UA112631C2 - STABILIZED CHEMICAL COMPOSITION - Google Patents

Abstract

The invention relates to stabilized liquid agrochemical compositions containing liquid, aqueous dispersion concentrates containing: a) a continuous aqueous liquid phase; b) at least one dispersed, solid phase containing a dispersion of polymeric matrix particles having an average particle size of at least one micron, where the outer surfaces of the particles contain a colloidal solid and where the particles have at least one agrochemically active ingredient distributed therein.

Description

ИО0О1| The present invention relates to stabilized liquid chemical compositions, the preparation of such compositions, and the method of using such compositions, for example, to control pests or as plant growth regulators.

BACKGROUND OF THE INVENTION

I0002| Agrochemically active ingredients (agrochemicals) are often provided in the form of concentrates suitable for dilution with water. Many forms of agricultural concentrates are known, and they consist of an active ingredient and a carrier, which may include various components. Water-based concentrates are obtained by dissolving, emulsifying and/or suspending agrochemically active substances in water. Due to the relatively complex supply system of crop protection products, such formulations of concentrates can be stored for long periods and can experience extreme temperature fluctuations, high shear rates and periodic vibration during storage and transportation. Under these delivery system conditions, the potential for formulation disturbances such as, for example, flocculation, thickening, and sedimentation may increase.

ИО00О3| In some cases, it may be desirable to combine different agrochemicals in one composition, taking advantage of the additive properties of each agrochemical separately, and optionally an auxiliary agent or a combination of auxiliary agents that provide optimal biological action. For example, transportation and storage costs can be minimized by using a formulation in which the concentration of active agrochemicals is high enough to be practical and in which any desired adjuvants are incorporated into the formulation, as opposed to each being in a tank mix separately. The higher the concentration of the active agrochemical, however, the higher the probability that the stability of the composition may be disturbed or that one or more components may phase-separate. In addition, it may be more difficult to avoid formulation disruption in the presence of multiple active ingredients due to physical or chemical incompatibility of these chemicals, such as when one active ingredient is an acid, base, oily liquid, hydrophobic crystalline solid, or hydrophilic crystalline solid, and other active ingredient(s) has or have other properties.

I0004| It may also be desirable to improve the effectiveness of agrochemicals through control

From the rate of release of the agrochemical from the warehouse at the application site. In particular, it may be desirable to combine agrochemicals in the same formulation and control their release rates independently, for example in cases where the modes of action of the agrochemicals become antagonistic when both are delivered at the same rates.

І0005| In addition, sprayed tank mixes may contain a variety of chemicals and auxiliaries that may interact and alter the effectiveness of one or more of the agrochemicals incorporated therein. Incompatibilities, poor water quality, and insufficient tank mixing can result in reduced spray efficiency, phytotoxicity, and can affect equipment performance.

IO006) Aqueous polymer dispersions containing pesticides, with an average dispersed particle size of 1000 nm, obtained by the method of miniemulsion polymerization of ethylene-unsaturated monomers are known, for example, from 5 2008/0171658. A limitation of polymer dispersions of this type is that miniemulsions are stabilized by traditional surfactants and therefore have a small particle size and a higher specific surface area, which can result in rapid release of the agrochemical(s) contained therein.

I0007| Given the diverse conditions and specific situations in which agrochemical liquid concentrate formulations are stored, transported, and used worldwide, there remains a need for aqueous polymer dispersions containing agrochemicals, including water-soluble, water-dispersible, or water-sensitive agrochemicals having an average dispersed particle size of 51,000 nm and which provide additional stability benefits under at least some of these conditions and situations. There is an additional need for such high loading formulations that are stable when dissolved in water under a wide range of service conditions. There is an additional need for such warehouses that have a controlled rate of release of agrochemicals from the warehouse at the application site and that work in complex water systems and in a variety of conditions.

II0008| Similar properties are required for formulations in non-agricultural areas, e.g. for the controlled delivery of pharmaceutically active ingredients, for the controlled delivery of food flavoring additives, for the controlled delivery of dyes or pigments, for the controlled release of fragrances from cosmetic or household chemical products, or for the controlled delivery enzymes and detergents in cleaning products. In these industries and others, there is a need for the ability to obtain stable formulations of components that can be released to the target site during application.

BRIEF DESCRIPTION OF THIS INVENTION

II0009| Stabilized liquid agrochemical compositions are provided, which contain liquid aqueous dispersion concentrates, which contain: a) a continuous aqueous liquid phase; B) at least one dispersed solid phase comprising polymeric particles having an average particle size of at least one (1) micron, wherein the outer surfaces of the particles comprise a colloidal solid and wherein the particles have at least one chemical agent dispersed therein. The polymer particles are obtained either from a vulcanizable resin, or from a polymerizable resin, or from a thermoplastic polymer that hardens. In one embodiment, the colloidal solid is present in the dispersed solid phase in an amount effective to stabilize the polymer resin in the emulsion state during the method used to obtain the dispersed phase. In another embodiment, surface-active substances are used in combination with a colloidal substance in order to more flexibly control the size of polymer particles. In another embodiment, the chemical agent is solid and distributed in a dispersed solid phase, or is liquid and distributed in a dispersed solid phase. In an additional embodiment, the continuous liquid phase is water or a mixture of water and either a water-miscible liquid or a water-soluble solid. In another embodiment, the polymer particles also contain a mobile, non-crosslinking chemical such that, upon extraction of the chemical from the dispersed solid phase, it becomes porous in a manner that allows the chemical agent to diffuse out of the dispersed phase. In another embodiment, the polymers forming the polymer particles contain hydrophilic groups that hydrate under the influence of water, thereby increasing the permeability of the polymer matrix and allowing the chemical agent to diffuse from the dispersed phase. In another embodiment, the dispersed solid phase contains polymer particles obtained by curing a thermoplastic polymer resin, curing a thermosetting resin, or polymerizing a thermoplastic resin. When at least one chemical agent is an agrochemically active ingredient, the compositions according to the present invention can be used directly or diluted to control pests or as plant growth regulators. 00101 According to one embodiment of the present invention, it has been found that aqueous dispersion concentrates of agrochemically active ingredients in an aqueous liquid can be obtained using a polymerized, vulcanized or cured polymer resin to entrap the agrochemically active ingredients in a polymer matrix when a colloidal solid is used for stabilization polymer resin in the emulsion state during the curing reaction or curing method. At least one agrochemically active ingredient can be distributed in a polymer matrix that is dispersed as particles with a continuous aqueous liquid phase. Other active ingredients can optionally be dispersed, dissolved, emulsified, microemulsified or suspended in a continuous phase. 0011) The rate of release of agrochemically active ingredients from the dispersed solid phase can be controlled by the optional inclusion in the dispersed phase of mobile, non-crosslinking molecules, where these molecules are chosen to be insoluble or partially soluble in the aqueous continuous phase, miscible or immiscible with the polymer resin, which will form a polymer matrix in the form of particles, soluble in water or any other environment to which the composition will be exposed during application, and with molecular sizes such that the pores they create in the dispersed phase during extraction allow the desired release agrochemically active ingredients. The mobile, non-crosslinkable molecules may be present in the dispersed solid phase either as a molecular dispersion (if they are miscible with the polymer resin) or as discrete inclusions (if they are immiscible with the polymer resin).

I0012| The rate of release of agrochemically active ingredients from the dispersed solid phase can be additionally controlled by optional inclusion of non-porous minerals in the form of particles as a diffusion barrier to the dispersed phase. For purposes of this invention, non-porous means that the mineral lacks pores larger than the individual molecules of the agrochemically active ingredients, such that the diffusion coefficient of the agrochemical through the mineral particles is less than 1075 mg/s.

I0013) Aqueous dispersible concentrates according to this invention have an effectively long protection period of water-soluble, water-dispersible, water-sensitive and other agrochemicals in such a way that the chemical and physical stability of the composition is improved, and which provides practical value in terms of storage, transportation and application. Dispersion concentrates according to the present invention also suitably allow the combination of several active ingredients in one composition, regardless of whether they are liquids or solids, by including them separately or together in polymer matrix particles that are mutually physically compatible. Dispersion concentrates according to the present invention also provide the ability to control the rate of release of agrochemicals from the concentrate or diluted composition for final application on the target site and enhance the biological effect against the target pests.

I0014) Aqueous dispersion concentrates according to this invention have value also outside the agricultural sphere, where there is a need to obtain stable compositions and delivery of chemicals to the target area. With regard to these goals, agrochemicals can be replaced by other chemicals if necessary. In the context of the present invention, chemical agents therefore include any catalyst, adjuvant, vaccine, genetic vector, drug, flavoring agent, food flavoring agent, enzyme, spore or other colony-forming unit (CFU), detergent, dye , pigment, adhesive additive or other component that requires the release of a chemical agent from the composition. In addition, aqueous dispersion concentrates can be dried to obtain a powder or granular product as desired. 0015) Polymerizable resins that are suitable for use in obtaining a dispersed-phase hardened polymer matrix can be selected from monomers, oligomers or prepolymers that are polymerized either to thermosetting or to thermoplastic polymer particles. According to this invention, the dispersed-phase polymer matrix can be formed by dissolving the polymers in a volatile, water-immiscible solvent that also contains at least one agrochemical, stabilizing this solution in water as an emulsion

Pickering using colloidal stabilizers, and then heating this emulsion to evaporate the volatile solvent and form a dispersed solid phase of the thermoplastic polymer matrix. In addition, the dispersed-phase polymer matrix can be formed by dissolving or suspending at least one agrochemically active ingredient in an anhydrous liquid mixture containing a melt of at least one suitable thermoplastic polymer, emulsifying said dispersed concentrate to an average droplet size of 1-200 microns in a heated aqueous liquid, which also contains a colloidal solid as a stabilizer

From an emulsion (Pickering); and cooling the emulsion to produce thermoplastic polymer particles.

I0016| The present invention further relates to polymer particles containing entrapped agrochemicals which are homogeneously or heterogeneously distributed in such particles or present in the form of domains in such particles and where the outer surface regions of the particles contain a colloidal solid.

I0017| The present invention also includes a method of controlling, or controlling pests, or regulating plant growth at a location, such as soil or foliage, which comprises treating said location with a dispersable concentrate according to the present invention, or dispersing the concentrate according to the present invention in water or a liquid fertilizer and treatment of the specified location with the resulting diluted aqueous composition for final use.

DETAILED DESCRIPTION OF THIS INVENTION

I0O018) Accordingly, in one of the variants of the implementation of the composition of aqueous liquid dispersion concentrates according to the present invention contain: a) a continuous aqueous liquid phase, which optionally contains at least one chemical agent; and

BYU) at least one dispersed solid phase containing polymer particles having an average particle size of at least one micron, wherein the outer surfaces of the particles contain a colloidal solid that is present in an amount effective to stabilize the polymer particles in the emulsion state during the process used for obtaining a dispersed phase and where the polymer particles have at least one chemical agent distributed in them. 0019) In one of the variants of implementation, the chemical agents are agrochemically active ingredients. 0020) In one embodiment, the colloidal solid is a colloidal Pickering emulsion stabilizer. 0021) In one of the variants, the polymer particles contain a captured agrochemical, which is either homogeneously or heterogeneously distributed in such particles or is present in the form of domains in such particles.

I0022| In the context of this invention, the average particle or droplet size indicates a weighted average value, usually denoted O(m,0.5). bo 0023) In one embodiment, the agrochemically active ingredient is a solid substance and distributed in a dispersed solid phase or is a liquid and distributed in a dispersed solid phase. (0024) In one embodiment, the agrochemically active ingredient (AI) in the dispersed phase is water-soluble, water-dispersible or water-sensitive.

In another embodiment, dispersive concentrates for use in compositions of liquid agrochemicals according to the present invention are those that are formed using vulcanizing agents, monomers, oligomers, prepolymers or their mixtures, which exhibit a slow hardening or polymerization reaction in combination with agents vulcanization under ambient conditions Specifically, vulcanizing agents, monomers, oligomers, prepolymers or mixtures thereof are suitable which do not show a significant increase in viscosity under ambient conditions over a period of at least 15 minutes, more specifically

30 minutes, more specifically 1 hour after mixing with the vulcanizing agent. (0026) According to one embodiment of the present invention, thermosetting polymerizable resins are understood to include all molecules that can be irreversibly polymerized or vulcanized to form a polymer matrix that does not melt or deform at elevated temperatures below the point thermal decomposition. The polymerization reaction can be initiated thermally by the addition of vulcanizing chemicals or by suitable irradiation to generate radicals or ions, such as visible light, ultraviolet, microwave or other electromagnetic irradiation, or electron beam irradiation. Examples include phenolic resins, ureas, melamines, epoxies, polyesters, silicones, rubbers, polyisocyanates, polyamines, and polyurethanes. In addition, bioplastic or biodegradable thermosetting resins can be used, including epoxy or polyester resins derived from natural substances such as vegetable oil, soybean or wood, etc.

I0027| According to another embodiment of the present invention, polymerizable thermoplastic resins are understood to include all molecules that can be polymerized or vulcanized to form a polymer matrix that can melt or deform at elevated temperatures below the thermal decomposition point. The polymerization reaction can be initiated thermally with the help of adding chemicals

By vulcanization or by suitable irradiation to generate radicals or ions, such as irradiation with visible light, ultraviolet or other electromagnetic irradiation, or irradiation with an electron beam. Examples of suitable ethylenically unsaturated monomers include styrene, vinyl acetate, x-methylstyrene, methyl methacrylate, which are described in O5 2008/0171658, etc. Examples of thermoplastic polymers for polymer particles obtainable in miniemulsion polymerization of ip-5:yi include polymethyl methacrylate, polystyrene, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, polyacrylate, polyalkylacrylate, polyalkylacetate, polyacrylonitrile, or copolymers thereof. (0028) According to another embodiment of the present invention, curable thermoplastic resins are understood to include all molecules that can be dissolved in a volatile solvent such that the solvent can be evaporated with the aid of heat to create a polymer matrix that can melt or deform at elevated temperatures below the thermal decomposition point. The volatile solvent is chosen to be immiscible with the continuous aqueous phase and sufficiently volatile to be adequately extracted from the composition by heating to a temperature below that at which any significant decomposition occurs. Examples include the polymers of ethylene-unsaturated monomers described above, as well as polymers such as acetyl cellulose, polyacrylates, polycaprolactone, and polylactic acid. Also mentioned are polymethyl methacrylate, polystyrene, polyvinyl acetate, acetyl cellulose, polyacrylate, polyacrylonitrile, polyamide, polyalkylene terephthalate, polycarbonate, polyester, polyphenylene oxide, polysulfone, polyimide, polyetherimide, polyurethane, polyvinylidene chloride, polyvinyl chloride, polypropylene and waxes, etc. In addition, bioplastic or biodegradable polymers such as thermoplastic starch, polylactic acid, polyhydroxyalkanoate, polycaprolactone, polyetheramide are also suitable for use in the production of polymer particles. Examples of volatile solvents include alkanes such as hexane and heptane, aromatic solvents such as benzene and toluene, and halogenated solvents such as dichloromethane and trichloromethane. Other examples of suitable polymers and solvents are described in UMO2011/040956A1.

I00291| According to the present invention, the polymer particles of the dispersed phase have an average particle size of from 1 to 200 microns, more specifically from 1 to 100 microns and most specifically from 2 to 80 microns. bo 0030) In one embodiment, suitable polymerizable resins and polymer solutions are those that are essentially immiscible with the aqueous liquid used in the continuous phase. 0031) In the context of this invention, a colloidal solid is one whose properties of interest are determined by its surface interactions with other substances. Colloidal solids, therefore, are necessarily those with a large specific surface area, mostly more than 10 me/g. For example, colloidal solids are able to stabilize emulsions of immiscible liquids, as described, for example, in UMO 2008/030749. In serving these purposes, such colloidal solids may be called Pickering colloids, colloidal emulsion stabilizers, or other equivalent terms. Functional tests for whether a colloidal solid can stabilize an emulsion as used herein are known. One such test is described in detail in paragraph 110 below. Not all colloidal solids are capable of stabilizing an emulsion of any given pair of immiscible liquids, and such a functional test can be used by those skilled in the art to identify a suitable colloid. (0032) As noted earlier, the rate of release of agrochemically active ingredients from the dispersed solid phase can be further controlled by optional inclusion of non-porous particulate minerals in the dispersed phase as a diffusion barrier. Under certain circumstances, the same non-porous mineral in the form of particles, which is used as a diffusion barrier in the dispersed phase, can also serve as a colloidal emulsion stabilizer.

In this situation, the mineral in the form of particles can be added at two separate points in the production process, as described below - firstly, to the dispersed-phase concentrate for the purpose of inclusion in the particles of the dispersed phase, and, secondly, to the aqueous continuous phase for the purpose emulsion stabilization.

I0033) In another embodiment, the affinity of aqueous liquids suitable for use in the continuous phase a) for the agrochemically active ingredient distributed in the dispersed solid phase B) is such that all the agrochemically active ingredients essentially remain in the dispersed solid phase and essentially do not move to the continuous phase. Those skilled in the art will be able to readily determine whether a particular aqueous fluid satisfies this criterion for the particular agrochemical active ingredient in question by following any standard test procedure for determining the partition coefficient of a compound (here

From the case of an agrochemically active ingredient of the dispersed phase) between the continuous phase and the dispersed solid phase. Accordingly, the dispersed solid phase B) is immiscible with the continuous phase a).

II0034| In an additional embodiment, aqueous liquids suitable for use in the continuous phase a) are solutions of water-soluble solutes in water.

I00351| Water-soluble solutes suitable for use in the continuous phase include salts such as ammonium halides, nitrates, sulfates, carbonates, phosphates, nitrites, sulfites, nitrides, and sulfides, and metals such as those in groups 1-12 of the periodic table. Other suitable solutions include sugars and osmolytes such as polysaccharides, proteins, betaines and amino acids.

I0036| In one of the variants of the implementation, aqueous liquids suitable for use in the continuous phase a) are a mixture of water and an essentially water-miscible anhydrous liquid. In the context of this invention, the expression "substantially miscible with water" means an anhydrous liquid that forms a single phase when present in water at a concentration of at least 50 wt. Fo.

I0037| Essentially water-miscible anhydrous liquids suitable for use in the continuous phase a) include, for example, propylene carbonate; a water-miscible glycol selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having a molecular weight of up to about 800; an acetylated glycol such as dipropylene glycol methyl ether acetate or propylene glycol diacetate; triethyl phosphate; ethyl lactate; gamma-butyrolactone; an alcohol miscible with water, such as propanol or tetrahydrofurfuryl alcohol; M-methylpyrrolidone; dimethyl lactamide; and their mixtures. In one of the variants, the anhydrous, essentially water-miscible liquid used in the continuous phase a) is a solvent for at least one optional agrochemically active ingredient. 0038) In another embodiment, the aqueous, substantially water-miscible liquid used in the continuous phase a) is completely miscible with water in all parts. Alternatively, the aqueous, substantially water-miscible liquid used in continuous phase a) is a waxy solid such as polyethylene glycol having a molecular weight above about 1000, and the mixture of this waxy solid and water is maintained in a liquid state by forming composition at elevated temperature. because I0039| Those skilled in the art will appreciate that the amounts of water and the nature and amount of anhydrous water-miscible liquid or water-soluble solute can be varied to provide mixed aqueous liquids suitable for use in continuous phase a) and these amounts can be determined without undue experimentation. In one embodiment, the aqueous continuous phase contains from 5 to 95 wt. 95, preferably from 30 to 90 weights. 95 ethylene glycol in equilibrium with water. In another embodiment, the aqueous continuous phase contains from 5 to 95 wt. 96, preferably from 3 to 90 weights. 95 glycerol in equilibrium with water. 0040) In one embodiment, when the concentrate is diluted in water, some agrochemicals slowly diffuse out of the polymer matrix particles. The rate of release of agrochemicals from emulsified polymer particles in the spray tank can be adjusted, for example, by changing the size of the dispersed polymer particles in the concentrate, the concentration of the active ingredient in the polymer, the pH of the dispersion in the spray tank, optional inclusion of non-porous minerals in the form of particles (as diffusion bars eriv) to the polymer matrix and the amount and nature of thermoplastic polymers or polymerizable resin, including monomers, oligomers, prepolymers and/or hardeners used to form the polymer particles. 0041) In this regard, the dispersed phase may also include one or more mobile chemicals that do not crosslink, such that during the extraction of this chemical from the dispersed phase, it becomes porous in such a way as to allow the chemical agent to diffuse out of the dispersed phase.

The mobile chemical can be chosen in such a way that it quickly diffuses into the composition of the concentrate so that the polymer matrix becomes so porous that the agrochemical is quickly released when diluted in water. Alternatively, the mobile chemical can be chosen to be of limited solubility in the aqueous continuous phase so that the mobile chemical slowly diffuses out of the polymer matrix after the formulation has been diluted in water or applied to the target site, thereby releasing the agrochemical. essentially only at the target location. Examples include surfactants, solvents, oligomers, polymers, copolymers, acids, bases, natural or synthetic oils, natural or synthetic alcohols, substantially water-soluble compounds, or substantially water-insoluble compounds. In a particular embodiment, the mobile chemical is chosen to have limited solubility in a particular aqueous continuous phase, for example an organic acid may be chosen,

Which is essentially insoluble in an acidic aqueous continuous phase, and already after dilution in water or after application to the target area, the pH is higher than in the dispersion concentrate, so the organic acid (mobile chemical) dissolves outside the polymer matrix, making it porous and allowing to release the active ingredient. In another specific embodiment, the mobile chemical is selected such that it has limited solubility in aqueous environmental conditions, but high solubility in waxy substances such as plant cuticles, such that the mobile chemical is essentially only extracted from the matrix upon contact with the plant leaf, and the active ingredient is then released mainly only to the surface of the leaf. (0042) In another embodiment, pH-sensitive release of an active agrochemical is achieved by creating a polymer matrix with excess amino groups. During dilution, amino groups hydrate, but the rate and degree of hydration increases at lower pH. The pH during dilution in the spray tank can be controlled by incorporating the main components into the dispersed phase, but after application the pH eventually becomes neutral and the release rate increases. Alternatively, the polymer matrix is created with excess acid groups or bases other than amines. The nature of the pH sensitivity can be further adjusted by selecting acidic or basic groups with variable corresponding pKa or rkr values. 0043) In another embodiment, the release profile of the active ingredient from the dispersed phase can be modified by including cross-linking monomers that contain hydrophilic groups, so that during dilution in water, the particles of the polymer matrix hydrate and expand, thus the matrix becomes more permeable. In a specific embodiment, the crosslinking monomers are an epoxy resin based on diglycidyl ether of glycerol. In another specific embodiment, the crosslinking monomers are an epoxy resin based on diglycidyl ether of polypropylene oxide.

I0044| The mobile, non-crosslinking chemical in the dispersed phase can optionally also be chosen to function as a surface-active substance or dispersant in a liquid dispersion concentrate, which is used to obtain liquid agrochemical compositions according to the present invention. Chosen in this way, the mobile chemical will be adsorbed to the surfaces of the particles present in the dispersion concentrate, and thanks to this, the dispersion of these particles will be stabilized. This behavior can be observed at least in one of (c;

in the following ways: the particles will be distributed individually rather than as clusters in the dispersion concentrate when observed with a microscope, the viscosity of the dispersion concentrate will decrease with the addition of a mobile chemical, or the particles will have a greater tendency to remain in the dispersed phase instead of being lost in the continuous phase during the formulation of liquid agrochemicals. Examples of suitable mobile chemicals suitable for this purpose include copolymers of o-olefin and M-vinylpyrrolidone, such as alkylated vinylpyrrolidone copolymers such as Adgiteg5 (eg, Adgiteg AI-22 based on 1-ethylenehexadecyl-2-pyrrolidinone) (Ipiegpaiopai

Zresianku Rhodysiv (I5P) Sogrohaiyop), or such copolymers of o-olefin and ethylene glycol, such as, for example, Ayoch 4914 from Stod Sogr, or such organosilicon surface-active substances as zZiiimei I -77 (Motepiime Repogtapse Spetisai!5). (0045) In one embodiment, the aqueous liquid dispersion concentrate compositions according to the present invention contain a mixture of polymer particles, each of which contains one or more chemicals (such as an agrochemically active ingredient). Each of the chemicals is contained in the same or different dispersed-phase polymer particles, and each respective dispersed-phase particle does not necessarily include a different mobile chemical and/or polymer matrix as described above, so each chemical or combination of agents has a different release profile . Not necessarily, each respective solid dispersed phase may have different particle sizes. (0046) In one of the implementation options, the aqueous liquid dispersion concentrate compositions according to the present invention contain a solid phase in the form of finely dispersed, suspended polymer particles that contain a colloidal solid substance on their outer surface and that contain at least one agrochemically active ingredient, where the average particle diameter such polymer particles are generally below 200 microns, often below 100 microns, for example in the range of 1 to 200, more specifically in the range of 1 to 100 and especially in the range of 2 to 80 microns.

I0047| The term "agrochemically active ingredient" refers to chemical and biological compositions such as those described herein that are effective in killing, preventing, or controlling the growth of undesirable pests such as plants, insects, mice, microorganism,

From algae, fungi, bacteria, etc. (such as pesticide active ingredients). The term can also be applied to compounds that act as excipients to promote absorption and delivery of other active compounds. The term can also be applied to compounds that control plant growth in a desired manner (eg, plant growth regulators), to a compound that mimics the natural systemic activated resistance response found in plant species (eg, plant activators), or to a compound that reduces phytotoxic reaction to a herbicide (for example, an antidote).

Where more than one such agrochemically active ingredient is present, the agrochemically active ingredients are independently present in a biologically effective amount when diluted in the composition, if necessary, in a suitable volume of a liquid carrier, such as water, and applied to the intended target, e.g. plant leaves or its location.

II0048| Examples of agrochemical active ingredients suitable for use in continuous phase a) or dispersed phase B) according to the present invention include, without limitation: fungicides such as azoxystrobin, chlorothalonil, cyprodinil, difenoconazole, fludioxonil, mandipropamide, picoxystrobin, propiconazole, pyraclostrobin, tebuconazole , thiabendazole and trifloxystrobin; herbicides such as acetochlor, alachlor, ametryn, anilophos, atrazine, azafenidine, benfluralin, benfuresate, benzulide, benzphendisone, benzofenap, bicyclopyrone, bromobutide, bromophenoxime, bromoxynil, butachlor, butaphenacil, butamiphos, butraline, butylate, cafenstrol, carbetamide, chloridazone, chlorpropham, chlorthal-dimethyl, chlorthiamide, cinidone-ethyl, cinmethylin, clomazone, clomeprop, cloransulam-methyl, cyanazine, cycloate, desmedifam, desmethrin, dichlobenil, diflufenican, dimepiperate, dimetachlor, dimethamethrin, dimethenamid, dimethenamid-P, dinitramine, dinoterb, diphenamide, dithiopyr, ERTS, esprocarb, etalfluralin, etofumesate, ethobenzanide, fenoxaprop-ethyl, fenoxaprop-R-ethyl, fentrazamide, flamprop-methyl, flamprop-M-isopropyl, fluazolate, fluchloralin, fluphenacet, flumiclorac-pentyl, flumioxazin, flurochloridone, flupoxam, flurenol, fluridone, flurtamone, fluthiacet-methyl, indanophan, isoxaben, isoxaflutol, lenacil, linuron, mefenacet, mesotrione, metamitron, metazachlor, metabenzthiazuron, methyldimron, metobenzuron , metolachlor, metosulam, metoxuron, metribuzin, molinate, naproanilid, napropamide, neburon, norflurazon, orbencarb, oryzalin, oxadiargil, oxadiazon, oxyfluorfen, pebulate, pendimethalin, pentanochlor, petxamide, pentoxazone, phenmedipham, pinoxaden, piperofos, pretilachlor, prodiamine, profluazole , prometon, promethrin, propachlor, bo propanil, propazine, propham, propisochlor, propizamide, prosulfocarb, pyraflufen-ethyl,

pyrazogyl, pyrazolinate, pyrazoxifene, pyributycarb, pyridate, pyriminobac-methyl, quinclorac, siduron, simazine, symetryn, 5-metolachlor, sulcotrione, sulfentrazone, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutrin, tenylchlor, thiazopyr, thidiazimin, thiobencarb, thiocarbazyl, trialate, triethazine, trifluralin and vernolate; herbicide antidotes such as benoxacor, dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr; alkali metal, alkaline earth metal, sulfonic or ammonium cation of mefenpyr; mefenpyr-diethyl and oxabetrinil; insecticides such as abamectin, clothianidin, emamectin benzoate, gamma-cyhalothrin, imidacloprid, cyhalothrin and its enantiomers such as lambda-cyhalothrin, tefluthrin, permethrin, resmethrin and thiamethoxam; nematicides such as fostiazate, fenamiphos and aldicarb.

I0049| In addition, such volatile agrochemically active ingredients as those with a vapor pressure of at least 1 Pa at ambient temperature are also properly captured in the dispersed phase B). Examples of such active ingredients include volatile nematicides such as methyl bromide, methyl iodide, chloropicrin, and 1,3-dichloropropene.

II0050| In one embodiment, the active ingredients in the continuous phase may be in the form of a solution, emulsion, microemulsion, microcapsule, or particle or fine particle. In the context of this invention, a finely dispersed particle is one that is substantially smaller than the solid polymer particles of the dispersed phase, so that many (at least 10) particles of active ingredients are present in each dispersed phase particle, while a non-finely dispersed particle is such, only slightly smaller than the size of the solid polymer particles of the dispersed phase, so each polymer particle contains only a few particles of active ingredients.

I0O51| Additional aspects of the present invention include a method of preventing or controlling pest infestation of plant species and regulating plant growth by diluting an amount of the concentrate composition in a suitable liquid carrier such as water or liquid fertilizer and applying it to the plant, tree, animal or location as desired. The compositions of this invention can also be combined in a continuous flow device with water in equipment for application by spraying, so a tank for keeping the diluted product is not needed.

From I0052| Aqueous liquid dispersion concentrate compositions can be conveniently stored in a container from which they are dispensed or pumped, or into which a liquid carrier is added prior to application.

II0053| Advantages of aqueous liquid dispersion concentrate compositions according to this invention include: stability during storage for long periods, for example, months or longer at room temperature; several agrochemicals in different physical states can be conveniently combined in dispersions of compatible solid particles; release profiles of agrochemicals can be flexibly and independently controlled; users are provided with the possibility of simple handling, because the dilution is done in water or another liquid carrier to obtain mixtures for application; reduced sedimentation of the suspension during storage or dilution; the compositions can be easily resuspended or redispersed with only a slight degree of agitation and do not undergo coalescence when diluted in fertilizer solutions to obtain application mixtures.

І0054| The rate of application of a composition according to the present invention will depend on a number of factors, including, for example, the active ingredients selected for application, the identity of the pests to be controlled or the plants whose growth is to be inhibited, and the formulations selected for application and whether compound by application to leaves, soil, or application for absorption by the roots, or by application of fertilizers with irrigation water. As a general guideline, however, a suitable application rate is between 1 and 2000 g of active ingredient per hectare, more specifically between 2 and 500 g of active ingredient per hectare. 0055) In one embodiment, suitable rates of agrochemical active ingredients used in the compositions according to the present invention are compared with available rates given on modern product labels for products containing such active substances.

For example, azoxystrobin under the trade name Optsaigih? can be applied at a rate of 112 g to 224 g a.i./hectare, and a premix of azoxystrobin (75 g/l)/propiconazole (125 g/l) under the trade name Otsi mM can be applied in rate from 0.75 to 1.5 l/ha. 0056) In one of the variants of the implementation of this invention, an additional component may be present to control the pH of the water used for diluting the composition before use.

II0057| If a solid agrochemically active ingredient is present, the solid active ingredient can be ground to the desired particle size before being dispersed in a polymerizable resin (monomers, oligomers and/or prepolymers, etc.) that will form the polymer matrix particles. The solid may be ground in the dried state using an air mill or other suitable equipment as necessary to achieve the desired particle size. The particle size may be an average particle size of from about 0.2 to about 20 microns, preferably from about 0.2 to about 15 microns, more preferably from about 0.2 to about 10 microns. 0058) As used in this document, the expression "agrochemically effective amount" means the amount of an agrochemically active compound that provides negative control or modification of target pests or regulates plant growth (ROC). For example, in the case of herbicides, a "herbicidally effective amount" is that amount of herbicide that is sufficient to control or modify plant growth. Controlling or modifying effects include all deviations from natural development, such as stunting, stunting, leaf blight, albinism, stunting, etc. The term plant refers to all physical parts of a plant, including seeds, seedlings, shoots, roots, tubers, stems, petioles, leaves and fruits. In the case of fungicides, the term "fungicide" will mean a substance that stops or substantially inhibits the growth, proliferation, division, reproduction or spread of fungi.

As used herein, the expression "fungicidally effective amount" or "amount effective to control or reduce the number of fungi" with respect to a fungicidal compound is an amount that will stop or substantially inhibit the growth, proliferation, division, reproduction or spread of a significant number of fungi. As used herein, the terms "insecticide," "nematicide," or "acaricide" shall mean a substance that stops or substantially inhibits the growth, proliferation, division, reproduction, or spread of insects, nematodes, or mites, respectively. An "effective amount" of an insecticide, nematicide or acaricide is that amount which will stop or substantially inhibit the growth, proliferation, division, reproduction or spread of a significant number of insects, nematodes or mites.

I0059)| In one aspect, as used herein, "that regulates (plant) growth", "plant growth regulator", ROK, "regulatory" or "regulation" includes the following plant responses; inhibition of cell elongation, for example, reduction of stem height and internodal distance, strengthening of the stem wall, thus increasing resistance to lying;

From compact growth of ornamental plants for economically profitable production of plants with improved qualities; stimulation of better fruiting; increasing the number of ovaries with the expectation of increasing productivity; stimulation of the aging of tissue formations, which give fruits the opportunity to fall; defoliation of greenhouse and decorative bushes and trees for parcel trade of fallow; defoliation of trees to interrupt parasitic chains of infection; acceleration of ripening with a view to planning the harvest by reducing the harvest to one or two harvests and interrupting the food chain of harmful insects.

I00O60) In another aspect, "plant growth regulator", "plant growth regulator", ROC, "regulatory" or "regulation" also includes the use of a composition as defined in accordance with the present invention to increase yield and/or improving the power of the agricultural plant. According to one of the variants of the implementation of the present invention, the compositions of the present invention are used for improved resistance to such stress factors as fungi, bacteria, viruses and/or insects, and such stress factors as heat stress, biogenic stress, cold stress . the level of pressure from pests, plant condition, weather conditions and growing conditions, as well as the activity of agrochemically active ingredients ingredients and any applicable labeled dose limitations.

I0062| The present invention also relates to liquid agrochemical compositions containing a) a continuous, aqueous liquid phase, optionally containing at least one agrochemically active ingredient (for example, in a state selected from a solution or a dispersion such as an emulsion, microemulsion and/or suspension of microcapsules or finely dispersed particles); and p) at least one dispersed, solid phase containing polymer particles obtained either from a vulcanizable resin, or from a polymerizable resin, or from a thermoplastic polymer that hardens, wherein the outer surfaces of the particles comprise a colloidal solid and wherein the particles have at least one agrochemically active ingredient distributed in them.

I0063)| An additional aspect of the present invention relates to a dilute aqueous spray composition for pest control or plant growth regulation in a location that contains a) a continuous aqueous phase containing a suitable liquid carrier such as water or liquid fertilizer in an amount sufficient to obtain the desired the final concentration of each of the active ingredients in the sprayed composition; p) at least one dispersed, solid phase containing polymer particles obtained either from a vulcanizable resin, or from a polymerizable resin, or from a thermoplastic polymer that hardens, where the outer surfaces of the particles contain a colloidal solid substance and where the particles have at least one agrochemically active ingredient distributed in them; and c) optionally at least one agrochemically active ingredient dispersed, dissolved, suspended, microemulsified and/or emulsified in a liquid carrier.

I0064| In another embodiment, this invention relates to a diluted pesticide and/or

ROaV compositions for use in ultra-low volumes (SHI M), containing: a) a continuous phase, which contains a carrier-solvent having an ignition temperature above 55"С, in an amount sufficient to obtain the desired final concentration of each of the active ingredients in ОИ M-composition;

B) at least one dispersed, solid phase containing polymer particles obtained either from a vulcanizable resin, or from a polymerizable resin, or from a thermoplastic that hardens, where the outer surfaces of the particles contain a colloidal solid substance and where the particles have at least one agrochemically active ingredient distributed in them.

І0065| The present invention also relates to a method of pest control or their prevention in agricultural crops of suitable plants, or the regulation of the growth of such crops, while the specified method includes: 1) treating a desired area, such as plants, plant parts or their locations, with a concentrate composition that contains: a) a continuous aqueous liquid phase, which optionally contains at least one agrochemically active ingredient, and which also optionally contains at least one acidic or basic component; p) at least one dispersed, solid phase containing polymer particles obtained either from a vulcanizable resin, or from a polymerizable resin, or from a thermoplastic that hardens, where the outer surfaces of the particles contain a colloidal solid substance and where the particles have at least one agrochemically active ingredient distributed in them; or 2) diluting the concentrate composition, if necessary, in a suitable vehicle such as water, a liquid fertilizer, or a solvent vehicle having a flash point above 55°C, in an amount sufficient to obtain the desired final concentration of each of the active ingredients; and then treating the desired area, such as plants, plant parts or their locations, with a diluted spray or CI M composition.

I006b6| The term plant refers to all physical parts of a plant, including seeds, seedlings, shoots, roots, tubers, stems, stems, leaves and fruits. The term location refers to where the plant grows or is expected to grow.

I0067| The composition according to the present invention is suitable for all application methods traditionally used in agriculture, for example, pre-emergence application, post-emergence application, post-harvest application and seed treatment. Compositions according to this invention are suitable for pre- and post-emergence application on the area of agricultural crops.

І0068| The compositions according to the present invention are particularly suitable for the control and/or prevention of crop pests of suitable plants or for regulating the growth of such plants. Preferred suitable plant crops include canola, cereals such as barley, oats, rye and wheat, cotton, corn, soybeans, sugar beets, fruits, berries, nuts, vegetables, flowers, trees, shrubs and turf. The components used in the composition according to the present invention can be introduced in various ways, known to specialists in this field of technology, at different concentrations. The dose at which the compositions are applied will depend on the specific type of controlled pests, the degree of control required and the timing and method of application.

I0069| Crops should be understood to also include crops that have become resistant to herbicides or classes of herbicides (eg AI 5-, (35-, ERBRO5-, PPO-, ASSase and HPRO-inhibitors) through traditional breeding methods or by genetic engineering An example of a crop that has been made resistant to imidazolinones such as imazamox by conventional breeding is the cypress (canola). Examples of crops that have been made resistant to herbicides by genetic engineering methods include, for example, glyphosate- and glufosinate-resistant varieties of corn, commercially available under the brand names KoshipadirgeaduFf and GirbeguiipkF).

I0070| Agricultural crops should also be understood as those that have been made resistant to harmful insects by means of genetic engineering methods, for example Wee maize (resistant to the corn borer), Wee cotton (resistant to the cotton boll weevil) and also Wee potatoes (resistant to the Colorado beetle). Examples of Vi corn are ICF corn hybrids

VI 176 (Zupdepia Zeei5z). B toxin is a protein formed naturally by the soil bacterium Vasiyv5 Ipyhipdiepviz. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EPA-451878, EPA-374753, MO 93/07278, MO 95/34656, MO 03/052073 and EPA-427529. Examples of transgenic plants containing one or more genes that encode resistance to insecticides and that express one or more toxins are KposkKoschke (maize), Miveii SagaF (maize), Mysoip3ZZVOU (cotton), VoiYidagF (cotton), Memeakyu (potato) , MaishighedagatF and RgoiehsiaF. Both the plant crop and its seed material can be resistant to herbicides and, at the same time, resistant to being eaten by insects ("packaged" transgenic objects). For example, a seed may have the ability to express the insecticidal Stu3 protein while still being resistant to glyphosate.

I0071| Agricultural crops should also be understood to include those obtained by traditional breeding methods or genetic engineering and which contain so-called original characteristics (eg improved storage stability, increased nutritional value and improved aroma).

I0072| Other suitable plants include turf grass, such as on golf courses, lawns, parks and roadsides, or grown commercially for sod, and ornamental plants such as flowers or shrubs.

I0073| Areas of agricultural crops represent land areas on which cultivated plants are already grown or on which the seeds of these cultivated plants have been sown, and also land areas on which it is planned to grow these cultivated plants. 0074) Other active ingredients such as herbicides, plant growth regulators, algocides, fungicides, bactericides, viricides, insecticides, acaricides, nematicides or molluscicides may be present in the formulations according to the present invention or may be added as tank mix partners with the formulations. 0075) Compositions according to the present invention may additionally contain other inert additives.

Such additives include thickeners, anti-caking agents, dispersants, emulsifiers, wetting agents, antifoams, biocides, lubricants, fillers, drift control agents, shear enhancers, adjuvants, evaporation retarders, antifreeze agents, odor attractants insects, UV protection products, fragrances, etc. The thickener can be a compound that is soluble or capable of swelling in water, such as, for example, xanthan polysaccharides (for example, such anionic heteropolysaccharides as KNOBBOROY F 23 (xanthan gum (KPoaia, Staprigu,

МХ)), alginates, guar or cellulose molecules; such synthetic macromolecules as modified cellulose-based polymers, polycarboxylate molecules, bentonite, montmorillonite, hectonite or attapulgite. Antifreeze can be, for example, ethylene glycol, propylene glycol, glycerin, diethylene glycol, sucrose, water-soluble salts such as sodium chloride, sorbitol, triethylene glycol, tetraethylene glycol, urea, or mixtures thereof. Typical defoamers are silicone oils, polydialkylsiloxanes, specifically polydimethylsiloxanes, fluoroaliphatic esters or perfluoroalkylphosphonic/perfluoroalkylphosphonic acid or its salts and mixtures thereof.

Suitable defoamers are polydimethylsiloxanes such as defoamer A Mom Sogpipdf), defoamer B or defoamer M5A. Typical biocides include 1,2-benzisothiazolin-3-one, available as REOHEI PHOHI (Agsp Spetisai!5). 0076) Compositions according to the present invention can be mixed with fertilizers and maintain their stability as before.

І0077| Compositions according to the present invention can be used in traditional agricultural methods. For example, the compositions of the present invention can be mixed with water and/or fertilizers and can be applied pre-emergence and/or post-emergence to the desired location by any means such as aircraft spray tanks, irrigation equipment, direct spray equipment spraying, knapsack spray tanks, livestock bathing tubs, farm equipment used for ground spraying (eg boom sprayers, hand sprayers), etc. The desired location can be soil, plants, etc. 0078) Within the scope of this invention are four different methods of obtaining dispersed or phase polymer particles containing chemicals, which are described in such a way, in which the chemicals are agrochemically active ingredients. Each method results in a dispersed phase that contains a solid polymer matrix with at least one agrochemically active ingredient dispersed therein, a colloidal solid on the surface, not necessarily a mobile, non-crosslinking chemical, so that during the extraction of this chemical from the dispersed solid phase, it becomes porous in such a way that it allows the agrochemically active ingredient(s) to diffuse from the dispersed phase, not necessarily a polymer matrix with hydrophilic groups that hydrate under the influence of water and make the matrix permeable in such a way that it allows the agrochemically active ingredient(s) ) |ingredient(s) to diffuse from the dispersed phase, and not necessarily a non-porous mineral that makes the dispersed phase more impermeable to the agrochemically active ingredient(s).

I0079| The first method includes the following steps: 1. obtaining a dispersion concentrate by dissolving or suspending at least one agrochemically active ingredient in an anhydrous vulcanizable liquid mixture containing at least one suitable crosslinkable resin (such as containing monomers, oligomers, prepolymers or their mixtures ), where the resin optionally contains hydrophilic groups, optionally a suitable hardener, catalyst or initiator, and one or more optional components selected from non-porous particulate minerals as a diffusion barrier and/or mobile chemicals that do not crosslinked, 2. emulsifying said dispersion concentrate to an average droplet size of 1-200 microns in an aqueous liquid which also contains a colloidal solid as an emulsion stabilizer (Pickering), and optionally some suitable hardener, catalyst or initiator capable of diffusing in a drop of dispersion unvulcanized resin; and

C. implementation of crosslinking or vulcanization of a mixture of crosslinkable resins to obtain vulcanized thermosetting polymer particles.

И00О80| The second method is essentially identical to the first, except that the dispersion concentrate contains a polymerizable resin as an anhydrous liquid instead of a crosslinking resin. Instead of the vulcanization reaction at stage C, dispersed-phase particles are formed by a polymerization reaction, so the resulting dispersed phase contains thermoplastic polymer particles, not thermosetting polymer particles.

Zo 00811 The third method includes the following steps: 1. dissolving or suspending at least one agrochemically active ingredient in an anhydrous liquid mixture that contains at least one suitable hardening polymer dissolved in a volatile solvent and one or more optional components selected from non-porous minerals in the form of particles as a diffusion barrier and/or mobile chemicals that do not cross-link; 2. emulsifying said solution to an average droplet size of 1-200 microns in an aqueous liquid that also contains a colloidal solid as an emulsion stabilizer (Pickering), and

C. evaporation of the volatile solvent by heating the emulsion to a temperature of about 30-1207C for about 0.1-10 hours to obtain solid thermoplastic polymer particles. (0082) The fourth production method includes the following steps: 1. obtaining a dispersion concentrate by dissolving or suspending at least one agrochemically active ingredient in an anhydrous liquid mixture that hardens, which contains a melt of at least one suitable thermoplastic polymer that hardens and one or more neobo binding components selected from non-porous minerals in the form of particles as a diffusion barrier and/or mobile chemicals that do not cross-link; 2. emulsifying the specified dispersion concentrate to an average droplet size of 1-200 microns in a heated aqueous liquid, which also contains a colloidal solid as an emulsion stabilizer (Pickering), and 3. cooling the emulsion to obtain thermoplastic polymer particles.

I0083) In one of the implementation options, the dispersion concentrate is obtained by: a. dissolving or suspending at least one agrochemically active ingredient in an anhydrous liquid mixture (premix) containing at least one suitable vulcanizable or polymerizable resin (containing monomers, oligomers, prepolymers or mixtures thereof), optionally a suitable hardener, catalyst or initiator, and one or more optional components selected from non-porous particulate minerals (as a diffusion barrier) and/or mobile non-crosslinking chemicals; r. emulsifying the specified solution or suspension to an average droplet size of 1-200 microns in an aqueous liquid, which also contains a colloidal solid as an emulsion (Pickering) stabilizer, and, optionally, some suitable hardener, catalyst or initiators capable of diffusing in a drop of dispersion unvulcanized or unpolymerized resin; and carrying out crosslinking, vulcanization or polymerization of a mixture of resins to obtain vulcanized thermosetting or polymerized polymer particles of thermoplastic resins, which have at least one agrochemically active ingredient distributed in them and at least one colloidal solid on their surfaces, and which are dispersed in an aqueous liquid after vulcanization.

I0084| In one of the implementation options, the dispersion concentrate is obtained by adding a hardener during the continuous phase, after the formation of the Pickering emulsion, so the dispersion-phase premix is unable to vulcanize. Alternatively, a primary, very low-reactive hardener can be used in the dispersion concentrate, and then a rapid vulcanization secondary hardener, accelerator additive or catalyst can be added during the continuous phase. These secondary agents are added to the continuous phase after emulsification of the dispersed phase, so they must be chosen to be miscible in the continuous phase. Suitable water-miscible rapid vulcanization hardeners include diethylenetriamine, triethylenetetramine, xylenediamine, polyethylene glycoldiamine, and poly(oxypropylene)diamine. Hardener mixtures can also be used due to increased flexibility.

I0085| In one of the implementation variants, the dispersion concentrate is obtained by adding the premix of the dispersed phase to the premix of the continuous phase, where: 1) the premix of the dispersed phases is obtained by mixing in a mixer with high shear forces: at least one agrochemically active ingredient, at least one suitable monomer, oligomer, resin prepolymer , vulcanizable or polymerizable, or mixtures thereof, a suitable hardener, catalyst or initiator, an optional mobile non-crosslinking chemical, and an optional non-porous particulate mineral as a diffusion barrier; 2) the premix of the continuous phase is obtained by mixing in a mixer with low shear forces: an aqueous liquid with a colloidal solid as an emulsion stabilizer.

I0086| Formed as a result of a mixture of dispersed-phase premix and continuous-phase

The premix is shaken under high shear conditions for a period of time suitable for the formation of a Pickering emulsion and then, as needed, heated or exposed to light or other conditions of electromagnetic radiation (UV, microwaves) in order to polymerize the dispersed phase. The shear rate and duration of emulsification can be easily determined by one skilled in the art based on the following observations: if the shear rate is too low, the emulsion and resulting polymer matrix particles are relatively large and may be larger than desired; if, on the other hand, the shear rate is too high or the duration too long, the emulsion-stabilizing colloid eventually becomes so depleted in the continuous phase that any new interface between the dispersed and continuous phases is virtually unprotected, resulting in rapid coalescence or heteroflocculation of the dispersed phase occurs, and the Pickering emulsion is practically lost. (0087) In one of the implementation options, the mixture of dispersed-phase premix and continuous-phase premix is shaken under conditions of high shear rate for 5-10 min and heated to a temperature of about 30-1207C for about 0.1-10 hours in order to carry out the vulcanization reaction.

I0088) In one of the implementation options, the dispersion concentrate is obtained by: a. dissolving or suspending at least one agrochemically active ingredient in an anhydrous liquid mixture containing at least one suitable polymer dissolved in a volatile solvent and one or more optional components selected from non-porous particulate minerals (as a diffusion barrier) and / (or mobile, non-crosslinking chemicals; r. emulsifying the specified solution to an average droplet size of 1-200 microns in an aqueous liquid, which also contains a colloidal solid as an emulsion stabilizer (Pickering), and c. evaporation of the volatile solvent by heating emulsion to a temperature of about 30-120°C for about 0.1-10 hours to produce solid thermoplastic polymer particles having at least one agrochemically active ingredient distributed therein and colloidal solids on their surfaces, and which are dispersed in an aqueous liquid. need, more liquid can be added to the continuous phase to compensate for any losses liquid during the evaporation method. because I0089| Suitable for use in the preparation of solid polymer particles of a dispersed solid phase of polymerizable resins include such thermosetting materials as epoxy resins, phenolaldehyde resins, aminoplasts and polyester resins.

I0090) Other polymerizable resins suitable for use in the preparation of solid polymer particles of a dispersed solid phase include thermoplastic resins such as styrenes, methyl methacrylates, and acrylic resins.

I0091| Suitable thermoplastic polymers include the thermoplastic resin polymers described above, as well as polymers such as acetyl cellulose, polyacrylates, polycaprolactone and polylactic acid.

I0092| With respect to epoxy resins, all conventional di- and polyepoxide monomers, prepolymers or mixtures thereof are epoxy resins suitable for practical use in accordance with the present invention. In one embodiment, suitable epoxy resins are those that are liquids at ambient temperatures. Di- and polyepoxides can be aliphatic, cycloaliphatic or aromatic compounds. Typical examples of such compounds are diglycidyl esters of bisphenol A, glycerol or resorcinol, glycidyl esters and p-methylglycidyl esters of aliphatic or cycloaliphatic diols or polyols, including those of hydrogenated bisphenol A, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1, 4-butanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, or 1,4-dimethylolcyclohexane, or 2,2-bis(4-hydroxycyclohexyl)propane, glycidyl ethers of di- and polyphenols, usually resorcinol, 4.4" - dihydroxydiphenylmethane, 4,4'"-dihydroxydiphenyl-2,2-propane, novolaks and 1,1,2, 2-tetrakis(4-hydroxyphenyl)ethane. Additional examples are M-glycidyl compounds, including diglycidyl compounds of ethyleneurea, 1,3-propyleneurea, or 5-dimethylhydantoin, or 4-methylene-5,5'-tetramethyldigydantoin, or such as, for example, triglycidyl isocyanurate, or biodegradable/ epoxy resins (based on vegetable oil) obtained from biological raw materials.

I0093| Additional glycidyl compounds of technical importance are glycidyl esters of carboxylic acids, especially dibasic and polybasic carboxylic acids.

Typical examples are glycidyl esters of succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, tetra- and hexahydrophthalic acid, isophthalic acid or trimellitic acid or

From partially polymerized, for example dimerized, fatty acids.

Y0094| Exemplary polyepoxides that differ from glycidyl compounds are diepoxides of vinylcyclohexene and dicyclopentadiene, 3-(324-epoxycyclohexyl)-8,9-epoxy-2,4-dioxaspiro|5,5|undecane, 3'4 -epoxycyclohexylmethyl ester of 3,4-epoxycyclohexanecarboxylic acid, butadiene diepoxide or isoprene diepoxide, epoxidized linoleic derivatives or epoxidized polybutadiene. 0095) Other suitable epoxy resins are diglycidyl ethers, or diglycidyl ethers of diatomic phenols, with improved properties, or diatomic aliphatic alcohols with 2-4 carbon atoms, preferably diglycidyl ethers or diglycidyl ethers of 2,2-bis(4-hydroxyphenyl)propane and bis(4-hydroxyphenyl)methane, with improved properties, or a mixture of these epoxy resins.

I0096)| A suitable hardener for use in epoxy resins according to the present invention can be any suitable hardener for epoxy resins, generally selected from primary and secondary amines and their adducts, cyanamide, dicyandiamide, polybasic carboxylic acids, polybasic carboxylic acid anhydrides, polyamines , polyaminoamides, polyadducts of amines, and polyepoxides, and polyols.

I0097| Various amine compounds (mono-, di- or polyamines) can be used as hardeners, such as aliphatic amines (diethylenetriamine, polyoxypropylenetriamine, etc.), cycloaliphatic amines (isophorondiamine, aminoethylpiperazine or diaminocyclohexane, etc.) or aromatic amines ( diaminodiphenylmethane, xylodiamine, phenylenediamine, etc.). Primary and secondary amines may well serve as curing agents, while tertiary amines generally act as catalysts.

II0098| Although epoxy hardeners are essentially amines, other options exist and will provide increased flexibility to accommodate chemicals that may have been unstable or soluble in the presence of the amine, or allow a wider range of cure rates to be achieved. 0099) For example, other suitable hardeners are anhydrides of polybasic carboxylic acids, mainly phthalic anhydride, nadicanhydride, methylnadicanhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and, in addition, tetrahydrophthalic anhydride and hexahydrophthalic anhydride. 60 001001 According to this invention, colloidal emulsion stabilizers can be used

Pickering of any type for stabilizing emulsions prior to the step of curing the dispersed phase into a solid polymer matrix, regardless of the type of polymer matrix, wherein the dispersed phase contains a chemical such as an agrochemically active ingredient, and wherein the dispersed phase optionally contains a matrix permeability control agent and hence the rate of release of the agrochemically active ingredient during application.

I00101| More specifically, solids such as silicas and clays have been reported in the literature to be used as viscosity modifiers in agrochemical formulations to inhibit gravity sedimentation or foam separation by forming a mesh or gel throughout the continuous phase, thereby increasing 'viscosity at low shear rate, and slowing down the movement of small particles, surfactant micelles or emulsion droplets.

The colloidal solids of the present invention, on the other hand, serve as a process additive to stabilize droplets containing resin monomers during curing by adsorbing to a variable liquid interface, thus forming a barrier around the vulcanizing droplets, hence the droplets , contacting or vulcanizing, are not capable of coalescence, regardless of whether or not the vulcanizing droplets have collected into a precipitate or foam layer.

It is possible to distinguish two different functions - modification of the rheological properties or stabilization of the emulsion with the help of such a functional test as described below. The effectiveness of a colloidal solid in stabilizing vulcanizable polymer droplet emulsions depends on particle size, particle shape, particle concentration, particle wettability, and particle interactions. The colloidal solids must be small enough so that they can cover the surfaces of the dispersed liquid vulcanizable polymer droplets, and the liquid vulcanizable droplets must be small enough for acceptable dispersion stability with respect to sedimentation of the resulting solid polymer particles if the dispersion a concentrate containing such particles diluted for use. The final polymer particles (and therefore colloidal solids) will also be required to be small enough to ensure acceptable uniform distribution of the product over the target site. The colloidal solid must also have sufficient affinity for both the liquids forming the dispersed and continuous phases so that they are able to adsorb to the variable liquid interface and thus stabilize the emulsion during solidification. These

From the wetting characteristics, particle shape and suitability for stabilizing an emulsion such as a Pickering emulsion can be readily determined by obtaining a control composition lacking colloidal solids as an emulsion stabilizer. In this case, vulcanizing liquid polymer droplets coalesce and form a cemented mass instead of a dispersion of finely dispersed solid polymer particles.

II00102| In one embodiment, the colloidal solids have an arithmetic mean weighted median particle diameter, as measured by scanning electron microscopy, of 0.01-2.0 microns, specifically 0.5 microns or less, more specifically 0.1 microns or less .

І00103| A wide variety of solids can be used as colloidal stabilizers for the dispersions of the present invention, including carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silicas, and clays.

Suitable colloidal stabilizers are insoluble in each of the liquid phases present in the composition of the concentrate. If the agrochemically active ingredient has a suitably low solubility in any liquid used to dilute the final formulation, both in the continuous and in the (variably) dispersed liquid phase, which is below about 100 parts per million at room temperature, and it can be obtained at a suitable particle size and has wetting properties suitable for variable liquid interface separation as described above, then it is probably also possible that this active ingredient can serve as a colloidal stabilizer. Examples of inorganic substances in the form of particles are such oxycompounds of at least one of calcium, magnesium, aluminum and silicon (or derivatives of such substances), such as silica, silicate, marble, clay and talc. Inorganic substances in the form of particles can either occur in nature or be synthesized in reactors. The particulate inorganic material may be a mineral selected from, without limitation, kaolin, bentonite, alumina, limestone, bauxite, gypsum, magnesium carbonate, calcium carbonate (either crushed or precipitated), perlite, dolomite, diatomite, gantite, magnesite, bomite, sepiolite, palygorskite, mica, vermiculite, illite, hydrotalcite, hectorite, halloysite, and gibbsite. Additional suitable clays (eg, aluminosilicates) include those containing kaolinite, montmorillonite, or illite groups of the clay mineral. Other specific examples are attapulgite, laponite, and sepiolite.

Polymers that flocculate colloids (such as xanthan in the case of colloidal kaolin) can also improve the stability of Pickering emulsions.

(00104) In one embodiment, non-porous particulate inorganic substances are distributed in the polymer particles together with an agrochemically active ingredient to serve as an optional diffusion barrier. A diffusion barrier is obtained by dissolving or suspending such substances together with (for example, a water-sensitive) agrochemically active ingredient in an anhydrous vulcanizable liquid mixture, which is used to obtain polymer particles of thermosetting or thermoplastic resins that serve as the dispersed phase B). Suitable non-porous particulate diffusion barrier materials include carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica, mica, and clays. 00105) In one aspect of the present invention, the particulate inorganic substance is kaolin clay. Kaolin clay is also known by the name of porcelain clay or hydrated kaolin and mainly contains the mineral kaolinite (АИ25и205(ОН)4), hydrated aluminum silicate (or aluminosilicate). 00106) In one of the aspects of this invention, the inorganic substance in the form of particles can be surface-modified. Surface-modified means that the surface of the inorganic particles has been modified to have reactive groups. The particle surface can be modified using a wide variety of chemicals with the general structure X-U-2, in which X is a chemical moiety with a high affinity for the particle surface; 7 is a (reactive) chemical fragment with desired functionality; and Y is a chemical moiety that binds X and 2 together. 00107) X can be, for example, an alkoxysilane group such as triethoxysilane, or trimethoxysilane, or trichlorosilane, which is particularly suitable when the particles have silanol (ZION) groups on their surface. X can also be, for example, an acid group (such as a carboxylic or acrylic acid group), which is particularly suitable when the particles have basic groups on their surface. X can also be, for example, a basic group (such as an amino group), an epoxy group or an unsaturated group (such as an acrylic or vinyl group).

II00108| M can be any chemical group that binds X and 7 together, for example, a polyamide, polyisocyanate, polyester or alkylene chain; more properly, it is an alkylene chain; and even more appropriately, it is a C 2 -C alkylene chain such as ethylene or propylene. 00109) Reactive groups 7 can be selected from any groups and can be different from Y, which can be used to react with the crosslinker.

ІОО110| The type and amount of colloidal solid matter is chosen to ensure acceptable physical stability of the composition during vulcanization, polymerization, solvent evaporation, or another method of polymer solidification. This can be readily determined by one skilled in the art by routine evaluation of a range of compositions having varying amounts of this component. For example, the ability of the colloidal solids to stabilize the composition can be verified by obtaining a test sample with the colloidal solid, and it can be confirmed that the droplet emulsion is stable and does not exhibit coalescence.

Coalescence is visible due to the formation of large drops visible to the eye, and ultimately due to the formation of a layer of liquid monomers, polymer melt or polymer solution in the composition. The physical stability of the composition during vulcanization, polymerization, evaporation of the solvent or other method of curing the polymer is acceptable in the absence of clearly expressed significant coalescence, and solid polymer particles are present as a fine dispersion.

ЙОО111| For example, in one embodiment, colloidal solids are used in an amount from 1 to 8095, specifically from 4 to 5095 by weight of the dispersed phase.

Mixtures of colloidal solids can be used. 00112) In one embodiment, one or more surfactants may optionally be used in addition to the Pickering emulsion colloidal stabilizers in order to conveniently control the emulsion droplet size according to the shear rate applied during the emulsification process. One or more surfactants, if present, are used in an amount of from 0.195 to 9095, specifically from 195 to 609o by weight of the Pickering emulsion colloidal stabilizers. In a particular embodiment, the surfactant is chosen to have a low NI B (hydrophilic-lipophilic balance), such as 6 or below. In another specific embodiment, the surfactant is a 2-molar alkylamine ethoxylate in which the alkyl group contains from about 8 to about 18 carbon atoms. (00113) The following examples further illustrate some aspects of this invention, but are not intended to limit its scope. Unless otherwise specified throughout this description and claims, percentages are by weight.

Examples 1-4 - Illustration of the use of different continuous-phase liquids 00114) Resin mixture A 19.1 g of thin epoxy resin 635 (05 Sotroziev M/evi) was obtained

Rait Weasp, RI) and 9.5g 21 epoxy hardener 556 (also 05 Sotrozige5). Then the following liquid continuous-phase samples of 10 g of liquid were obtained, each by vortex mixing with 0.2 g of fused silica Aerosil 200 as a colloidal stabilizer: 9:1 ethylene glycol:water, 9:11 RES200:water, 9:1 glycerin:water and water 0.2 g of resin mixture A was then introduced into each continuous-phase sample and dispersed by vortexing.

The samples were placed on a platform shaker overnight at room temperature and then examined by light microscopy. In each case, the presence of a dispersion of epoxy resin particles with a diameter of approximately 100 microns was confirmed. These examples show that fine particles of solid epoxy resin can be formed in a variety of different liquid continuous phases.

Examples 5-7. Illustration of the use of different colloids to stabilize the resin before vulcanization. 00115) Resin mixture B was obtained by mixing 9 g of fine epoxy resin 635, 1.5 g of finely ground difenoconazole, and 4.5 g of 21 epoxy hardener 556. The following liquid continuous phases were then obtained, each by vortex mixing: 0.2 g of fused silica Aerosil 200 in 9.8 g of water and 0.2 g of mordanted alumina in 9.8 g of water. 0.2 g of resin mixture B was then introduced into each continuous-phase sample and dispersed by vortex mixing. Samples were placed on a platform shaker overnight at room temperature and then examined by light microscopy. In each case, the presence of finely dispersed epoxy resin particles with a diameter of approximately 100 microns was confirmed. In addition, the sample was obtained when the liquid continuous phase did not contain any colloidal solids, and as a result, a large deposit of solid epoxy adhered to the container wall. This example shows that a variety of different colloidal solids can be used to stabilize epoxy resin dispersions, but if no colloidal solids are used, the resin readily coalesces and eventually hardens to a solid mass.

From Examples 8-16. Incorporation of various AIs into the polymer matrix

I00116| Nine different individual resin blends were prepared by mixing 8 g of fine epoxy resin 635, 4 g of 2:11 epoxy hardener 556, and 1.0 to 1.5 g of the following finely divided active ingredients: atrazine, azoxystrobin, bicyclopyrone, cyproconazole, difenoconazole , mesotrione, prodiamine, thiabendazole, thiamethoxam. During direct inspection, it was found that bicyclopyrone and mesotrione completely dissolved in liquid resin at these concentrations, most of cyproconazole dissolved, and other AIs dissolved slightly. 1 g of each of these resin mixtures was separately dispersed by vortexing in 10 g of continuous-phase liquid samples containing 0.2 g of fused silica each

Aerosil 200, dispersed in 9.8 g of water. Samples were placed on a platform shaker overnight at room temperature and then examined by light microscopy. In each case, the presence of a dispersion of epoxy resin particles with a diameter of approximately 100 microns was confirmed. Crystals of the active ingredients were visible within the epoxy particles under polarized light, except that in the cases of bicyclopyrone and mesotrione individual crystals were not visible because these active ingredients were dissolved in the epoxy resin - in these cases the entire epoxy resin particle was slightly birefringent, indicating the presence of crystal domains in the matrix. These examples show that a wide variety of different active ingredients can be effectively entrapped onto epoxy resin particles, regardless of whether they are insoluble, partially insoluble, or completely soluble in the resin, and without the need for either significant process modification or the presence of other components.

Examples 17-18 Illustrating the entrapment of the active ingredient to polystyrene and polyacrylate matrices.

A. Obtaining a composition

I00117| The dispersed phase is premixed in a mixer, which provides high shear stress, as described in Table 1 below. The continuous phase is premixed in a low shear mixer. The premixed dispersed phase is added to the continuous phase and then mixed in a mixer with high shear forces for 5-10 min. For the purpose of polymerization, the emulsified composition is treated at a high temperature (70"C) for 8 hours.

The average value of the diameter of the particles was determined with the help of the particle size analyzer because Maimegp? Maziegwieg.

Table 1 77771111 Examples7///// | Examples 8.////: GIO

Atrazine 690 Atrazine 690

Dispersed phase | Styrene monomer 14,790 Methyl methacrylate monomer 14,790

Methyl ethyl ketone peroxide 0.390 Methyl ethyl ketone peroxide 0.390

Aerosil AZOO Zoo Aerosil AZOO Zoo

Continuous phase |IFosphoric acid (895) 0.0590 Phosphoric acid (895) 0.059 water 75.9595 water 75.9595 particles (μm)

Examples 19-20 Illustrating release rate control by incorporating a non-crosslinking mobile chemical molecule into a polymer matrix and Examples 21-22 illustrating entrapment of liquid active ingredients.

A. Preparation of composition 00118) The dispersed phase is premixed in a low shear mixer as described in Table 2 below. The continuous phase is premixed in a low shear mixer. The premixed dispersed phase is added to the continuous phase and then mixed in a mixer with high shear forces for 5-10 min. To accelerate the hardening reaction of the epoxy resin, the mixed composition was treated at a high temperature (707C) for 3 hours. The average value of the diameter of the particles was determined using a particle size analyzer MaiYimegp? Mawiegwi2eg.

B. Release Rate 00119) Vulcanized compositions 19 and 20 were diluted in water with appropriate emulsifiers (Tohity! TA-b, eierias 8180 and Tohity! 8320, etc.) in a glass vial and shaken.

The concentration of the active ingredient was monitored using HPLC analysis.

Table 2 77711111 | Example 19 Example 2O | Example 2! | Apply

Thiamethoxam

Thiamethoxam ze

God Epoxy Mefenoxam 590 5-metolachlor 590

Disperse Epoxy resin 635 995 Epoxy Epoxy

Hardener 556 | resin 635 1095 resin 635 1095 phase resin 635 1075 4.59 Hardener 556 | Opener 556

Hardener 556 | . lverju lverju

Bo Polyethylene glycol |59Uo Bo (mol. weight-200) 1.595 phase water 7895 water 7895 water 7895 water 7895

The average value of the diameter of 55 45 25 27 particles (μm) of the particle | 0111 release of bod. | -:/ 09 | 77/87 Y7777171142 gЯ4h. | 12 | 77723711!

And 48 hours. | 14 | 25 2 Sh | 56

Examples 21-24 Illustration of Pickering emulsions using clay and flocculating polymers

A. Obtaining a composition

I00120| The dispersed phase is premixed in a mixer that provides high shear stress, as described in Table C below. The continuous phase is premixed in a low shear mixer. The premixed dispersed phase is added to the continuous phase and then mixed in a mixer with high shear forces for 5-10 min. For the purpose of polymerization, the emulsified composition is treated at a high temperature (70"C) for 8 hours.

The average particle diameter was determined using a particle size analyzer

Maimegp? Maziegwieg.

Table C 11111112 23

Mefenoxam.//////777111111111111111111111111 1761 1 v-metolachlor.////777777777777777111111111111111111111111 1751

Тефлутрин//////7777771111111111111111111111111111111111111101и75ІЇ ни Пропконазол.///7777777771111111111111111111111111111 рив ефіррезодцину.ї//-/-/:///с1111111111111111111111 111 фаза Фосфорнакислота(855) 33333331 1 10 1 |Середнявеличинарозміручастинок(імкм)ї г | 30|25| 17 | 30 00121) Although only some of the exemplary embodiments of the present invention have been described in detail above, those skilled in the art will readily appreciate that many modifications to the exemplary embodiments are possible without substantially departing from the novel ideas. and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the following claims.

Claims (12)

FORMULA OF THE INVENTION 1. An aqueous liquid dispersion concentrate composition containing: (a) a continuous aqueous liquid phase and (b) at least one dispersed, solid phase that contains polymer matrix particles having an average particle size of at least one micron and obtained from or resin that cures from either a polymerizable resin or a curable thermoplastic polymer, wherein the outer surfaces of the polymer matrix particles contain a colloidal solid selected from carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silicas, and clays, and wherein the polymer matrix particles have at least one agrochemically active ingredient distributed therein. 2. The composition according to claim 1, in which the agrochemically active ingredient contains a solid substance and is distributed in a dispersed solid phase or is a liquid and is distributed in a dispersed solid phase. 3. The composition according to any of the previous items, in which the dispersed phase contains at least 30 one mobile, non-crosslinking chemical, so that during the extraction of this chemical from the dispersed phase, it becomes porous in such a way as to allow the active ingredient to diffuse outward. 4. A composition according to any of the preceding items, in which the polymer molecules comprising the polymer matrix particles contain hydrophilic groups that hydrate under the influence of water in such a way that it makes the polymer matrix particles more permeable, thereby allowing the active ingredient to diffuse outside. 5. The composition according to any of the previous items, in which each dispersed phase optionally contains at least one non-porous mineral in the form of particles, which acts as a diffusion barrier to slow down the release of the active ingredient. 6. The composition according to any of the previous items, in which the continuous phase (a) contains water; and (b) a substantially water-miscible anhydrous liquid or water-soluble solute. 7. The composition according to any one of claims 1-6, in which the continuous phase (a) additionally contains at least one agrochemically active ingredient, and this active ingredient is in a state, selected from a solution, emulsion, microemulsion or suspension of microcapsules or fine particles. 8. The composition according to any of the previous items, in which each dispersed phase (b) contains a hardened epoxy resin polymer; hardened polymer of phenolaldehyde resin; hardened polyurethane polymer; hardened polyurea resin polymer; hardened aminoplast polymer; resin polymer based on complex polyester or based on complex vinyl ether; thermoplastic polystyrene or polyacrylate polymer or biodegradable thermoplastic polymer. 9. A method of preventing or combating the infection of plant species by pests, or regulating plant growth by diluting an effective amount of the concentrate composition according to any of claims 1-8, in an aqueous liquid carrier selected from water and liquid fertilizer, and applying the diluted composition to the species plants or their locations. 10. The method of obtaining an aqueous liquid dispersion concentrate according to claim 1, which includes the stages of: a) dissolving or suspending at least one agrochemically active ingredient in a liquid resin that solidifies, hardens or polymerizes; b) combining the specified solution or suspension with an aqueous liquid containing a colloidal solid emulsion stabilizer selected from carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica, and clays, and optionally a chemical hardening agent, and the application of mechanical stirring sufficient to form an emulsion of said solution or suspension; and c) carrying out curing, solidification or polymerization of the resin to obtain an aqueous liquid dispersion of polymer matrix particles, which contains at least one agrochemically active ingredient and a colloidal solid distributed on the surface of the polymer matrix particles. 11. The method of obtaining an aqueous liquid dispersion concentrate according to claim 1, which includes the stages of: a) dissolving or suspending at least one agrochemically active ingredient in a thermoplastic polymer solution in a volatile solvent; b) combining the specified solution or suspension with an aqueous liquid containing a colloidal solid emulsion stabilizer selected from carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica, and clays, and using mechanical stirring sufficient to forming an emulsion of the specified solution or suspension; and c) thermal exposure to evaporate the volatile solvent to obtain an aqueous liquid dispersion of polymer matrix particles, which contains at least one agrochemically active ingredient and a colloidal solid distributed on the surface of the polymer matrix particles. 12. The method of obtaining an aqueous liquid dispersion concentrate according to claim 1, which includes the stages of: a) dissolving or suspending at least one agrochemically active ingredient in a thermoplastic polymer melt; b) combining said solution or suspension with an aqueous liquid containing a colloidal solid emulsion stabilizer selected from carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica, and clays, and applying mechanical agitation sufficient to form emulsions of the specified solution or suspension; and c) cooling the emulsion to solidify the dispersed phase and thereby obtain an aqueous liquid dispersion of polymer matrix particles that contains at least one agrochemically active ingredient and a colloidal solid distributed on the surface of the polymer matrix particles.