at 45 ° C. is mixed with PAPI 135 (10 g) and 45 ° C. in 440 g of water containing 10 g of Gohsenol GH20 and 10 g of Gohsenol GL05. And emulsified. About 1. A 4 μm v md emulsion resulted. This was added to diethylene triamine (3. 5 g) and a solution of Atlox 4913 (20 g) was added to form about 1. An encapsulated product containing about 600 g / l chlorpyrifos having a particle size of 4 μm was prepared. The product did not show significant crystallization after two weeks of storage. Example 8: Chlorpyrifos (615 g) melted at 45 ° C. is mixed with PAPI 135 (20 g) and 50 ° C. in 440 g of water containing 10 g of Gohsenol GH20 and 10 g of Gohsenol GL05. And emulsified. About 1. A 4 μm vmd emulsion resulted. To this was added a solution of diethylene triamine (7 g) and Atlox 4913 (20 g) in water (79 g) to give about 1. An encapsulated product containing about 600 g / l chlorpyrifos with a particle size of 4 μm was prepared. The product did not show significant crystallization after two weeks of storage. Example 9: Chlorpyrifos (615 g) melted at 45 ° C. is mixed with PAPI 135 (10 g) and 45 ° C. in 440 g of water containing 10 g of Gohsenol GH20 and 10 g of Gohsenol GL05. And emulsified. About 1. A 4 μm vmd emulsion resulted. To this was added a solution of tetraethylene pentamine (3 g) in water (70 g) and Atlox 4913 (20 g) to give about 1. An encapsulated product containing about 600 g / l chlorpyrifos having a particle size of 4 μm was prepared. The product did not show significant crystallization after two weeks of storage. Example 10: Chlorpyrifos (615 g) melted at 50 ° C. is mixed with PAPI 135 (20 g) and Solvesso 200 (200 g) and added to 390 g of water containing 20 g of Atlox 4991 Emulsified at 50 ° C. About 1. A 5 μm vmd emulsion resulted. To this was added a solution of diethylenetriamine (7 g) and Atlox 4913 (20 g) in water (130 g) to give about 1. An encapsulated product containing about 45% w / w chlorpyrifos having a particle size of 5 μm was prepared. The product did not show significant crystallization after two weeks of storage. Comparative examples made by emulsification of the same amounts of chlorpyrifos and Solvesso 200 in the same surfactant solution but without encapsulation crystallized upon storage at laboratory temperature. Example 11: Chlorpyrifos (615 g) melted at 45 ° C. is mixed with PAPI 135 (30 g) and 20 g of a 10,000% molecular weight 10,000% hydrated polyvinyl alcohol (PVA) and 20 g of Atlox 4913 Was emulsified at 45 ° C. in 430 g of water containing About 1. A 65 μm vmd emulsion resulted. To this, a solution of diethylenetriamine (10 g) in water (70 g) was added to give about 1. An encapsulated product containing about 600 g / l chlorpyrifos having a particle size of 63 μm was prepared. The product did not show significant crystallization after 4 weeks of storage. Example 12: Trifluralin (462 g) melted at 50 ° C. was mixed with PAPI 135 (7. 4g) and emulsified at 50 ° C. in 430 g of water containing 60 g of polystyrene sulfonate (sodium salt). This gave a vmd emulsion of about 6 μm. To this, add diethylenetriamine (2. 5 g) of the solution was added to produce an encapsulated product containing about 45% w / w trifluralin. The product did not show significant crystallization after two weeks of storage. Comparative examples made by emulsification of the same amount of trifluralin into the same surfactant solution crystallized on standing overnight at laboratory temperature. Example 13: Trifluralin (515 g) melted at 50 ° C. was mixed with PAPI 135 (8. 2g) and emulsified at 50 ° C. in 380 g of water containing 67 g of polystyrene sulfonate (sodium salt). This gave a vmd emulsion of about 4 μm. To this, add diethylenetriamine (2. 7g) was added to produce an encapsulated product containing about 45% w / w trifluralin. The product did not show significant crystallization after two weeks of storage. Comparative examples made by emulsification of the same amount of trifluralin into the same surfactant solution crystallized on standing overnight at laboratory temperature. Example 14: Chlorpyrifos (615 g) melted at 50 ° C was mixed with PAPI 135 (10 g) and emulsified at 50 ° C in 450 g of water containing 80 g of polystyrene sulfonate (sodium salt). About 4. A 2 μm vmd emulsion resulted. To this, add diethylenetriamine (2. 7 g) was added to produce an encapsulated product containing about 50% w / w chlorpyrifos. The product did not show significant crystallization after two weeks of storage. Example 15: Chlorpyrifos (615 g) melted at 50 ° C was mixed with PAPI 135 (10 g) and emulsified at 50 ° C in 450 g of water containing 125 g of PVP K-30. About 1. A 49 μm vmd emulsion resulted. To this, add diethylenetriamine (2. The solution of 7 g) was added to produce an encapsulated product containing about 50% w / w chlorpyrifos. The product did not show significant crystallization after two weeks of storage. Example 16: Chlorpyrifos (615 g) melted at 50 ° C. is mixed with PAPI 135 (10 g) and Hyvis 30 (30 g) and 450 g containing 100 g Sopropon T-36 Emulsified in water at 50 ° C. About 1. A 2 μm vmd emulsion resulted. To this, add diethylenetriamine (2. 5 g) was added to produce an encapsulated product containing about 50% w / w chlorpyrifos. The product did not show significant crystallization after two weeks of storage. Example 17: Chlorpyrifos melted at 50 ° C. is mixed with Voronate M-220 (20 g) and emulsified at 50 ° C. in 550 g of water containing 100 g of Sopropon T-36. did. About 1. An 8 μm vmd emulsion resulted. To this was added a solution of diethylenetriamine (5 g) in water (100 g) to produce an encapsulated product containing about 47% w / w chlorpyrifos. The product did not show significant crystallization after two weeks of storage. Example 18: Chlorpyrifos (615 g) melted at 50 ° C was mixed with Voronate M-220 (30 g) and emulsified at 50 ° C in 400 g of water containing 40 g of Gohsenol GL03. . About 1. An 84 μm emulsion resulted. To this, a solution of diethylenetriamine (10 g) in water (120 g) was added to add about 51. An encapsulated product containing 5% w / w chlorpyrifos was prepared. The product did not show significant crystallization after two weeks of storage. Example 19: Chlorpyrifos (615 g) melted at 50 ° C. is mixed with Voronate M-220 (10 g) and contains 20 g of Gohsenol GL03 and Morwet EFW (5 g). And emulsified at 50 ° C. in 300 g of water. About 1. A 7 μm vmd emulsion resulted. To this was added a solution of diethylenetriamine (3 g) in water (250 g) to produce an encapsulated product containing about 51% w / w chlorpyrifos. The product did not show significant crystallization after two weeks of storage. Example 20: Chlorpyrifos methyl (42g) was dissolved in methyl oleate (20g) at 35 ° C and then added to 3g of Voronate M-22. This oil phase is emulsified in 40 g of water containing 4 g of Gohsenol GL03 at about 35 ° C. for about 2. A 4 μm vmd emulsion resulted. To this, 1 g of diethylenetriamine in 10 g of water was added to produce an encapsulated product containing about 35% chlorpyrifosmethyl (about 53% encapsulated oil). Example 21: Chlorpyrifosmethyl was dissolved at 35 ° C in Solvesso 200 (20 g) and then added to 3 g of Voronate M-229. This oil phase is emulsified at 40 ° C. in 40 g of water containing 4 g of Gohsenol GL03 at about 35 ° C. for about 1. A 9 μm emulsion resulted. To this, 1 g of diethylenetriamine in 10 g of water was added to produce an encapsulated product containing about 35% chlorpyrifosmethyl (about 53% encapsulated oil). Example 22: Chlorpyrifosmethyl (42 g) was dissolved in Solvesso 200 (20 g) and Hyvis 30 (3 g) at 35 ° C. and then added to 3 g of Voronate M-229. . This oil phase is emulsified in 40 g of water containing 4 g of Gohsenol GL03 at about 35 ° C. for about 2. A 25 μm vmd emulsion resulted. To this, 1 g of diethylenetriamine in 10 g of water was added to produce an encapsulated product containing about 34% chlorpyrifosmethyl (about 55% encapsulated oil). Example 23: Chlorpyrifosmethyl (42 g) was dissolved at 35 ° C in Solvesso 200 (20 g) and then added to 1 g of Voronate M-229. This oil phase is emulsified in 40 g of water containing 4 g of Gohsenol GL03 at about 35 ° C. for about 2. A 98 μm vmd emulsion resulted. To this, 0 g in 10 g of water. 33 g of diethylenetriamine were added to produce an encapsulated product containing about 35% chlorpyrifosmethyl (about 53% encapsulated oil). Example 24: Chlorpyrifosmethyl (42 g) was dissolved at 35 ° C. in Solvesso 200 (20 g) and then added to 1 g of Voronate M-229. This oil phase is emulsified at 40 ° C. in 8 g of Gohsenol GL03 at about 35 ° C. at about 35 ° C. This gave a 69 μm vmd emulsion. To this, 0 g in 10 g of water. 33 g of diethylenetriamine were added to produce an encapsulated product containing about 35% chlorpyrifosmethyl (about 55% encapsulated oil). Example 25: Chlorpyrifosmethyl (42 g) was dissolved at 35 ° C. in Solvesso 200 (20 g) and then added to 1 g of Voronate M-229. This oil phase is emulsified in 40 g of water containing 6 g of Gohsenol GL03 at about 35 ° C. for about 1. A 38 μm vmd emulsion resulted. To this, 0 g in 10 g of water. 33 g of diethylenetriamine were added to produce an encapsulated product containing about 35% chlorpyrifosmethyl (about 55% encapsulated oil). Samples from Examples 20-25, all stored at −5 ° C. for 2 weeks, showed no crystallization, while emulsions made from the same oil and water phase were typical of supersaturated oil phases. Crystallization was indicated. Example 26: Chlorpyrifos (300 g) and Lindane (120 g) were dissolved in trimethylcyclohexanone and Solvesso 100. 67 g of this oil phase was mixed with PAPI 135 (20 g). This was emulsified in 300 g of water containing Anonaid HF (10 g) and Atlox 4991 (20 g) to give about 0. A 62 μm vmd emulsion resulted. To this was added 7 g of diethylenetriamine and 30 g of Atlox 4913 in 150 g of water to produce a product containing 300 g / l chlorpyrifos and 120 g / l lindane. The product was stored at -5 ° C for one week and then tested by dilution into cold water (5 ° C) and passing through a 45 μm sieve. No crystals were observed. Parallel testing with emulsions made by the same route resulted in significant crystallization of both chlorpyrifos and lindane over the same period. Example 27: Melted chlorpyrifos (480 g) is mixed with Voronate M-220 (25 g), Solvesso 200 (107 g) and Hyvis 04 (25 g), and 50 g of gohsenol (Gohsenol) emulsified in 400 g of water containing GL03. About 1. A 64 μm vmd emulsion resulted. To this was added a solution of diethylene triamine (18 g) and propylene glycol (40 g) in water (100 g total) to produce an encapsulated product containing about 480 g / l chlorpyrifos. The product did not show significant crystallization after two weeks of storage. Example 28: Melted chlorpyrifos (480 g) is mixed with Voronate M-220 (25 g), Solvesso 200 (107 g) and Hyvis 04 (25 g), and 45 g of gohsenol (Gohsenol) GL03 and 30 g of Gohseran L-3266 were emulsified in 400 g of water. About 0. An 82 μm vmd emulsion resulted. To this was added a solution of diethylenetriamine (18 g) and propylene glycol (40 g) in water (100 g total) to produce an encapsulated product containing about 480 g / l chloropyrifos. The product did not show significant crystallization after two weeks of storage. Example 29: Trifluralin as eutectic (55. 9g) and etalfluralin (11. 3g) at 40 ° C and 7. 5 g of methylene diisocyanate was added to it. This oily phase is combined with sodium polyacrylate (1. 5g) was added to water (60g) at 40 ° C with high shear. A vmd emulsion of approximately 5 μm resulted. Add water (8. Diethylenetriamine (5 g) in 5 g) was added. The mixture was stirred at 40 ° C. for 30 minutes. The capsules produced were storage stable.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, L U, MC, NL, PT, SE), OA (BF, BJ, CF) , CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, S D, SZ, UG, ZW), EA (AM, AZ, BY, KG) , KZ, MD, RU, TJ, TM), AL, AM, AT , AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, F I, GB, GE, GH, HU, IL, IS, JP, KE , KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, M X, NO, NZ, PL, PT, RO, RU, SD, SE , SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (72) Inventors Banks, Graham             Oxon S7 UK             Ruen Huarlindon Uwinton             Craven Common 12 (72) Inventor Smith, Geofree William             Oxon S7 UK             -N. Farringdon, Backland             New Road 5 Wisteria Cottage (72) Winkle, Joseph Raymond             46260 Inns in Indiana, United States             Dianapolis Kenwood Court 110 (72) Inventors Uziek, Dennis Jioji             46077 Zai, Indiana, United States             Onsville Oakland Drive 9970 (72) Inventors Bousier, Raymond Everett, J             Unia             46240 Inns in Indiana, United States             Dianapolis Haverhill Drive 2934

Claims (1)

[Claims] 1. A method for producing a storage-stable aqueous dispersion of a water-insoluble substance, comprising: Emulsify the non-aqueous phase containing the solution or melt of Forming emulsion particles having a median diameter of the particles, and conducting the polymerization process to form the emulsion particles Forming an aqueous dispersion of microcapsules from Wherein the capsule is contained therein in the form of a supersaturated solution or a supercooled melt. With a water-insoluble substance and secure the dispersion with a non-micellarized surfactant. Wherein the stabilized dispersion is a micellar surfactant The above-mentioned production method, which is essentially free of an agent. 2. The method of claim 1, comprising storing the stabilized dispersant. . 3. 2. The method of claim 1, further comprising the step of packaging said aqueous dispersion in a closed container. Or the method according to claim 2. 4. Any of the preceding claims wherein the median volume particle size does not exceed 5 μm The method according to any one of the above. 5. 5. The method according to claim 4, wherein the median volume particle size does not exceed 2 [mu] m. 6. Any of the preceding claims, wherein a surfactant is added prior to the polymerization step. The method according to claim 1. 7. Any of the preceding claims, wherein a surfactant is added prior to the emulsification step. The method according to claim 1. 8. The surfactant is a polymeric surfactant with a weight average molecular weight of at least 10,000 The method according to any one of the preceding claims. 9. When the surfactant is poly (vinylpyrrolidone), copoly (vinyl alcohol / Acetate) PVA, copoly (vinyl pyrrolidone / acetate), copoly (vinyl Pyrrolidone / acetate / alcohol), copoly (acrylic acid / grafted polyether) Tylene oxide), copoly (alkyl (meth) acrylate), lignosulfone And copoly (maleic anhydride / methyl vinyl ether), copoly (maleic anhydride) Acid / diisobutylene), carboxylated PVA, poly (styrenesulfonate) ), Poly (alkylcellulose) or poly (carboxyalkylcellulose) ). The method according to any one of the preceding claims, wherein 10. The surfactant is a lignosulfonate with a weight average molecular weight of at least 2,000 A method according to any one of claims 1 to 7. 11. Microcapsules polymerizing a polymerizable substance in an interfacial reaction, Or by coating the emulsion particles with a crosslinkable substance by a coacervation method, Any of the preceding claims, formed by subsequently crosslinking the crosslinkable substance The method according to claim 1. 12. The method according to claim 11, wherein the interfacial reaction is a condensation reaction. 13. Any of the preceding claims, wherein the water-insoluble substance is a pesticide The method according to one. 14． 14. The aqueous dispersion of claim 13, wherein the aqueous dispersion includes an additional pesticide. the method of. 15. The additional pesticide is in the form of an emulsion particle as a solid dispersion. Claim 1 which is present in a solution or contained in a microcapsule. 4. The method according to 4. 16. The preceding aqueous dispersion comprises an additional non-micellarized surfactant. A method according to any one of the preceding claims. 17． A method according to any one of the preceding claims, wherein the aqueous dispersion comprises an antifreeze. the method of. 18. Water-insoluble substances exceeding 6 μm in the form of supersaturated solutions or supercooled melts Contained in microcapsules with no median volume particle size, aqueous dispersion Additionally contains a non-micellarized surfactant to stabilize the dispersion and Of a water-insoluble substance essentially free of a surfactant in which the A storage-stable aqueous dispersion. 19. 19. The aqueous dispersion according to claim 18, which is packaged in a closed container. 20. The surfactant is a polymeric surfactant having a weight average molecular weight of at least 10,000. An aqueous dispersion according to claim 18 or claim 19. 21. When the surfactant is poly (vinylpyrrolidone), copoly (vinyl alcohol / Acetate) PVA, copoly (vinyl pyrrolidone / acetate), copoly (vinyl) Rupyrrolidone / acetate / alcohol), copoly (acrylic acid / grafted poly) Ethylene oxide), copoly (alkyl (meth) acrylate), lignosulfo Nate, copoly (maleic anhydride / methyl vinyl ether), copoly (male anhydride) Acid / diisobutylene), carboxylated PVA, poly (styrenesulfone) G), poly (alkyl cellulose) or poly (carboxyalkyl cellulose) The aqueous dispersion according to any one of claims 18 to 20, wherein the aqueous dispersion is: 22. The surfactant is a lignosulfonate with a weight average molecular weight of at least 2,000 An aqueous dispersion according to any one of claims 18 and 19. 23. 23. The method of claims 18 to 22 comprising an additional non-micellarized surfactant. The aqueous dispersion according to any one of the above. 24. 24. The method according to claim 18, wherein the water-insoluble substance is a pesticidal substance. An aqueous dispersion according to any one of the preceding claims. 25. Claims additionally comprising an additional pesticidal substance dispersed in the aqueous phase. 25. The aqueous dispersion according to item 24. 26. Water-insoluble substance contains said substance as supersaturated solution or supercooled melt Water containing water-insoluble substances present in the dispersion in the form of microcapsules Of non-micellarized surfactants to inhibit crystallization of the substance from ionic dispersions . 27. When the surfactant is poly (vinylpyrrolidone), copoly (vinyl alcohol / Acetate) PVA, copoly (vinyl pyrrolidone / acetate), copoly (vinyl) Rupyrrolidone / acetate / alcohol), copoly (acrylic acid / grafted poly) Ethylene oxide), copoly (alkyl (meth) acrylate), lignosulfo Nate, copoly (maleic anhydride / methyl vinyl ether), copoly (male anhydride) Acid / diisobutylene), carboxylated PVA, poly (styrenesulfone) G), poly (alkyl cellulose) or poly (carboxyalkyl cellulose) 27. The use according to claim 26, wherein 28. Claims 24. A method of controlling or eradicating a disease, the method comprising: Or diluting the aqueous dispersion according to claim 25 to a concentration effective for pesticidal control. The resulting dispersion should be disease or disease controlled A method comprising applying to the field that is. 29. Removing the aqueous dispersion from the container, pest control of the dispersion Dilution to an effective concentration and apply the resulting dispersion to the disease. 24 or claim 24 packaged in a closed container comprising: A method for treating a disease using the dispersion of the pesticidal substance according to box 25.