RU2801250C2 - Stabilized chemical composition - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: methods for obtaining agrochemical compositions containing a continuous phase and at least one dispersed phase include a. obtaining a non-aqueous curable liquid containing at least one cross-linkable resin or polymerizable resin containing monomers, oligomers, prepolymers or mixtures thereof, the resin optionally containing hydrophilic groups, optionally a hardener, catalyst, plasticizer or activator; or obtaining a non-aqueous liquid containing at least one hardenable polymer dissolved in a volatile solvent, and one or more optional plasticizers; or obtaining a non-aqueous curable liquid containing a melt of at least one curable thermoplastic polymer and optionally a plasticizer; or obtaining a dispersion concentrate by dissolving or suspending at least one agrochemical active ingredient in a non-aqueous curable liquid mixture containing a melt of at least one curable thermoplastic polymer and optionally a plasticizer or containing at least one cross-linkable resin or a polymerizable resin containing monomers, oligomers, prepolymers or mixtures thereof, wherein the resin optionally contains hydrophilic groups, optionally a hardener, catalyst, plasticizer or activator; or dissolving or suspending at least one agrochemical active ingredient in a non-aqueous liquid mixture containing at least one settable polymer dissolved in a volatile solvent and one or more optional plasticizers, b. emulsifying the non-aqueous curable liquid to an average droplet size of 1-200 microns in an aqueous liquid, wherein the aqueous liquid contains a colloidal solid as an emulsion stabilizer, optionally contains a plasticizer, and optionally a hardener, catalyst or initiator capable of diffusing into the dispersed uncured resin droplets; or emulsifying a non-aqueous liquid or a non-aqueous curable liquid to an average droplet size of 1-200 microns in an aqueous liquid or in a heated aqueous liquid, wherein the aqueous liquid contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; or emulsifying the dispersion concentrate to an average droplet size of 1-200 microns in an aqueous liquid, where the liquid contains a colloidal solid as an emulsion stabilizer, optionally contains a plasticizer and optionally a hardener, catalyst or activator capable of diffusing into the droplets of the dispersed uncured resin; or emulsifying the solution to an average droplet size of 1-200 microns in an aqueous liquid, where the liquid contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; or emulsifying the dispersion concentrate to an average droplet size of 1-200 microns in a heated aqueous liquid that contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer, c. allowing the cross-linkable resin mixture to crosslink or cure, and then optionally impregnating with a plasticizer to form an emulsion containing the cured thermoset polymer particles and the colloidal solid material on the surface of the particle; or ensuring evaporation of the volatile solvent by heating the emulsion to a temperature of 30-120°C for 0.1-10 hours and then optional impregnation with a plasticizer to obtain solid thermoplastic polymer particles and a colloidal solid material on the surface of the particle or then optional impregnation with a plasticizer to obtain solid thermoplastic polymer particles with at least one agriculturally active ingredient distributed in them, and colloidal solid material on the surface of the particle; or cooling the emulsion and then optionally impregnating with a plasticizer to form thermoplastic polymer particles in the emulsion and a colloidal solid material on the surface of the particle; or allowing the cross-linkable resin mixture to crosslink or cure and then optionally impregnate with a plasticizer to form emulsions comprising cured thermoset polymer particles with at least one agriculturally active ingredient dispersed therein and a colloidal solid material on the surface of the particle; or cooling the emulsion and then optionally impregnating with a plasticizer to form thermoplastic polymer particles with at least one agriculturally active ingredient dispersed therein and a colloidal solid material on the surface of the particle, d. adding an agriculturally active ingredient to an emulsion to produce cured thermoset polymer matrix microparticles or thermoplastic polymer matrix microparticles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with an agrochemical active ingredient or ingredients distributed in them.

EFFECT: inventions make it possible to obtain compositions that are stable when diluted with water in a wide range of field conditions, and which are also characterized by an excellent ability to adhere to the surface of foliage, seeds or plant parts for vegetative propagation.

19 cl, 8 dwg, 19 tbl, 14 ex

Description

[0001] The present invention relates to stabilized liquid chemical compositions, the preparation of such compositions, and a method of using such compositions, for example, in pest control or as plant growth regulators.

BACKGROUND OF THE INVENTION

[0002] Agriculturally active ingredients (agrochemicals) are often supplied as concentrates suitable for dilution with water. Many types 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 agricultural active ingredients in water. Due to the relatively complex crop protection supply chain, such concentrate formulations may be stored for long periods and may be subjected during storage and transport to extreme temperature fluctuations and repetitive high shear vibration patterns. Under such conditions in the supply chain, the possibility of deterioration of the composition, such as, for example, flocculation, thickening and sedimentation, can increase.

[0003] In some cases, it may be necessary to combine different agrochemicals in a single formulation, taking advantage of the additive properties of each individual agrochemical and optionally the adjuvant or combination of adjuvants that provide optimal biological performance. For example, transport and storage costs can be minimized by using a formulation in which the concentration of the active agrochemical(s)(s)(s) is as high as practicable and in which any necessary excipients are "built-in" in the composition, as opposed to separately received in the form of a tank mix. However, the higher the concentration of the active(s) agrochemical(s) means(s), the higher the likelihood that the stability of the composition may be impaired, or that one or more components may exfoliate. In addition, it may be more difficult to avoid deterioration of the formulation in the presence of multiple active ingredients due to the physical or chemical incompatibility of these chemicals, such as, for example, when one active ingredient is an acid, a base, an oily liquid, a hydrophobic crystalline solid, or a hydrophilic crystalline solid. substance, and the other(s) active(s) ingredient(s) has or have other properties.

[0004] In addition, the mixtures in the tank sprayer may contain a number of chemicals and excipients that can interact and change the effectiveness of one or more agrochemicals included in them. Incompatibilities, poor water quality, and insufficient mixing in the tank can lead to reduced sprayer performance, phytotoxicity, and can affect equipment performance.

[0005] Given the range of conditions and specific situations in which agrochemical liquid concentrate formulations are stored, transported, and used worldwide, there remains a need for improved liquid polymer dispersions containing agrochemicals, including water-soluble, water-dispersible, or water-sensitive agrochemicals having an average dispersed particle size of >1000 nm and providing additional stability benefits under at least some of these conditions and situations. There is a further need for such high content formulations that are stable when diluted with water over a wide range of field conditions.

[0006] Upon delivery to the end user, the agrochemical composition should work as intended. In particular, the formulation must be brought into contact with the surface of the plant part to which it has been applied so that the active ingredient can be delivered to the plant part or pest. Preferably the composition will adhere so that it will not be easily washed off by rain or other water applications. In some cases, the formulation will be applied to seeds or plant parts for vegetative propagation. For these cases, the composition will need to adhere to the surface of the vegetative propagation seeds or plant parts in such a way that it does not wear off during treatment and is present when the vegetative propagation seeds or plant parts are planted. Thus, it will be preferable to obtain a composition which is characterized by an excellent ability to adhere to its target surface, for example, the surface of foliage, seeds or plant parts for vegetative propagation.

[0007] Known technologies for producing polymer particles or modifying the properties of polymer particles include coacervation, melt-cooling, solvent evaporation, grinding of monolithic polymer blocks, interfacial polymerization, impregnation with polymers such as latex, and the use of mobile molecules to increase the permeability of the polymer particle. However, all of these technologies have disadvantages that the technology of the present invention seeks to overcome, as described below.

[0008] Coacervation is a method of obtaining a dispersed phase in a liquid suspension by forming molecules that are in solution in the liquid phase to be deposited on the surface of the dispersed phase. Obvious limitations inherent in this method include the difficulty in forming particles of uniform composition and size, since the mechanism that causes precipitation must correspond to the mass transfer rate at which the precipitated molecules can collide with existing particles of the dispersed phase. If the rate is too low, the precipitating molecules will become supersaturated and simply form particles from that one molecule. Coacervation is generally not compatible with the technology of the present invention, where polymer particles are formed from multiple molecules (e.g., one monomer and a plasticizer), while coacervation does not provide the ability to independently control different settling and mass transfer rates of different molecules, so the method is inherently inappropriate. In one embodiment, the technology of the present invention overcomes these limitations because the monomer and plasticizer are homogeneous throughout the dispersed phase of the emulsion prior to the crosslinking reaction that forms the polymer matrix.

[0009] Evaporation of the solvent includes forming a polymer solution in a volatile solvent, emulsifying this solution in an immiscible second solvent, and then removing the volatile solvent to obtain a dispersion of polymer particles. A practical disadvantage of the process is that the volatile solvent either leaks to the atmosphere or needs to be recovered either option is costly and the diluted volatile solvent will typically be flammable and/or hazardous.

[0010] It is known that homogeneous matrix particles can be obtained by grinding large blocks, however, the technology of the present invention includes gel-like matrix particles of a plasticized polymer. It is optional and impossible to grind the soft particles, since such grinding is not a practicable method of obtaining.

[0011] Interfacial polymerization occurs when a dispersed phase of one monomer is in solution of a second monomer, and the rate of reaction of the two monomers is substantially faster than mass transfer, such that they essentially react at surfaces where the concentration of the second monomer essentially drops to zero. It is characteristic of this method that the dispersed phase is not homogeneous because the second monomer cannot diffuse into the center before it reacts, and this results in a dispersed phase with a polymer shell around a substantially polymer-free liquid. Deformation of such polymer-encapsulated droplets can break and release the contents. The technology of the present invention overcomes this disadvantage by providing a significant uniformity of the polymer matrix in the discontinuous phase, and as just described, this uniformity is incompatible with the reaction kinetics that leads to interfacial polymerization.

[0012] Pre-formed dispersions of polymer particles in water, ie. latex, are the traditional means of delivering film-forming polymers capable of adhering to surfaces. It is known that latexes can absorb an organic phase and therefore, in principle, can be used to ensure that this organic phase, which may contain an active ingredient, adheres to a surface. One limitation with the impregnation of polymers such as latex is that under extreme conditions, either due to cycling temperature or dilution in a high electrolyte fertilizer, the loss of dispersion stability of the impregnated latex causes the polymer particles to solidify into in the form of glued agglomerates, which will cause catastrophic clogging of equipment. Another limitation is that the dried deposits of impregnated latex particles are in fact tacky adhesive coatings that cannot be removed and will render the equipment unusable. In contrast, the formulations of the technology of the present invention are very stable when in aqueous dispersion. Dried films are not sticky and can be washed off if necessary.

[0013] It is known that the permeability of a polymer matrix particle can be increased by including mobile molecules that can dissolve in the liquid in which the particles are placed, while the removal of mobile molecules provides for the creation of cavities or pores through which the active ingredient can diffuse. The present invention contemplates incorporating plasticizers into the polymer matrix for substantially the period during which they have beneficial properties due to their plasticity. Mobile molecules that are released from the polymer matrix to form pores cannot serve as a plasticizer, and thus the two functions, plasticizer and penetrating agent, are incompatible within the context of this document. A plasticized polymer matrix that has a low degree of crosslinking is generally not a diffusion barrier. Thus, mobile molecules that diffuse out of the polymer matrix according to the technology of the present invention will not significantly increase its permeability, and therefore it will not be able to function as a permeation agent.

BRIEF DESCRIPTION OF THE INVENTION

[0014] The technology of the present invention relates to the selection of gel emulsion formulations that contain soft, gel-like, plastic microparticles of a polymer matrix with a hardness of more than 0.001 MPa and less than 6 MPa and loaded with at least one agrochemical active ingredient (AI), and to the use of these gelled microparticulate (GM) formulations for application to plant parts, eg, foliage applications, and for treating plant parts for vegetative propagation, including seeds. In one embodiment, the technology of the present invention relates to the reduction of attrition in seed treatments. In another embodiment, the technology of the present invention relates to improving plant adhesion, rain washout resistance for foliar applications, and reducing Foliar Runaway Residue (DFR) on sprayed crops. In another embodiment, the technology of the present invention relates to an agrochemical formulation that provides improved safety (e.g., reduced phytotoxicity) to a crop while maintaining pesticidal efficacy against the target pest. Such improvement includes application to seeds or to an established or growing plant.

[0015] Provided stabilized liquid agrochemical compositions that contain flowable liquid dispersion concentrates containing a) a continuous aqueous liquid phase; b) at least one dispersed phase containing GM, characterized by an average particle size of at least 1 micron to at least 100 microns and a hardness of more than 0.001 MPa and less than 6 MPa, while the outer surfaces of the particles contain a colloidal solid material, and when this particles contain at least one chemical agent distributed in them. GM is made from either a curable or polymerizable resin or a curable thermoplastic polymer.

[0016] In one embodiment, the colloidal solid material is present in the discontinuous phase in an amount effective to stabilize the polymer resin in an emulsified state during the process used to obtain the discontinuous phase. In other embodiments, the dispersed phase comprises polymer particles obtained by curing a thermoplastic polymer resin, curing a thermosetting resin, or polymerizing a thermoplastic resin. In another embodiment, the chemical agent is a solid and distributed in the discontinuous phase, or is a liquid and distributed in the discontinuous phase. In a further embodiment, the continuous liquid phase is water or a mixture of water and either a water-miscible liquid or a water-soluble solid. In some embodiments, the continuous liquid phase is non-aqueous.

[0017] In some embodiments, GM is produced in the presence of a plasticizer to produce GM that has a hardness greater than 0.001 MPa and less than 6 MPa. In some embodiments, GM is produced using an appropriate polymer composition option (e.g., polymer chemistry and/or cross-linked structure) to produce GM that has a hardness greater than 0.001 MPa and less than 6 MPa. The properties of the polymer network can be monitored, for example, using differential scanning calorimetry (DSC), nanoindentation and/or rheological techniques. Provided that at least one chemical agent is an agrochemically active ingredient, the compositions of the present invention can be used directly or in dilution for pest control or as plant growth regulators.

[0018] In accordance with one embodiment of the present invention, it has been found that liquid dispersion concentrates of agrochemically active ingredients in a liquid can be obtained by using a polymerized, hardened or hardened polymer resin to incorporate the agrochemically active ingredients in a polymer matrix, using a colloidal solid to stabilize the polymer resin emulsified during the curing reaction or curing process. In the polymer matrix, which is dispersed in the form of particles in a continuous liquid phase, at least one agrochemically active ingredient can be distributed. Other active ingredients may optionally be dispersed, dissolved, emulsified, microemulsified or suspended in the continuous phase.

[0019] The liquid dispersion concentrates of the present invention have such a long effective period of protection against water-soluble, water-dispersible, water-sensitive and other agrochemicals that the chemical and physical stability of the composition is improved, and which provides practical value regarding storage, transportation and applications. Dispersible concentrates according to the technology of the present invention also conveniently provide a combination of several active ingredients in one formulation, whether they are liquids or solids, by incorporating them separately or together in GMs that are physically mutually compatible.

[0020] The aqueous dispersion concentrates of the present invention also have non-agricultural applications where there is a need for stable formulations and delivery of chemicals to a targeted site. For these purposes, agrochemical agents, if necessary, can be replaced by other chemical agents. In the context of the present invention, chemicals thus include any catalyst, adjuvant, vaccine, genetic vector, drug, flavor, flavor, enzyme, spore or other colony forming unit (CFU), dye, pigment, adhesive or other component, if release of the chemical agent from the composition is required. In addition, aqueous dispersion concentrates can be dried to obtain a powder or granular product, if necessary.

[0021] Polymerizable resins suitable for use in preparing the dispersed phase of the cured polymer matrix can be selected from monomers, oligomers, or prepolymers that are polymerizable to either thermoset or thermoplastic polymer particles. In accordance with the present invention, the polymer matrix that makes up the discontinuous phase can be formed by dissolving the polymers in a volatile water-immiscible solvent which also contains at least one agrochemical agent, stabilizing this solution in water in the form of a Pickering emulsion using colloidal stabilizers, and then heating this emulsion with the evaporation of a volatile solvent and the formation of a dispersed phase of a thermoplastic polymer matrix. In addition, the polymeric matrix that makes up the dispersed phase can be formed by dissolving or suspending at least one agrochemical active ingredient in a non-aqueous liquid mixture containing a melt of at least one suitable thermoplastic polymer, emulsifying said dispersion concentrate to an average droplet size of 1- 200 microns in a heated aqueous liquid that also contains a colloidal solid as an emulsion stabilizer (Pickering); and cooling the emulsion to form thermoplastic polymer particles.

[0022] The present invention also relates to "gel" or "gel-like" polymer matrix particles containing an incorporated agrochemical that is either uniformly or non-uniformly distributed in such a particle or is present as domains in such a particle, and where the areas of the outer surfaces of the particles contain colloidal solid material. The term "gelled" and "gelled" as used herein means a non-limiting generic identifier, and is not a definition or limitation of "gelled" and "gelled" for a polymer particle.

[0023] The present invention also includes a method of controlling or controlling pests or regulating plant growth in a locus such as soil or foliage, which comprises treating said locus with a dispersion concentrate according to the present invention or dispersing the concentrate according to the present invention in water or liquid fertilizer and treatment of the specified place of growth with the obtained diluted aqueous composition for the final application.

BRIEF DESCRIPTION OF GRAPHICS

[0024] FIG. 1 is a schematic representation of a gel particle with a clayey colloidal solid according to the present invention.

[0025] FIG. 2 is a schematic cross-sectional view of FIG. 1.

[0026] FIG. 3 is a schematic representation of a gel particle with a substantially spherical colloidal solid according to the present invention.

[0027] FIG. 4 is a schematic cross-sectional view of FIG. 3.

[0028] FIG. 5 is a schematic cross-sectional view of a gel particle with a clay colloidal solid and a solid active ingredient dispersed in a polymer matrix according to the present invention.

[0029] FIG. 6 is a graph showing the data of Table 6a.

[0030] FIG. 7 is a graph showing the data of Table 6b.

[0031] FIG. 8 is a graph showing the data of Table 6c.

DETAILED DESCRIPTION OF THE INVENTION

[0032] Accordingly, in one embodiment, the liquid dispersion concentrate compositions of the present invention comprise:

a) a continuous liquid phase, optionally containing at least one chemical agent and optionally a polymeric dispersant; And

b) at least one dispersed phase containing a polymer matrix microparticle, wherein the polymer matrix microparticle has a hardness of more than 0.001 MPa and less than 6 MPa, and the outer surfaces of the particle contain a colloidal solid material and optionally contain a plasticizer, and the polymer particles contain at least one chemical agent distributed therein.

[0033] In one embodiment, the chemicals are agrochemically active ingredients.

[0034] In one embodiment, the colloidal solid material is a colloidal Pickering emulsion stabilizer.

[0035] In one embodiment, the GMs comprise an incorporated agrochemical that is either uniformly or unevenly distributed within such particles or present as domains within such particles.

[0036] In the context of the present invention, average particle or droplet size means volume-weighted average, commonly referred to as Dv50, as determined by dynamic light scattering.

[0037] In the context of the present invention, particle hardness is measured using a nanoindenter technique. The nanoindenter technique has been widely used to determine the mechanical properties of materials on the surface. It is based on the following standards for instrumentation: ASTM E2546 and ISO 14577. Nanoindentation uses an established technique in which an indenter tip (usually conical for relatively soft specimens) of known geometry is pressed into a specific location in the material by applying an increasing normal load. Once the predetermined maximum value has been reached, the normal load is reduced until full relaxation occurs. During the experiment, the position of the indenter relative to the sample surface is precisely controlled by a high-precision capacitive sensor. The resulting load/displacement curves provide data representative of the mechanical nature of the material. Established physical models are used to calculate the hardness, modulus of elasticity, and other mechanical properties of the material. The high spatial resolution of nanoindentation enables testing of local mechanical properties. Accordingly, in one embodiment, the polymeric matrix microparticle has a hardness greater than 0.001 MPa and less than 5 MPa. Accordingly, in another embodiment, the polymeric matrix microparticle has a hardness greater than 0.01 MPa and less than 5 MPa.

[0038] In one embodiment, the agrochemically active ingredient is a solid and distributed in the discontinuous phase, or is a liquid and distributed in the discontinuous phase.

[0039] In another embodiment, the dispersion concentrates for use in the liquid agrochemical compositions of the present invention are those formulated using curing agents, monomers, oligomers, prepolymers, or mixtures thereof, which exhibit a slow curing or polymerization reaction when combined with curing agents in environmental conditions. Particularly suitable are those curing agents, monomers, oligomers, prepolymers, or mixtures thereof, which do not exhibit a significant increase in viscosity at ambient conditions for a period of at least 15 minutes, more particularly 30 minutes, most particularly 1 hour, after mixing with the curing agent.

[0040] According to one embodiment of the present invention, polymerizable thermoset resins are intended to include all molecules that can be irreversibly polymerized or cured to form a polymer matrix that does not melt or deform at elevated temperatures below the thermal degradation point. The polymerization reaction can be initiated thermally by the addition of chemical curing agents or by suitable irradiation to produce radicals or ions, such as visible light, ultraviolet, microwave or other electromagnetic irradiation, or electron beam irradiation. Examples include phenolic resins, ureas, melamines, epoxy resins, polyesters, silicones, rubbers, polyisocyanates, polyamines and polyurethanes. In addition, bioplastic or biodegradable thermoset resins can be used, including epoxy or polyester resins derived from natural materials such as vegetable oil, soy or wood, etc.

[0041] According to another embodiment of the present invention, polymerizable thermoplastic resins are intended to include all molecules that can be polymerized or cured to form a polymer matrix that can melt or deform at elevated temperatures below the thermal degradation point. The polymerization reaction can be initiated thermally by adding chemical curing agents α or by suitable irradiation to produce radicals or ions, such as irradiation with visible light, ultraviolet or other electromagnetic irradiation or electron beam irradiation. Examples of suitable ethylenically unsaturated monomers include styrene, vinyl acetate, α-methylstyrene, methyl methyl acrylate as described in US 2008/0171658, etc. Examples of thermoplastic polymers for polymer particles that can be obtained by in-situ miniemulsion polymerization include polymethyl methacrylate, polystyrene, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, polyacrylate, polyalkyl acrylate, polyalkyl acetate, polyacrylonitrile, or copolymers thereof.

[0042] In accordance with another embodiment of the present invention, it is understood that the curable thermoplastic resins include all molecules that can be dissolved in a volatile solvent, so that the solvent can be evaporated using heat to obtain a polymer matrix that can melt or deform at elevated temperatures below the thermal degradation point. The volatile solvent is chosen to be immiscible with the continuous aqueous phase and volatile enough to be suitably removed from the composition by heating to a temperature below that at which any significant decomposition occurs. Examples include polymers of the ethylenically unsaturated monomers described above, as well as polymers such as cellulose acetate, polyacrylates, polycaprolactone, and polylactic acid. Mention may also be made of polymethyl methacrylate, polystyrene, polyethyl vinyl acetate, cellulose acetate, polyacrylate, polyacrylonitrile, polyamide, polyalkylene terephthalate, polycarbonate, polyester, polyphenylene oxide, polysulfone, polyimide, polyetherimide, polyurethane, polyvinylidene chloride, polyvinyl chloride, polypropylene, and waxes, etc. In addition, bioplastics or biodegradable polymers such as thermoplastic starch, polylactic acid, polyhydroxyalkanoate, polycaprolactone, polyamide ester 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 WO 2011/040956 A1.

[0043] The term "polymer matrix particle" or "polymer matrix microparticle" as used herein means a polymer particle that is substantially uniform in density and polymer composition throughout the particle.

[0044] The term "microparticle" is a term commonly used to describe particles that are microscopic in size. The particles of the polymer matrix according to the technology of the present invention differ from microcapsules, which consist of a well-defined shell wall and a hollow core. In accordance with the present invention, the dispersed phase polymer matrix microparticles have a particle size Dv50 (median diameter) of 1 to 200 microns, more specifically 1 to 100 microns, and most specifically 1 to 80 microns, 1 to 50 microns, and 1-30 microns. .

[0045] In one embodiment, suitable polymerizable resins and polymer solutions are those that are substantially immiscible with the fluid being used in the continuous phase.

[0046] In the context of the present invention, a colloidal solid is one whose properties of interest are determined by its surface interactions with other substances. Therefore, colloidal solids are necessarily those which have a high specific surface area, typically above 10 m ² /g. For example, colloidal solids are capable of stabilizing emulsions of immiscible liquids, as described, for example, in WO 2008/030749. Such colloidal solids serving this purpose may be referred to as Pickering colloids, colloidal emulsion stabilizers, or other equivalent terms. Functional tests are known to determine whether colloidal solids can stabilize an emulsion, as used herein. Not all colloidal solids are capable of stabilizing the 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.

[0047] In another embodiment, where the continuous phase is aqueous, the affinity of aqueous liquids suitable for use in the continuous phase a) for the agrochemically active ingredient distributed in the dispersed phase b) is such that substantially all of the agrochemically active ingredient remains in the dispersed solid phase and there is practically no movement to the continuous phase. Those skilled in the art will be able to readily determine whether a particular aqueous liquid satisfies this criterion for the particular agrochemical active ingredient under consideration by following any standard test procedure to determine the partition ratio of a compound (in this case, the dispersed phase agrochemically active ingredient) between the continuous phase and the discontinuous phase. solid phase. Accordingly, the dispersed solid phase b) is immiscible with the continuous phase a).

[0048] In a further embodiment, aqueous liquids suitable for use in continuous phase a) are solutions of water-soluble solutes in water.

[0049] Water-soluble solutes suitable for use in the continuous phase include salts such as halides, nitrates, sulfates, carbonates, phosphates, nitrites, sulfites, nitrides, and sulfides of ammonium and metals, such as metals from groups 1-12 of the periodic table. Other suitable solutes include sugars and osmolytes such as polysaccharides, proteins, betaines and amino acids.

[0050] In one embodiment, the aqueous liquids suitable for use in continuous phase a) are mixtures of water and a substantially water-miscible non-aqueous liquid. In the context of the present invention, the term "substantially miscible with water" means a non-aqueous liquid which forms a single phase when present in water at a concentration of not more than at least 50% by weight.

[0051] Substantially water-miscible non-aqueous liquids suitable for use in 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 not more than about 800; an acetylated glycol such as dipropylene glycol methyl ether acetate or propylene glycol diacetate; triethyl phosphate; ethyl lactate; gamma-butyrolactone; a water-miscible alcohol such as propanol or tetrahydrofurfuryl alcohol; N-methylpyrrolidone; dimethyl lactamide; and their mixtures. In one embodiment, the non-aqueous substantially water-miscible liquid used in continuous phase a) is a solvent for at least one optional agrochemically active ingredient.

[0052] In another embodiment, the aqueous substantially water-miscible liquid used in continuous phase a) is completely water-miscible in all proportions. Alternatively, the aqueous substantially water-miscible liquid used in the continuous phase a) is a waxy solid, such as polyethylene glycol, having a molecular weight greater than about 1000, and the mixture of this waxy solid with water is maintained in a liquid state by forming the composition at elevated temperature.

[0053] In another embodiment, the continuous liquid phase is a non-aqueous liquid. In another embodiment, the continuous liquid phase is a substantially water-miscible non-aqueous liquid. The water-immiscible non-aqueous liquid may be selected from petroleum distillates, vegetable oils, silicone oils, methylated vegetable oils, purified paraffinic hydrocarbons, alkyl lactates, mineral oils, alkyl amides, alkyl acetates, and mixtures thereof.

[0054] In another embodiment, the continuous phase contains a substantially water-miscible non-aqueous liquid. The water-miscible non-aqueous liquid may be selected from the group consisting of propylene carbonate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, hexylene glycol, polyethylene glycols having a molecular weight of not more than about 800, di(propylene glycol) methyl ether acetate, propylene glycol diacetate , triethyl phosphate, ethyl lactate, gamma-butyrolactone, propanol, tetrahydrofurfuryl alcohol, N-methylpyrrolidone, dimethyl lactamide, and mixtures thereof.

[0055] Those skilled in the art will appreciate that the amounts of water and the nature and amount of the non-aqueous water-miscible liquid or water-soluble solute can be varied to produce mixed aqueous liquids suitable for use in the continuous phase a), and these amounts can be determined without excessive experimentation. In one embodiment, the aqueous continuous phase contains from 5 to 95 wt. %, more preferably from 30 to 90 wt. % ethylene glycol in equilibrium with water. In another embodiment, the aqueous continuous phase contains from 5 to 95 wt.%, more preferably from 30 to 90 wt.% glycerol in equilibrium with water.

[0056] In one embodiment, the compositions of the liquid dispersion concentrates of the present invention contain a mixture of GM, each of which contains one or more chemicals (such as an agrochemical active ingredient). Each of the chemicals is contained within the same or different GM discontinuous phase, and each respective discontinuous phase particle optionally contains a different polymer matrix, as described above. Optionally, each respective dispersed phase may have different particle sizes.

[0057] In one embodiment, the liquid dispersion concentrate compositions of the present invention comprise a discontinuous phase in the form of highly dispersed, suspended polymer particles containing a colloidal solid material on their outer surface and containing at least one agrochemically active ingredient.

[0058] The advantages of the compositions of liquid dispersion concentrates (eg, gel emulsions) of the present invention include stability during storage for long periods, several agrochemicals with different physical states can be combined in a dispersion of mutually compatible particles; improved adhesion to surfaces where deposits can dry out; reduced potential for crop damage due to the presence of solvents or other phytotoxic agents; improved acute toxicity; ease of handling, which makes it possible for users to obtain mixtures for application, since dilution occurs with water or other liquid carrier; the compositions can be easily resuspended or redispersed with only slight agitation and do not stick together when diluted with fertilizer solutions to form application mixtures. The term "storage stability" as used herein means that a given composition has a Dv50 that changes by less than about 20% over a period of 6 months at 70°F.

Agrochemically active ingredients

[0059] The term "agrochemically active ingredient" refers to chemicals and biological compositions, such as those described herein, that are effective in killing, preventing, or controlling the growth of unwanted pests such as plants, insects, mice, microorganism, algae, fungi, bacteria, etc. (such as pesticidally active ingredients). The term can also be applied to compounds that act as adjuvants to aid in the 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 an activated natural systemic resistance response found in plant species (eg, a plant activator), or to a compound that reduces phytotoxicity. reaction to herbicides (for example, an antidote). If more than one is present, the agrochemically active ingredients are independently present in an amount that is biologically effective when diluted with the composition, if necessary, in a suitable volume of a liquid carrier, such as water, and applied to the intended target, such as the foliage of a plant or its locus.

[0060] Examples of agrochemical active ingredients suitable for use in the continuous phase a) or dispersed phase b) according to the present invention include, without limitation, fungicides such as azoxystrobin, benzovindiflupyr, chlorothalonil, cyproconazole, cyprodinil, difenoconazole, fenpropidine, fludioxonil, mandipropamide, mefenoxam, paclobutrazol, picoxystrobin, propiconazole, pyraclostrobin, sedaxan, tebuconazole, thiabendazole and trifloxystrobin; herbicides such as acetochlor, alachlor, ametrin, anilophos, atrazine, azaphenidin, benfluralin, benfuresate, bensulide, benzfendison, benzofenap, bicyclopyrone, bromobutide, bromophenoxime, bromoxynil, butachlor, butafenacil, butamiphos, butralin, butylate, cafenstro l, carbetamide, chloridazone, chlorpropham, chlorthal-dimethyl, chlorothiamide, cynidone-ethyl, cinmethylin, clomazone, clomeprop, cloransulam-methyl, cyanazine, cycloate, desmedifam, desmetrin, dichlobenil, diflufenican, dimepiperate, dimethachlor, dimethamethrin, dimethenamid, dimethenamid-R, dinitramine, dinoterb , diphenamide, dithiopyr, EPTC, esprocarb, ethalfluralin, etofumesate, etobenzanide, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, flamprop-methyl, flamprop-M-isopropyl, fluazolate, fluchloralin, flufenacet, flumiclorac-pentyl, flumioxazine, flurochloridone , flupoxam, flurenol, fluridone, flurtamone, fluthiacet-methyl, indanophane, isoxaben, isoxaflutol, lenacil, linuron, mefenacet, mesotrione, metamitron, metazachlor, metabenzthiazuron, methyldymron, methobenzuron, metolachlor, methosulam, methoxsuron, metribuzin, molinate, naproanil d, napropamide, Neburon, Norflurazon, Orbenkarb, Orizalin, oxadiargil, oxadiazone, oxifluorphen, pebulat, pendimetalin, pentanochlor, petoxamid, pentoxazone, fenmedifam, pinoxsaden, piperofos, praylchlor, podiamin, vocationalizer, vintelin, prophetor, rampant, rampant, rampant, rampart, rampart , proofam, propizochlor, propizamide, prosulfocarb, pidiflumethofen, pyraflufen-ethyl, pyrazogyl, pyrazolinate, pyrazoxyfen, pyributicarb, pyridate, pyriminobac-methyl, quinclorac, sidurone, simazine, simetrin, S-metolachlor, sulcotrione, sulfentrazone, tebutam, tebuthiuron, terbacil, ter bumeton, terbutylazine, terbutrin, tenylchlor, thiazopyr, thidiazimin, thiobencarb, thiocarbazil, triallat, trietazine, trifluralin and vernolat; herbicide safeners such as benoxacor, dichlormide, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr; an alkali metal, alkaline earth metal, sulfonium or ammonium cation of mefenpyr; mefenpyr-diethyl and oxabethrinil; insecticides such as abamectin, clothianidin, cyantraniliprole, cyantraniliprole, 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.

[0061] In one embodiment, the active ingredients in the continuous phase may be in the form of a solution, emulsion, microemulsion, microcapsule, particle, or fine particle. In the context of the present invention, a fine particle is a particle with a substantially smaller size than the GM dimensions of the discontinuous phase such that a plurality (at least 10) of active ingredient particles reside within each particle of the discontinuous phase, while a particle other than the fine particle , is a particle with dimensions only slightly smaller than the GM dimensions of the discontinuous phase, so that each polymer particle contains only a few active ingredient particles.

[0062] Additional aspects of the present invention include a method of preventing or controlling infestation of plant species by pests and regulating plant growth by diluting an amount of the concentrate composition with a suitable liquid carrier, such as water or liquid fertilizer, and applying to a plant, tree, animal, or habitat at need. The compositions of the present invention can also be combined with water in a continuous flow device in spray application equipment so that there is no need for a reservoir to store the diluted product.

[0063] Liquid dispersion concentrate compositions can conveniently be stored in a container from which they are poured or pumped out, or to which a liquid carrier is added prior to use.

[0064] If a solid agrochemical active 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 GM. The solid may be dry ground using an air mill or other equipment as needed to achieve the desired particle size. The particle size may be a Dv50 particle size of from about 0.2 to about 20 microns, suitably from about 0.2 to about 15 microns, more suitably from about 0.2 to about 10 microns.

[0065] As used herein, the term "agrochemically effective amount" means an amount of an agrochemically active compound that downregulates or modifies the target pest or provides plant growth regulation (PGR). For example, in the case of herbicides, a "herbicidally effective amount" is an amount of herbicide sufficient to control or modify plant growth. Effects in relation to control or modification include all deviations from natural development, for example, destruction, inhibition of development, leaf scorching, albinism, dwarfing, etc. The term "plants" refers to all physical parts of a plant, including seeds, seedlings, shoots, roots, tubers, stems, stalks, foliage, and fruits. In the case of fungicides, the term "fungicide" means a material that kills or substantially inhibits the growth, proliferation, division, reproduction or expansion of fungi. As used herein, the term "fungicidally effective amount" or "an amount effective to control or reduce the growth rate of fungi" in relation to fungicidal compounds is an amount that will kill or substantially inhibit the growth, proliferation, division, propagation or growth of a significant the number of mushrooms. As used herein, the terms "insecticide", "nematocide", or "acaricide" will mean a substance that kills or substantially inhibits the growth, proliferation, division, reproduction, or spread of insects, nematodes, or mites, respectively. An "effective amount" of an insecticide, nematocide, or acaricide means an amount that kills or substantially inhibits the growth, proliferation, reproduction, or spread of a significant number of insects, nematodes, or mites.

[0066] In one aspect, as used herein, the terms "regulating growth (of plants)", "plant growth regulator", PGR, "regulating", or "regulating" include the following plant responses: distances, strengthening the stem wall, thus increasing resistance to lodging; compact growth of ornamental plants for cost-effective production of plants with improved qualities; stimulation of better fruiting; increase in the number of ovaries based on an increase in yield; stimulating the aging of tissue formations that provide fruits with the opportunity to fall off; deleafing of greenhouse and ornamental bushes and trees for mail-order litter trade; deleafing trees to break parasitic chains of infection; accelerating maturation for harvest planning by reducing the number of harvests to one or two harvests and interrupting the food chain of harmful insects.

[0067] In another aspect, "regulating growth (plants)", "plant growth regulator", "PGR", "regulating" or "regulating" also includes the use of a composition, as defined in accordance with the present invention, to increase yield and/or increase the vitality of the agricultural plant. In accordance with one embodiment of the present invention, the compositions of the present invention are used to increase resistance against stress factors such as fungi, bacteria, viruses and/or insects, and stress factors such as heat stress, nutrient stress, cold stress, induced stress. drought, UV stress and/or salt stress in an agricultural plant.

[0068] The choice of application rates associated with providing the desired level of pesticidal activity of the composition of the present invention is a routine procedure for a person skilled in the art. Application rates will depend on factors such as pest exposure, plant health, weather and growing conditions, as well as the potency of the agrochemically active ingredients and any associated label rate limits.

Embodiments

[0069] The present invention also relates to gel emulsion agrochemical compositions containing:

a) a continuous aqueous liquid phase, optionally containing at least one agrochemically active ingredient; And

b) at least one dispersed phase containing polymer particles obtained either from a curable or polymerizable resin or a hardenable thermoplastic polymer and containing a colloidal solid material on its outer surface, while the particle hardness is more than 0.001 MPa and less than 6 MPa, and when this particles contain at least one agrochemically active ingredient, distributed in them.

[0070] A further aspect of the present invention relates to a diluted aqueous spray composition for pest control or plant growth control in situ, comprising:

a) a continuous aqueous phase containing a suitable liquid carrier, such as water or liquid fertilizer, in an amount sufficient to obtain the desired final concentration of each active ingredient in the spray composition;

b) at least one dispersed phase containing polymer particles obtained either from a curable or polymerizable resin or a hardenable thermoplastic polymer and containing a colloidal solid material on its outer surface, while the particle hardness is more than 0.001 MPa and less than 6 MPa, and when this particles contain 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 carrier liquid.

[0071] In another embodiment, the present invention provides a diluted pesticide and/or ultra low volume (ULV) PGR composition comprising:

a) a continuous phase containing a carrier solvent with a flash point above 55° C. in an amount sufficient to obtain the required final concentration of each of the active ingredients in the ULV composition;

b) at least one dispersed phase containing polymer particles obtained either from a curable or polymerizable resin or a hardenable thermoplastic polymer and containing a colloidal solid material on its outer surface, while the particle hardness is more than 0.001 MPa and less than 6 MPa, and when this particles contain at least one agrochemically active ingredient, distributed in them.

[0072] The present invention also relates to a method for controlling or preventing the occurrence of pests in agricultural crops of useful plants or regulating the growth of such crops, this method includes:

1) treating the desired site, such as plants, parts of plants or their places of growth, with a concentrate composition containing:

a) a continuous aqueous liquid phase, optionally containing at least one agrochemically active ingredient, and optionally containing at least one acidic or basic component;

b) at least one dispersed phase containing polymer particles obtained either from a curable or polymerizable resin or a hardenable thermoplastic polymer and containing a colloidal solid material on its outer surface, while the particle hardness is more than 0.001 MPa and less than 6 MPa, and when this particles contain at least one agrochemically active ingredient, distributed in them; or

2) if necessary, diluting the concentrate composition in a suitable vehicle, such as water, liquid fertilizer or a carrier solvent with a flash point above 55° C., in an amount sufficient to obtain the desired final concentration of each of the agrochemically active ingredients; and then treating the site of interest, such as plants, parts of plants or their habitats, with the diluted spray composition or ULV composition.

[0073] The term "plants" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, flowers, stalks, leaves, and fruits. The term "place of growth" refers to the place where the plant grows or where it is expected to grow.

[0074] The composition of the present invention is suitable for all application methods commonly used in agriculture, such as pre-emergence application, post-emergence application, post-harvest application and seed dressing. Compositions in accordance with the present invention are suitable for pre- and post-emergence applications to cultivated crop areas.

[0075] The compositions of the present invention are also suitable for pest control and/or for the prevention of pests in crops of useful plants or for regulating the growth of such plants. In some embodiments, the compositions can be applied by any method that is commonly used, including spraying, dripping, and soaking. One advantage of the GM formulations of the present invention is that their small size provides uniform coverage of the stems and foliage of plants where the distance between the particles of the formulation is small. Thus, the composition is more effective when brought into contact with pests that damage the plant.

[0076] Preferred beneficial plant crops include corn, canola, cereals such as barley, oats, rye and wheat, cotton, soybeans, sugar beets, fruits, berries, nuts, vegetables, flowers, trees, shrubs, and turf. The components used in the composition of the present invention can be used in various concentrations known to those skilled in the art. The rate at which compositions are applied will depend on the particular type of pest to be controlled, the degree of control required, and the timing and method of application.

[0077] It should be understood that crops also include those crops that have been made tolerant to herbicides or herbicide classes (e.g., ALS-, GS-, EPSPS-, PPO-, ACCase-, and HPPD-inhibitors) using conventional breeding techniques. or through genetic engineering. An example of a crop that has been made tolerant to imidazolinones, such as imazamox, using traditional breeding methods is Clearfield® rape (canola). Examples of crops that have been genetically engineered to tolerate herbicides include, for example, glyphosate and glufosinate resistant maize varieties commercially available under the RoundupReady® and LibertyLink® trademarks.

[0078] Also, crops should be understood as those that have been made resistant to harmful insects using genetic engineering methods, such as Bt-maize (resistant to corn borer), Bt-cotton (resistant to cotton weevil), as well as varieties of Bt- potatoes (resistant to the Colorado potato beetle). Examples of Bt maize are Bt 176 NK® maize hybrids (Syngenta Seeds). Bt toxin is a protein that is naturally produced by the soil bacteria Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP-A-451878, EP-A-374753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427529. Examples of transgenic plants containing one or more genes encoding insect resistance and expressing one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato varieties), NatureGard® and Protexcta®. Agricultural crops of plants or their seed material can be both resistant to herbicides and at the same time resistant to eating by insects (transgenic objects with "packaged" genes). For example, a seed may have the ability to express the insecticidal Cry3 protein while being tolerant to glyphosate.

[0079] It should also be understood that crops include those obtained by traditional breeding or genetic engineering methods and possessing so-called added traits (eg, improved storage stability, higher nutritional value, and improved taste).

[0080] Other useful plants include turf grass, such as on golf courses, lawns, parks and roadsides, or commercially grown for turf, and ornamental plants, such as flowers or shrubs.

[0081] Cultivated crop areas are areas of land on which cultivated plants are already grown or on which the seeds of these cultivated plants have been sown, as well as land areas on which these cultivated plants are intended to grow.

[0082] Other active ingredients such as a herbicide, plant growth regulator, algaecide, fungicide, bactericide, viricide, insecticide, acaricide, nematocide, or molluscicide may be present in the formulations of the present invention or may be added to the formulations as a tank mix counterpart.

[0083] the Compositions of the present invention may additionally contain other inert additives. Such additives include thickeners, anti-caking agents, dispersants, emulsifiers, wetting agents, antifoam agents, biocides, lubricants, fillers, flow control agents, settling enhancers, auxiliary agents, evaporation retardants, freeze protection agents, attractants insects with a specific smell, UV protection products, fragrances, etc. The thickener may be a compound that can dissolve or swell in water, such as, for example, xanthan polysaccharides (for example, anionic heteropolysaccharides such as RHODOPOL® 23 (xanthan gum) (Rhodia, Cranburi, NJ)), alginates, guars, or cellulose; synthetic macromolecules such as modified cellulose-based polymers, polycarboxylates, bentonites, montmorillonites, hectonites or attapulgites. The antifreeze agent can be, for example, ethylene glycol, propylene glycol, glycerol, diethylene glycol, sucrose, water-soluble salts such as sodium chloride, sorbitol, triethylene glycol, tetraethylene glycol, urea, or mixtures thereof. Illustrative defoamers are silicone oils, polydialkylsiloxanes, in particular polydimethylsiloxanes, fluoroaliphatic esters or perfluoroalkylphosphonic/perfluoroalkylphosphonic acids, or salts thereof, and mixtures thereof. Suitable antifoams are polydimethylsiloxanes such as Antifoam A, Antifoam B, or Dow Corning® MSA Antifoam. Exemplary biocides include 1,2-benzisothiazolin-3-one available under the name PROXEL® GXL (Arch Chemicals). Conventional surfactants can only be present at low concentrations due to their ability to form micelles in the aqueous phase as these micelles extract the solvent, plasticizer and/or active ingredient from the GM. Thus, while conventional surfactants are useful for controlling the viscosity of GM dispersions, at higher concentrations they are able to extract components from the particles and eliminate their benefits. Thus, compositions according to the technology of the present invention may not contain conventional surfactants in concentrations above that at which they form micelles, and this concentration is called the critical micelle concentration (CMC). For this reason, non-micellar polymeric dispersants are preferred for controlling the viscosity of GM dispersions. Examples of common surfactants that form micelles are linear and branched alcohol ethoxylates and their acid esters, tristyrylphenol ethoxylates and their acid esters, alkyl phenol ethoxylates and their acid esters, linear or branched alkyl aryl sulfonates, such as dodecylbenzenesulfonate, fatty acid ethoxylates, alkylamine ethoxylates, ethylene oxide block copolymers and higher alkylene (propylene, butylene) oxides. Examples of non-micellar polymeric dispersants include 15-120 kDa polyvinylpyrrolidone homopolymer, polyvinylpyrrolidone-vinyl acetate random copolymer, lignosulfonates, sulfonated urea-formaldehyde condensates, styrene-acrylic copolymers, comb polymers with an alkyl backbone and polyacrylic acid side chains, alkylated polyvinylpyrroles don and others conventional non-emulsifying dispersants.

[0084] Dispersants are well known in the art and their choice will depend on various factors depending on the composition. Preferred dispersants as noted above include, but are not limited to, 15-120 kDa polyvinylpyrrolidone homopolymer, polyvinylpyrrolidone-vinyl acetate random copolymer, lignosulfonates, sulphonated urea-formaldehyde condensates, styrene-acrylic copolymers, comb polymers with an alkyl backbone and polyacrylic acid side chains. , alkylated polyvinylpyrrolidone and other conventional non-emulsifying dispersants.

[0085] The compositions of the present invention can be mixed with fertilizers and still retain their stability.

[0086] the Compositions of the present invention can be used in traditional agricultural methods. For example, the compositions of the present invention may be mixed with water and/or fertilizers and may be applied to the desired pre-emergence and/or post-emergence habitat/habitat in any manner such as aircraft spray tanks, irrigation equipment, spray direct injection equipment, knapsack spray tanks, livestock bathing barrels, farm equipment used in ground spraying (e.g. boom sprayers, hand sprayers), etc. The required habitat/habitat may be soil, plants, etc.

[0087] The technology of the present invention also includes a method of treating seeds or plant parts for vegetative propagation, including bringing said seeds or plant parts for vegetative propagation into contact with the composition of the present invention. The technology of the present invention can be applied to a seed or plant part for vegetative propagation in any physiological state at any time between seed collection and seed sowing; during or after sowing; and/or after germination. Preferably, the seed or part of the plant for vegetative propagation is in a sufficiently stable state that during processing it is not subjected to damage or minimal damage, including physical damage or biological damage. The composition can be applied to seeds or plant parts for vegetative propagation using conventional coating or coating techniques and devices such as fluidized bed techniques, roller mill processes, rotostatic seed dressers and coaters. Before coating, seeds or plant parts for vegetative propagation may be pre-sorted by size. After coating, the seeds or plant parts for vegetative propagation are typically dried and then transferred to a grading machine for size grading. Such procedures are known in the art. In some embodiments, the composition of the present invention is applied as a single coating ingredient to seeds or plant parts for vegetative propagation. Treated seeds can also be covered with a film top coat to protect the coating. Such topcoats are known in the art and can be applied using conventional fluid bed and drum coating techniques, for example.

[0088] Within the scope of the present invention are various methods for producing a dispersed phase GM containing chemicals, which are described as chemicals that are agriculturally active ingredients. Each method provides a dispersed phase that contains GM having a particle hardness greater than 0.001 MPa and less than 6 MPa with at least one agriculturally active ingredient dispersed therein and a colloidal solid material on the surface of the particle.

[0089] The first method includes the following steps:

1. obtaining a dispersion concentrate by dissolving or suspending at least one agrochemically active ingredient in a non-aqueous curable liquid mixture containing at least one suitable crosslinkable resin (containing monomers, oligomers, prepolymers or mixtures thereof), while the resin optionally contains hydrophilic groups, optionally a suitable hardener, catalyst, plasticizer or activator;

2. emulsifying said dispersion concentrate to an average droplet size of 1-200 microns in an aqueous liquid, where the liquid contains a colloidal solid as an emulsion stabilizer, optionally contains a plasticizer and optionally certain suitable hardener, catalyst or activator capable of diffusing into the droplets of the dispersed uncured resin; And

3. providing crosslinking or curing of the crosslinkable resin mixture and optionally then impregnating with a plasticizer to obtain cured thermoset polymer particles with a particle hardness of more than 0.001 MPa and less than 6 MPa with at least one agriculturally active ingredient distributed therein and a colloidal solid material on the particle surface.

[0090] The second method is essentially identical to the first, except that the dispersion concentrate contains a polymerizable resin instead of a crosslinkable resin as a non-aqueous liquid. Instead of a vulcanization reaction in step 3, the discontinuous phase particles are formed by a polymerization reaction such that the resulting discontinuous phase contains thermoplastic polymer particles rather than thermoset polymer particles.

[0091] The third method includes the following steps:

1. dissolving or suspending at least one agrochemically active ingredient in a non-aqueous liquid mixture containing at least one suitable hardening polymer dissolved in a volatile solvent and one or more optional plasticizers;

2. emulsifying said solution to an average droplet size of 1-200 microns in an aqueous liquid, wherein the liquid contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; And

3. allowing the volatile solvent to evaporate by heating the emulsion to a temperature of about 30-120°C for about 0.1-10 hours and then optionally impregnating with a plasticizer to obtain thermoplastic polymer particles with a hardness of more than 0.001 MPa and less than 6 MPa with at least one an agriculturally active ingredient distributed therein, and a colloidal solid material on the surface of the particle.

[0092] The fourth production method includes the following steps:

1. obtaining a dispersion concentrate by dissolving or suspending at least one agrochemically active ingredient in a non-aqueous curable liquid mixture containing a melt of at least one suitable curable thermoplastic polymer and optionally a plasticizer;

2. emulsifying said dispersion concentrate to an average droplet size of 1-200 microns in a heated aqueous liquid which contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; And

3. Cooling the emulsion and then optionally impregnating with a plasticizer to produce thermoplastic polymer particles with a hardness greater than 0.001 MPa and less than 6 MPa with at least one agriculturally active ingredient dispersed therein and a colloidal solid material on the surface of the particle.

[0093] In situations where the active ingredient is soluble or miscible with a plasticizer, each of the variant methods above can be modified so that the active ingredient is added after the step of curing, solidifying or extracting the solvent from the liquid emulsion droplets, so that the active ingredient impregnates or is dissolved in GM after formation, and is not present in the dispersion concentrate initially. Four examples of methods for producing such GM include the following.

[0094] The first method includes the following steps:

1. obtaining a non-aqueous curable liquid containing at least one suitable crosslinkable resin (containing monomers, oligomers, prepolymers or mixtures thereof), while the resin optionally contains hydrophilic groups, optionally a suitable hardener, catalyst, plasticizer or activator;

2. emulsifying said non-aqueous curable liquid to an average droplet size of 1-200 microns in an aqueous liquid, wherein the aqueous liquid contains a colloidal solid as an emulsion stabilizer, optionally contains a plasticizer and optionally certain suitable hardener, catalyst or initiator capable of diffusing into the droplets of dispersed uncured resins;

3. allowing the crosslinkable resin mixture to crosslink or cure and then optionally impregnate with a plasticizer to form an emulsion containing the cured thermoset polymer particles and colloidal solid material on the surface of the particle; And

4. adding at least one agricultural active ingredient to the emulsion to obtain cured thermosetting polymer particles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agricultural active ingredient dispersed therein.

[0095] The second method is essentially identical to the first, except that the dispersion concentrate as a non-aqueous liquid contains a polymerizable resin instead of a crosslinkable resin. Instead of a vulcanization reaction in step 3, the discontinuous phase particles are formed by a polymerization reaction such that the resulting discontinuous phase contains thermoplastic polymer particles rather than thermoset polymer particles.

[0096] The third method includes the following steps:

1. obtaining a non-aqueous liquid containing at least one suitable hardening polymer dissolved in a volatile solvent, and one or more optional plasticizers;

2. emulsifying said non-aqueous liquid to an average droplet size of 1-200 microns in an aqueous liquid, wherein the aqueous liquid contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer;

3. allowing the volatile solvent to evaporate by heating the emulsion to a temperature of about 30-120° C. for about 0.1-10 hours and then optionally impregnating with a plasticizer to form solid thermoplastic polymer particles and a colloidal solid material on the surface of the particle; And

4. adding at least one agricultural active ingredient to the emulsion to obtain thermoplastic polymer particles with a particle hardness that is more than 0.001 MPa and less than 6 MPa, with the agricultural active ingredient dispersed therein.

[0097] The fourth production method includes the following steps:

1. obtaining a non-aqueous curable liquid containing a melt of at least one suitable curable thermoplastic polymer and optionally a plasticizer;

2. emulsifying said non-aqueous curable liquid to an average droplet size of 1-200 microns in a heated aqueous liquid, the aqueous liquid containing a colloidal solid as an emulsion stabilizer and optionally containing a plasticizer; And

3. cooling the emulsion and then optionally impregnating with a plasticizer to form thermoplastic polymer particles in the emulsion and a colloidal solid material on the surface of the particle; And

[0098] adding at least one agriculturally active ingredient to an emulsion to obtain thermoplastic polymer particles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient dispersed therein.

[0099] In another embodiment, each of the above methods can be modified so that the active ingredient is added before the step of curing, solidifying or extracting the solvent from the liquid emulsion droplets, and also after the step of curing, solidifying or extracting the solvent from the liquid emulsion droplets, so that additional active the ingredient or ingredients were impregnated with or dissolved in GM after formation. The active ingredients may be the same or different. Four examples of methods for producing such GM include the following.

[0100] The first method includes the following steps:

1. obtaining a dispersion concentrate by dissolving or suspending at least one agrochemically active ingredient in a non-aqueous curable liquid mixture containing at least one suitable crosslinkable resin (containing monomers, oligomers, prepolymers or mixtures thereof), while the resin optionally contains hydrophilic groups, optionally a suitable hardener, catalyst, plasticizer or activator;

2. emulsifying said dispersion concentrate to an average droplet size of 1-200 microns in an aqueous liquid, where the liquid contains a colloidal solid as an emulsion stabilizer, optionally contains a plasticizer and optionally certain suitable hardener, catalyst or activator capable of diffusing into the droplets of the dispersed uncured resin; And

3. allowing the crosslinkable resin mixture to crosslink or cure and then optionally impregnate with a plasticizer to form emulsions containing cured thermoset polymer particles with at least one agriculturally active ingredient dispersed therein and a colloidal solid material on the surface of the particle; And

4. adding an additional amount of the agriculturally active ingredient to the emulsion to obtain cured thermosetting polymer particles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient or ingredients dispersed therein.

[0101] The second method is essentially identical to the first, except that the dispersion concentrate contains a polymerizable resin instead of a crosslinkable resin as a non-aqueous liquid. Instead of a vulcanization reaction in step 3, the discontinuous phase particles are formed by a polymerization reaction such that the resulting discontinuous phase contains thermoplastic polymer particles rather than thermoset polymer particles.

[0102] The third method includes the following steps:

1. dissolving or suspending at least one agrochemically active ingredient in a non-aqueous liquid mixture containing at least one suitable settable polymer dissolved in a volatile solvent and one or more optional plasticizers;

2. emulsifying said solution to an average droplet size of 1-200 microns in an aqueous liquid, wherein the liquid contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer;

3. allowing the volatile solvent to evaporate by heating the emulsion to a temperature of about 30-120°C for about 0.1-10 hours and then optionally impregnating with a plasticizer to form solid thermoplastic polymer particles with at least one agriculturally active ingredient, distributed in them, and colloidal solid material on the surface of the particle; And

4. adding an additional amount of agriculturally active ingredient to the emulsion to obtain thermoplastic polymer particles with a particle hardness that is more than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient or ingredients dispersed therein.

[0103] The fourth production method includes the following steps:

1. obtaining a dispersion concentrate by dissolving or suspending at least one agrochemically active ingredient in a non-aqueous curable liquid mixture containing a melt of at least one suitable curable thermoplastic polymer and optionally a plasticizer;

2. emulsifying said dispersion concentrate to an average droplet size of 1-200 microns in a heated aqueous liquid which contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; And

3. cooling the emulsion and then optionally impregnating with a plasticizer to form thermoplastic polymer particles with at least one agriculturally active ingredient distributed therein and a colloidal solid material on the surface of the particle; And

4. adding an additional amount of agriculturally active ingredient to the emulsion to obtain thermoplastic polymer particles with a particle hardness that is more than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient or ingredients dispersed therein.

[0104] In one embodiment, the dispersion concentrate is obtained by:

A. dissolving or suspending at least one agrochemically active ingredient in a non-aqueous liquid mixture (premix) containing at least one suitable curable or polymerizable resin (containing monomers, oligomers, prepolymers, or mixtures thereof), optionally a suitable hardener, plasticizer, catalyst, or activator;

b. emulsifying said solution or suspension to an average droplet size of 1-200 microns in an aqueous liquid that also contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer, certain suitable hardener, catalyst or activators capable of diffusing into the droplets of the dispersion uncured or unpolymerized resin; And

c. allowing the resin mixture to be crosslinked, cured or polymerized and optionally then impregnated with a plasticizer to form cured thermoset or polymerized thermoplastic resinous polymer particles with a hardness greater than 0.001 MPa and less than 6 MPa with at least one agriculturally active ingredient dispersed therein, and colloidal solid material on the surface of the particle, and which, after curing, are distributed in an aqueous liquid.

[0105] In one embodiment, the dispersion concentrate is made by adding a curing agent through the continuous phase after the Pickering emulsion is formed so that the dispersion phase premix is incapable of curing. Alternatively, a first very weakly reactive hardener can be used in the dispersion concentrate and then a second fast hardening hardener, accelerator or catalyst can be added to the continuous phase. These second agents are added to the continuous phase after the discontinuous phase has been emulsified, so they must be chosen to be miscible in the continuous phase. Suitable water-miscible fast acting hardeners include diethylenetriamine, triethylenetetramine, xylenediamine, polyethylene glycoldiamine, isophoronediamine, and polyoxypropylenediamine. For additional flexibility, mixtures of hardeners can also be used.

[0106] In one embodiment, the dispersion concentrate is obtained by adding a premix of the discontinuous phase to a premix of the continuous phase, where

1) a dispersed phase premix is obtained by mixing with a high shear mixer at least one agriculturally active ingredient, at least one suitable curable or polymerizable monomer, oligomer, resin prepolymer or mixture thereof, a suitable hardener, catalyst or activator;

2) a continuous phase premix is prepared by mixing an aqueous liquid with a colloidal solid as an emulsion stabilizer using a low shear mixer.

[0107] The resulting mixtures of the dispersed phase premix and the continuous phase premix are stirred at high speeds for a suitable period of time to form a Pickering emulsion, and then heated or exposed to light or other electromagnetic radiation conditions (UV, microwaves) as needed for polymerization of the dispersed phase. The shear rate and duration of emulsification can be readily 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 coarse and may be larger than desired; if the shear rate, on the contrary, is too high or too long, then the emulsion-stabilizing colloid eventually decreases so much in the continuous phase that any new interface between the dispersed and continuous phases is effectively unprotected, resulting in rapid coalescence or heteroflocculation of the discontinuous phase. , and the Pickering emulsion becomes inhomogeneous.

[0108] In one embodiment, a mixture of the discontinuous phase premix and the continuous phase premix is mixed under high shear conditions for 5-10 minutes and heated to a temperature of about 30-120°C for about 0.1-10 hours to influence the curing reaction.

[0109] In one embodiment, the dispersion concentrate is obtained by:

a. dissolving or suspending at least one agrochemically active ingredient in a non-aqueous liquid mixture containing at least one suitable polymer dissolved in a volatile solvent;

b. emulsifying said 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. allowing the volatile solvent to evaporate by heating the emulsion to a temperature of about 30-120°C for about 0.1-10 hours to produce thermoplastic polymer particles with a hardness greater than 0.001 MPa and less than 6 MPa with at least one agriculturally active ingredient distributed in them, and colloidal solid material on the surface of the particles, and which are dispersed in an aqueous liquid. If necessary, more liquid can be added to the continuous phase to replace any liquid lost during the evaporation process.

[0110] Preferred polymerizable resins for use in making dispersed phase polymer particles include thermosets such as epoxy resins, phenolic resins, aminoplasts, polyester resins, polyacrylate, biodegradable polymer, polyurethane, and polyurea. Epoxy resins are particularly preferred. Combinations of these resins can also be used to achieve miscibility with other components of the continuous phase and to control polymerization kinetics.

[0111] Other suitable polymerizable resins for use in preparing discontinuous phase polymer particles include thermoplastic resins such as styrenes, methyl methacrylates, and acrylics. Combinations of these resins can also be used to achieve miscibility with other components of the continuous phase.

[0112] Preferred thermoplastic polymers include those of the thermoplastic resins described above, as well as polymers such as cellulose acetate, polyacrylates, polycaprolactone, and polylactic acid.

[0113] The polymerization reaction can be initiated thermally, by adding curing chemicals and/or catalysts, or by using suitable irradiation such as visible, UV, microwave, or other electromagnetic radiation, electron beam irradiation, or sonication to produce reactive particles such as radicals or ions.

[0114] Suitable monomers for the present invention include vinylaromatic monomers such as styrene, α-methylstyrene, divinylbenzene, etc., esters of α,β-monoethylenically unsaturated mono- and dicarboxylic acids, in particular acrylic acid esters such as ethyl acrylate, n-butyl acrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, and methacrylic acid esters such as ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, etc. Suitable monomers are furthermore vinyl esters and allyl esters of aliphatic carboxylic acids, for example vinyl acetate and vinyl propionate, vinyl halides such as vinyl chloride and vinylidene chloride, conjugated diolefins such as butadiene and isoprene. Examples of suitable unsaturated monomers also include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, N-vinylformamide, and N-vinylpyrrolidone, as well as acrylic acid, methacrylic acid, styrenesulfonic acid, and vinylphosphonic acid.

[0115] Additional examples of polymers suitable for use in preparing GM of the present invention include phenolic resins, ureas, melamines, epoxy resins, silicones, polyisocyanates, polyamines and polyurethanes, polycarbonate, polyalkylene terephthalate, polyphenylene oxide, polysulfone, polyimide, polyetherimide, polyhydroxyalkanoate, polycaprolactone, polyamide ester and polylactic acid. In addition, a biopolymer or biodegradable resins derived from natural materials such as plants, algae, microbes, or animals, including vegetable or algal oils, lignin, humic acid, glycoproteins, proteins, polypeptides, polysaccharides, cellulose or hemicellulose, etc., can be used. d.

[0116] With regard to epoxy resins, all conventional mono-, di- and polyepoxy monomers, prepolymers, or mixtures thereof are suitable epoxy resins for practicing the present invention. In one embodiment, suitable epoxy resins are resins that are liquid at ambient temperature. The di- and polyepoxides can be aliphatic, cycloaliphatic or aromatic compounds. Typical examples of such compounds are diglycidyl ethers of bisphenol A, glycerol or resorcinol, glycidyl ethers and β-methylglycidyl ethers of aliphatic or cycloaliphatic diols or polyols, including 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' dihydroxyphenyl-2,2-propane, novolacs and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Additional examples are N-glycidyl compounds, including diglycidyl compounds of ethylene urea, 1,3-propylene urea or 5-dimethylhydantoin or 4,4' methylene-5,5' tetramethyldigidantoin, or such as triglycidyl isocyanurate, or biodegradable/bioepoxy resins (based on vegetable oils). ). Preferably, the epoxy resin is bisphenol A diglycidyl ether, glycerin, polypropylene oxide, neopentyl, resorcinol, cyclohexanedimethanol, butanediol, polyethylene oxide or polyalkylene oxide, or a mixture of two or more of these esters.

[0117] Additional glycidyl compounds of industrial importance are glycidyl esters of carboxylic acids, especially di- and polycarboxylic 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 partially polymerized, for example dimerized, fatty acids.

[0118] Examples of polyepoxides other than glycidyl compounds are vinylcyclohexene and dicyclopentadiene diepoxides, 3-(3',4'-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.

[0119] Other suitable epoxy resins are diglycidyl ethers or higher diglycidyl ethers of dihydric phenols or dihydric aliphatic alcohols with 2-4 carbon atoms, preferably diglycidyl ethers or higher diglycidyl ethers of 2,2-bis(4-hydroxyphenyl)propane and bis(4 -hydroxyphenyl)methane or mixtures of such epoxy resins.

[0120] Suitable epoxy curing agents for the practice of the present invention may be any suitable epoxy curing agent, generally selected from primary and secondary amines and their adducts, cyanamide, dicyandiamide, polycarboxylic acids, polycarboxylic acid anhydrides, polyamines, polyaminoamides, polyamine adducts, and polyepoxides, and full of fish.

[0121] As a curing agent, a number of amino compounds (mono-, di- or polyamines) can be used, such as aliphatic amines (diethylenetriamine, polyoxypropylene triamine, etc.), cycloaliphatic amines (isophoronediamine, aminoethylpiperazine or diaminocyclohexane, etc.) or aromatic amines (diaminodiphenylmethane, xylene diamine, phenylenediamine, etc.). Primary and secondary amines may well serve as curing agents, while tertiary amines usually act as catalysts.

[0122] Although epoxy curing agents are typically amines, other options exist and will provide particular flexibility in application to provide chemicals that may be unstable or soluble in the presence of an amine, or allow a wider range of cure rates to be achieved.

[0123] For example, other suitable curing agents are polycarboxylic acid anhydrides, typically phthalic anhydride, nadic anhydride, methyl nadic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and in addition tetrahydrophthalic anhydride and hexahydrophthalic anhydride.

[0124] Certain epoxy resins are preferred for the present invention. Preferred epoxy resins are polymerized products from one or more preferred epoxy monomers and one or more preferred amine hardeners. Preferred epoxy monomers include cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, bisphenol A diglycidyl ether, resorcinol diglycidyl ether, glycerol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 3,4-epoxycyclohexyl methyl, 3.4 -epoxycyclohexanecarboxylate, diglycidyl-1,2-cyclohexanedicarboxylate, isosorbide diglycidyl ether and 1,6-hexanediol diglycidyl ether. Preferred amine hardeners include polyoxypropylenediamine, polyoxypropylenetriamine, polyoxyethylenediamine, N-aminoethylpiperazine, trimethyl-1,6-hexanediamine, isophoronediamine, N,N-dimethyl-1,3-diaminopropane, diethylenetriamine, N,N'-dimethylethylenediamine, and hexamethylenediamine.

[0125] Suitable catalysts such as tertiary amines, boron trifluoride, monoethylamine, imidazoles, triethanolamine, aminoethylpiperazine, tri(dimethylaminomethyl)phenol, bis(dimethylaminomethyl)phenol, and dicyandiamides can optionally be used to accelerate the curing reaction of the resin.

colloidal solids

[0126] In accordance with the present invention, any type of Pickering colloidal emulsion stabilizers can be used to stabilize emulsions prior to the step of solidifying the discontinuous phase into a polymer matrix, regardless of the type of polymer matrix, where the discontinuous phase contains a chemical agent, such as an agrochemical active ingredient.

[0127] More specifically, solids such as silicic acid fillers and clays are known in the literature for use as viscosity modifiers in agrochemical formulations to suppress gravity sedimentation by gravity or to separate layers of emulsion by forming a network or gel throughout the volume of a continuous phase, thereby increasing viscosity at low shear rate, and slowing down the movement of fine particles, surfactant micelles or emulsion droplets. The colloidal solids of the present invention instead act to stabilize droplets comprising resin monomers during curing by adsorption to the liquid-liquid interface, thus forming a barrier around the curable droplets such that adjoining or adjacent curable droplets are unable to stick together, regardless of whether cured droplets have precipitated or not. The colloidal solids also serve to prevent GM from hardening under extreme conditions, as seen when plasticizers are impregnated with conventional latex dispersions. With a functional test such as described below, two different functions can be differentiated - rheological change or stabilization of emulsions and dispersions. The effectiveness of a colloidal solid in stabilizing curing polymer droplet emulsions depends on particle size, particle shape, particle concentration, particle wettability, and particle-to-particle interaction. The colloidal solids must be small enough to cover the surfaces of the dispersed curable liquid polymer droplets, and the curable liquid droplets must be small enough to be used in conventional application equipment. The final polymer particles (and hence the colloidal solids) must also be small enough to provide an acceptable uniform distribution of the product to the target site. The colloidal solid must also have sufficient affinity with both liquids forming the dispersed and continuous phases so that they are capable of being adsorbed at the liquid-liquid interface and thereby stabilize the emulsion during curing. This wetting property, particle shape and suitability for stabilizing a Pickering emulsion type emulsion can be readily assessed by preparing a control formulation devoid of a colloidal solid as an emulsion stabilizer. In such a case, the curable liquid polymer droplets stick together and form a densified mass instead of a dispersion of polymer particles.

[0128] In one embodiment, the colloidal solids have a number-weighted average particle diameter as measured by scanning electron microscopy of 0.001-2.0 microns, preferably 0.5 microns or less, more preferably 0.1 microns or less.

[0129] A wide variety of solids can be used as colloidal stabilizers to prepare the dispersions of the present invention, including carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica, mica, modified hydrophobic silica, a mixture of dioxide silicon and alumina and types of clay. Suitable colloidal stabilizers are insoluble in any of the liquid phases present in the preparation of the concentrated formulation. If the agrochemical active ingredient has a suitable low solubility in any liquid used to dilute the final composition, and in both continuous and (transitional) discontinuous liquid phase, that is below about 100 ppm at room temperature, and can be obtained with a suitable particle size, and also has suitable wetting properties for the liquid-liquid interface as described above, then it is also possible that this active ingredient can serve as a colloidal stabilizer. Examples of particulate inorganic materials are hydroxy compounds of at least one of calcium, magnesium, aluminum and silicon (or derivatives thereof) such as silica, silicate, marble, clays and talc. Particulate inorganic materials may be either naturally occurring or 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 ground or precipitated), perlite, dolomite, diatomite, ganthite, magnesite, bomite , sepiolite, palygorskite, mica, vermiculite, illite, hydrotalcite, hectorite, halloysite and gibbsite. Additional suitable clays (eg, aluminosilicates) include those containing groups of kaolinite, montmorillonite, or illite 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. Other polymers suitable as colloidal solids include cross-linked star polymers such as those exemplified in Saigal et al. [Trishna Saigal, Alex Yoshikawa, Dennis Kloss, Masanari Kato, Patricia Lynn Golas, Krzysztof Matyjaszewski, Robert D. Tilton "Stable emulsions with thermally responsive microstructure and rheology using poly(ethylene oxide) star polymers as emulsifiers", Journal of Colloid and Interface Science 394 (2013) 284-292]. In a preferred embodiment, the colloidal solid is kaolin clay, alumina or hydrophilic fumed silica, and more preferably hydrophilic fumed silica or kaolin clay.

[0130] The type and amount of colloidal solid is chosen to provide acceptable physical stability of the composition during curing, polymerization, solvent evaporation, or other means of causing the polymers to solidify. The colloidal solid must also be present in an amount to provide a stably dispersed composition. The term "stably dispersed" as used herein means that when viewed by optical microscopy, the particles are essentially round spheres (in suspension) and when diluted are visually easily distinguishable from each other. This can be easily determined by a person skilled in the art by routine evaluation of a number of compositions containing varying amounts of this component. For example, the ability of colloidal solids to stabilize a composition can be tested by making a test sample with a colloidal solid and it can be shown that the droplet emulsion is stable and does not show sticking. Coalescence is noticeable by the formation of large droplets visible to the eye and, ultimately, by the formation of a layer of liquid monomers, polymer melt and polymer solution in the composition. The physical stability of the composition during and after curing, polymerization, solvent evaporation, or other polymer solidification is acceptable if no significant blocking is evident and GM is present as a dispersion.

For example, in one embodiment, colloidal solids are used in an amount of 1 to 80%, in particular 4 to 50% by weight of the discontinuous phase. Mixtures of colloidal solids can be used.

Plasticizers

[0131] The desired mechanical properties of the present invention can be achieved by one or a combination of means. In some embodiments, a plasticizer is used. Plasticizers are relatively small, non-reactive molecules (less than 1000 Da) that partially dissolve polymer molecules to allow movement of the segments, while imparting flexibility and reducing the rigidity of the entire polymer matrix. Plasticizers are chemically different and vary according to the polymer matrix in question, being necessarily miscible with any monomers and finished polymer matrix. Plasticizers may be added to the monomers or polymers prior to the formation of the GM, or they may be added to the continuous phase after the formation of the polymer matrix particles. In other embodiments, the type of polymer used for the composition may provide the desired mechanical properties. Selecting polymers with relatively long (greater than about 5 bond lengths) segments between potential intermolecular bridging sites such that these segments have a short persistence length (less than the segment length) and a low tendency to form organized crystal-like domains while still providing flexibility to the overall polymer matrix. In other embodiments, some or all of the monomers or copolymers used may, instead of being multifunctional to provide branching or crosslinking of the polymer matrix, have a low degree of functionality such that upon curing reaction these monomers reduce the overall degree of crosslinking while still producing a microparticle of the polymer matrix. with hardness from 0.001 MPa to 6 MPa. In the case of crosslinked thermoset epoxy polymer matrices, preferred methods for reducing the degree of crosslinking include blending monoglycidyl ethers with conventional polyglycidyl ethers and/or blending one or more primary monoamines, secondary mono- or diamines with conventional primary di-, triamine or amine curing agents with many functional groups. Specific preferred mono-epopoxides are butillycidyl ether, 2-ethyl hecticlicidyl ether, third-tubothyllycidyl ether, phenyllycidyl ether, orth-coalcidyl ether, ₁₂ -С ₁₄ alkylicidydyl ether, octylenexide, allelicicidydal, stirlicidydal. , pentadecylphenol glycydyl ether and epoxidized soy oil.

[0132] In some embodiments of the technology, the inclusion of a particular plasticizer will not be required to obtain the required particle hardness. By way of example and without limitation, the agrochemical active ingredient itself may have chemical and physical properties that would render the inclusion of a plasticizer unnecessary or allow the active ingredient itself to function as a plasticizer. Other components of the polymer particle may also have the same effect/function.

EXAMPLES

[0133] The following examples further illustrate some of the aspects of the present invention, however, are not intended to limit its scope. Unless otherwise indicated in this specification and claims, percentages are by weight.

[0134] Example 1. Preparation of the composition of the emulsion of the gel particles

[0135] Load all of the oil phase ingredients listed in Table 1 into a beaker followed by moderate shear mixing until they form a uniform and clear oil phase. In a separate beaker, load the ingredients of the aqueous phase and then homogenize with a high shear mixer. Add the premixed oil phase to the aqueous phase followed by shearing with an UltraTurrax mixer (0.5 inch diameter, 10k rpm) until the target particle size (10 µm) is obtained. Allow the monomer emulsion to polymerize at high temperature (80° C.) for 7-15 hours. A dispersing agent may be added and the composition subjected to shear forces with a gear mixer until it becomes a flowable liquid.

[0136] Example 2 Preparation of gel particle emulsion with different AI and different colloids

[0137] It is possible to obtain gel emulsions of the present invention containing various AI and various colloids to stabilize the monomers in the emulsified state in the course of the method that is used to obtain the dispersed phase. As an example, gel emulsions were prepared according to the methods described in Example 1 using the ingredients listed in Table 2 below.

[0138] Example 3. Preparation of gel particle emulsions without plasticizer

[0139] The gel emulsions of the present invention can also be made without a plasticizer. As an example, gel emulsions were prepared according to the methods described in Example 1 using the ingredients listed in Table 3:

[0140] Example 4 Incorporating Multiple AIs into a Polymer Matrix

[0141] More than one AI can be included in the gel emulsions of the present invention. As an example, gel emulsions were prepared similarly to the method described in Example 1 using the ingredients listed in Table 4 below.

[0142] Example 5 Improved crop safety while maintaining the fungicidal efficacy of gel particle emulsions

[0143] Two formulations based on benzovindiflupyr were prepared to compare the phytotoxicity (% damage) and fungicidal efficacy (% control) of the two formulations. The first composition was obtained in the form of an emulsifiable concentrate, and the second in the form of a gel emulsion composition according to the technology of the present invention. Comparative formulations were applied at 4x norm equivalent (1x=13.07 oz emulsifiable concentrate/acre=40.3 g AI/acre) to butternut squash plants about three weeks after planting. Phytotoxicity and fungicidal efficacy values were taken four days after application. The results of such tests are shown in Table 5. Surprisingly and unexpectedly, the formulation of the present invention provides 0% plant injury while maintaining 100% disease control.

[0144] Example 6 Improved Rain Wash Resistance of the Invention

[0145] Six agrochemical formulations containing difenoconazole were prepared to compare adhesion properties. The suspension concentrate, which contains difenoconazole and is sold under the tradename Quadris®Top, was used for comparison purposes. Six agrochemical formulations were prepared as gel emulsion formulations with improved particle softness as shown in Table 6b. Hardness was measured using a nanoindenter technique. Gel emulsions were prepared according to Table 6a with varying proportions of neopentyl diglycidyl ether and resorcinol diglycidyl ether to control hardness.

[0146] Examples 6a, 6b. Quadris®Top and six gel emulsions were applied to soybean leaves. Rain simulation was applied using the following parameters: flat nozzle (TeeJet 11008 EVS) for large droplets, spray rate: 0.8 g per minute, nozzle height: 20 inches, spray speed: 3 mph. Before the simulation, the beaker was placed in the precipitation chamber. The imitation of precipitation was stopped after the leaves received 1 cm of precipitation. The leaves were then dried for an hour before sampling for difenoconazole retention analysis.

[0147] Example 6a.

[0148] Example 6b.

[0149] Example 6c (average of 6a and 6b).

[0150] Example 7. Comparison of organic liquid impregnation capability of conventional latex and gel emulsion

[0151] The following mixtures shown in Table 10 were prepared from commercial latex products with the organic hydrophobic liquid herbicide S-metolachlor. The mixtures were designed so that each of the finished compositions contained approximately the same amount of polymer.

[0152] All 3 samples were left to mix overnight, after which they were homogeneous dispersions of latex with low viscosity. Also, all samples were physically unchanged after 4 months at ambient temperature. The particle size determination Dv50 by light scattering was 0.43, 0.48 and 12.4 microns, respectively. The results of these observations show that, in each case, S-metolachlor can easily impregnate polymer particles that contain conventional latexes, and that the resulting compositions have good dispersion properties under ambient conditions, as previously disclosed in other works.

[0153] Empty GM (no active ingredient), ID 1.4, was prepared as follows. 24.1 g of bisphenol A diglycidyl ether was mixed with 11.9 g of Jeffamine D-400, i. e. 25% molar excess of bisphenol A monomer to reduce crosslinking. 32 g of this liquid was dispersed with high shear in an aqueous phase containing 38.8 g of water, 3.4 g of 2% xanthan gel in water, 1.3 g of Infilm 939 Pickering kaolin stabilizer and 4.5 g of glycerol. The formulation was allowed to cure at 50° C. overnight, 0.4 g of Agrimer 30 dispersant was added and the resulting GMs had a particle size of Dv50, determined by light scattering, volume weighted average of 208 microns. Although relatively large, this sample had excellent stability at ambient conditions and remained a flowable liquid after 4 months.

[0154] Empty GM, ID 1.4, was divided into three aliquots of 10 g, S-metolachlor was added in amounts corresponding to 38%, 50% and 58%, and these aliquots were gently mixed over the weekend. In each case, the dispersed phase thickened and formed one soft rubbery plug that was relatively clean and uniform. The results of these observations showed that S-metolachlor impregnated the epoxy of the empty GMs and did not remain dispersed in the aqueous phase, but the GM polymer particles did not remain dispersed.

[0155] This example shows that while conventional latex compositions in which the latex is stabilized with conventional surfactants can effectively impregnate an oily liquid and remain dispersed, it is not necessarily possible to impregnate with an oily liquid GM containing a cross-linked colloid-stabilized epoxy. Pickering on its surface. The reason for the failure of the GM impregnation process is not exactly known here, and no explanation is offered; this example is presented as evidence that GM and impregnated latex technologies are fundamentally different, the behavior and benefits of a technology cannot be used to anticipate or predict the behavior of the other.

[0156] Example 8 Physical Stability of Impregnated Latexes and GM

[0157] GM was prepared according to the present invention with a composition similar to the empty GM described above in example 7, ID 1.4, but with S-metolachlor, now combined with monomers, before the formation of the dispersed phase and crosslinking. 7.2 g of bisphenol A diglycidyl ether was mixed with 3.6 g of Jeffamine D-400, i. 25% molar excess of bisphenol A to reduce the degree of crosslinking. This mixture of monomers was divided into two 4.5 g aliquots. One aliquot was combined with 10.5 g of S-metolachlor and the other was combined with 10.5 g of Hallcomid M-8-10 solvent. 13.3 g of these mixtures were dispersed with high shear into a mixture of 17 g of water, 2 g of 2% xanthan gel in water and 1 g of Infilm 939 Pickering kaolin stabilizer. ID 1.5 and 1.6 containing either S-metolachlor or Hallcomid M-8-10, respectively. These respective particle sizes Dv50, determined by light scattering, were 14 and 27 microns. The result for sample ID 1.5 may differ from the above attempt to impregnate S-metolachlor on a sample of empty GM ID 1.4, which, although containing essentially the same components, does not produce a discontinuous phase. The difference again shows the difference between the present invention and known methods involving impregnation with polymer latexes.

[0158] Latex impregnated formulations 1.1, 1.2 and 1.3 of Example 7 were compared with GM formulations 1.5 and 1.6 in terms of their physical stability and performance. The samples were subjected to a freeze-thaw cycle of 24 hours for two months, after which they were evaluated for fluidity, and then washed on a 50 mesh wire sieve. Acceptability for the application of agricultural sprays requires that the samples essentially leave no sediment on the sieve. The results are shown below in Table 11.

[0159] These five samples were also compared with respect to their compatibility with concentrated fertilizer solutions that are commonly used in agriculture. In this test, 5 g of each sample was combined in measuring cylinders with 95 ml of "10-34-0" fertilizer solution, these numbers represent the weight. % elements N, P, K. After standing overnight, the number of inversions needed to re-homogenize the mixtures was recorded, and the resulting mixture was then washed on a 50 mesh wire sieve. Acceptability requires that the samples essentially leave no sediment on the sieve. The results are shown below in Table 12.

[0160] The results of these observations indicated that the impregnated latex preparations, although having good dispersion properties and stability under ambient conditions, have unacceptable physical stability under extreme conditions, and then tend to agglomerate and unsatisfactory dispersion, so that they can no longer be sprayed, as required for agrochemicals. On the contrary, the compositions of the present invention have excellent physical stability under various commercially reasonable extreme conditions.

[0161] Example 9 Films Formed from Impregnated Latexes, Pickering Emulsions, Solid Polymeric Microparticles, and GM

[0162] Pickering's emulsion of S-metolachlor in aqueous glyphosate was prepared as described in Example 2 of WO 2008/030753 and the sample was designated ID 1.7. A solid polymeric microparticle containing a dispersed phase of 21.2 wt% mefenoxam (expressed as a percentage of the total composition), 12.2 wt% resorcinol diglycidyl ether and 6.6 wt% Jeffamine D-230 was prepared and designated ID 1.8. dispersed in 47 wt.% water, 6 wt.% kaolin clay and 7 wt.% 2% xanthan gel. The gel emulsion was prepared according to example 4 and was designated as 1.9.

[0163] 0.5 ml of each of the following samples was placed on pre-weighed plastic slides, allowed to dry overnight at ambient conditions, and the weight was recorded. One set of slides was washed in running water for 30 s, dried and then weighed. The second set of slides were soaked in water overnight, washed, dried and weighed. It should first be noted that samples 1.1 and 1.2 produced very tacky clear films, as expected from plasticized film-forming latexes. The tackiness of these films will pose serious problems if any dry residue of impregnated latexes is allowed to form on the plastic surface.

[0165] For samples 1.1, 1.2, and 1.3, the impregnation weight loss is less than the percentage of S-metolachlor present in the compositions, indicating that while some of the partially water-soluble S-metolachlor was released from the films, essentially no polymer component was removed.

[0166] The results of these observations have shown that dried films formed from impregnated conventional latexes are very persistent on plastic surfaces to the point that they cannot be effectively removed. This is not surprising since such latexes are commonly used as film formers in paints. Given the predominance of plastic surfaces in containers and agricultural equipment, this means that impregnated latexes are impractical for pesticide delivery, and of course latexes do not appear to be used in commercial applications for this purpose. Dried residues will accumulate in sticky films, rendering equipment unusable and containing unwanted pesticide residues.

[0167] In contrast, the conventional Pickering emulsion, ID 1.7, is very easy to redisperse, and of course this is an advantage of this technology in situations where redispersion is required. The hard polymeric microparticle, ID 1.8, can also be easily removed from plastic surfaces, even when they form dry films, because the colloid on the surfaces of the polymer particles prevents the particles from coalescing because the particles are rigid.

[0168] The GMs of the present invention are very different from these other technologies. Films containing GM according to the technology of the present invention are non-tacky to the touch due to the colloidal coating on the polymer particles. Their properties can be adjusted, as reported herein, to have the desired intermediate adhesiveness so that there is improved adhesion to surfaces, but not to the extent that dried residues cannot be removed.

[0169] Example 10 Microcapsules versus Stabilized Pickering Microcapsules

[0170] Microcapsules and stabilized Pickering microcapsules are generally known in the art. When a Pickering colloid is added to a microcapsule, the microparticle's adhesiveness to said surface is generally expected to decrease. Examples 10-1 and 10-2 are given in this document to show such a result.

[0171] Examples 10-1. S-metolachlor polyurea microcapsules with the compositions shown in Table 10a were prepared using the following procedure. All ingredients of the oil phase were loaded into a beaker followed by mixing with moderate shear until they form a homogeneous and clear oil phase. A separate beaker was charged with the ingredients of the aqueous phases and then homogenized using a high shear mixer. The premixed oil phase was added to the aqueous phase followed by shearing with an UltraTurrax high shear agitator (0.5 inch diameter, 10k rpm) until the desired emulsion particle size was achieved. The hardener was added to the emulsion to form the wall of the polymer shell. The polymerization reaction was carried out at room temperature for 14 hours with moderate stirring. If necessary, a dispersant was added.

[0172] An analysis for adhesion and resistance to rain washout of two microcapsule formulations was performed on sesame leaves. Diluted formulations (1 g AI/L) were prepared and then sprayed onto the leaves. The treated leaves were dried for 2 hours at room temperature and then subjected to 1 cm of artificial rain (water spray equivalent to 1 cm of precipitation). The active ingredient (AI) remaining on the leaves was extracted and analyzed by HPLC. The data in Table 10b shows the retention of AI before rain. The data in Table 10c shows the retention of AI after rain, expressed as the percentage of AI sprayed. In both tables, the Pickering microcapsule (CS-2) has a lower AI retention than the non-Pickering microcapsule (CS-1). This shows that the Pickering emulsion system itself does not provide increased tackiness or resistance to rain washout on leaf surfaces.

[0173] Examples 10-2. Tefluthrin polyurea microcapsule, TFT CS-1, was prepared using the following procedure. All of the oil phase ingredients listed in Table 10d were loaded into a beaker followed by moderate shear mixing until they form a uniform and clear oil phase. A separate beaker was charged with the aqueous phase ingredients and then homogenized using a high shear mixer. The premixed oil phase was added to the aqueous phase followed by shearing with an UltraTurrax high shear agitator (0.5 inch diameter, 10k rpm) until the desired emulsion particle size was obtained. The hardener was added to the emulsion to form the wall of the polymer shell. The polymerization reaction was carried out at room temperature for 14 hours with moderate stirring.

[0174] Rain wash resistance analyzes of the microcapsule and gel emulsion formulations of the present invention were performed on a glass plate (Table 10e). Diluted formulations (1 g AI/L) were prepared and then sprayed onto glass plates. The treated glass plates were dried for 2 hours at room temperature and then subjected to 1 cm of artificial rain (water spray equivalent to 1 cm of precipitation). The AI content remaining on the glass plates was extracted and analyzed by HPLC.

[0175] The data in Table 10e shows the retention of AI after rain, expressed as the percentage of AI applied, where the TFT gel emulsion showed 2.5 times better resistance to rain washout than microcapsule (TFT CS-1). The results showed that the softness property of GM is beneficial for rain resistance.

[0176] While only a few illustrative embodiments of the present invention have been described in detail above, those skilled in the art will readily appreciate that numerous modifications to the illustrative embodiments are possible without substantially departing from the innovative ideas and advantages of the present invention. Accordingly, all such modifications are intended to be included within the scope of the present invention as defined in the following claims.

Claims (51)

1. A method for producing an agrochemical composition containing a continuous phase and at least one dispersed phase, including: a. obtaining a non-aqueous curable liquid containing at least one crosslinkable resin containing monomers, oligomers, prepolymers, or mixtures thereof, while the resin optionally contains hydrophilic groups, optionally a hardener, catalyst, plasticizer or activator; b. emulsifying said non-aqueous curable liquid to an average droplet size of 1-200 microns in an aqueous liquid, wherein the aqueous liquid contains a colloidal solid as an emulsion stabilizer, optionally contains a plasticizer, and optionally a hardener, catalyst or initiator capable of diffusing into the dispersed uncured resin droplets; c. allowing the crosslinkable resin mixture to crosslink or cure, and then optionally impregnating with a plasticizer to form an emulsion containing the cured thermoset polymer particles and the colloidal solid material on the surface of the particle; And d. adding at least one agriculturally active ingredient to the emulsion to form cured thermoset polymer matrix microparticles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient dispersed therein. 2. A method for producing an agrochemical composition containing a continuous phase and at least one dispersed phase, including: a. obtaining a non-aqueous curable liquid containing at least one polymerizable resin containing monomers, oligomers, prepolymers or mixtures thereof, while the resin optionally contains hydrophilic groups, optionally a hardener, catalyst, plasticizer or activator; b. emulsifying said non-aqueous curable liquid to an average droplet size of 1-200 microns in an aqueous liquid, wherein the aqueous liquid contains a colloidal solid as an emulsion stabilizer, optionally contains a plasticizer, and optionally a hardener, catalyst or initiator capable of diffusing into the dispersed uncured resin droplets; c. causing the crosslinkable resin mixture to crosslink or cure, and then optionally impregnating with a plasticizer to form an emulsion containing the cured thermosetting polymer particles and the colloidal solid material on the surface of the particle; And d. adding at least one agriculturally active ingredient to the emulsion to form cured thermoset polymer matrix microparticles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient dispersed therein. 3. A method for producing an agrochemical composition containing a continuous phase and at least one dispersed phase, including: a. obtaining a non-aqueous liquid containing at least one hardenable polymer dissolved in a volatile solvent, and one or more optional plasticizers; b. emulsifying said non-aqueous liquid to an average droplet size of 1-200 microns in an aqueous liquid, wherein the aqueous liquid contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; c. allowing the volatile solvent to evaporate by heating the emulsion to a temperature of 30-120° C. for 0.1-10 hours and then optionally impregnating with a plasticizer to form solid thermoplastic polymer particles and a colloidal solid material on the particle surface; And d. adding at least one agriculturally active ingredient to the emulsion to produce thermoplastic polymer matrix microparticles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient dispersed therein. 4. A method for producing an agrochemical composition containing a continuous phase and at least one dispersed phase, including: a. obtaining a non-aqueous curable liquid containing a melt of at least one curable thermoplastic polymer and optionally a plasticizer; b. emulsifying said non-aqueous curable liquid to an average droplet size of 1-200 microns in a heated aqueous liquid, the aqueous liquid containing a colloidal solid as an emulsion stabilizer and optionally containing a plasticizer; And c. cooling the emulsion and then optionally impregnating with a plasticizer to form thermoplastic polymer particles in the emulsion and a colloidal solid material on the surface of the particle; And d. adding at least one agriculturally active ingredient to the emulsion to produce thermoplastic polymer matrix microparticles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient dispersed therein. 5. A method for producing an agrochemical composition containing a continuous phase and at least one dispersed phase, including: a. obtaining a dispersion concentrate by dissolving or suspending at least one agrochemically active ingredient in a non-aqueous curable liquid mixture containing at least one crosslinkable resin containing monomers, oligomers, prepolymers, or mixtures thereof, while the resin optionally contains hydrophilic groups, optionally a hardener, a catalyst , plasticizer or activator; b. emulsifying said dispersion concentrate to an average droplet size of 1-200 microns in an aqueous liquid, wherein the liquid contains a colloidal solid as an emulsion stabilizer, optionally contains a plasticizer and optionally a hardener, catalyst or activator capable of diffusing into the dispersed uncured resin droplets; And c. causing the crosslinkable resin mixture to crosslink or cure, and then optionally impregnating with a plasticizer to form emulsions comprising cured thermoset polymer particles with at least one agriculturally active ingredient dispersed therein and a colloidal solid material on the surface of the particle; And d. adding the agriculturally active ingredient to the emulsion to form cured thermoset polymer matrix microparticles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient or ingredients dispersed therein. 6. A method for producing an agrochemical composition containing a continuous phase and at least one dispersed phase, including: a. obtaining a dispersion concentrate by dissolving or suspending at least one agrochemically active ingredient in a non-aqueous curable liquid mixture containing at least one polymerizable resin containing monomers, oligomers, prepolymers or mixtures thereof, the resin optionally containing hydrophilic groups, optionally a hardener, a catalyst , plasticizer or activator; b. emulsifying said dispersion concentrate to an average droplet size of 1-200 microns in an aqueous liquid, wherein the liquid contains a colloidal solid as an emulsion stabilizer, optionally contains a plasticizer and optionally a hardener, catalyst or activator capable of diffusing into the dispersed uncured resin droplets; And c. causing the crosslinkable resin mixture to crosslink or cure, and then optionally impregnating with a plasticizer to form emulsions comprising cured thermoset polymer particles with at least one agriculturally active ingredient dispersed therein and a colloidal solid material on the surface of the particle; And d. adding the agriculturally active ingredient to the emulsion to form cured thermoset polymer matrix microparticles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient or ingredients dispersed therein. 7. A method for producing an agrochemical composition containing a continuous phase and at least one dispersed phase, including: a. dissolving or suspending at least one agrochemically active ingredient in a non-aqueous liquid mixture containing at least one settable polymer dissolved in a volatile solvent and one or more optional plasticizers; b. emulsifying said solution to an average droplet size of 1-200 microns in an aqueous liquid, wherein the liquid contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; c. ensuring evaporation of the volatile solvent by heating the emulsion to a temperature of 30-120°C for 0.1-10 h and then optionally impregnating with a plasticizer to obtain solid thermoplastic polymer particles with at least one agriculturally active ingredient distributed therein, and colloidal solid material on the particle surface; And d. adding the agriculturally active ingredient to the emulsion to form thermoplastic polymer matrix microparticles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient or ingredients dispersed therein. 8. A method for producing an agrochemical composition containing a continuous phase and at least one dispersed phase, including: A. obtaining a dispersion concentrate by dissolving or suspending at least one agrochemically active ingredient in a non-aqueous curable liquid mixture containing a melt of at least one curable thermoplastic polymer and optionally a plasticizer; b. emulsifying said dispersion concentrate to an average droplet size of 1-200 microns in a heated aqueous liquid which contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; And c. cooling the emulsion and then optionally impregnating with a plasticizer to form thermoplastic polymer particles with at least one agriculturally active ingredient dispersed therein and a colloidal solid material on the surface of the particle; And d. adding the agriculturally active ingredient to the emulsion to form thermoplastic polymer matrix microparticles with a particle hardness that is greater than 0.001 MPa and less than 6 MPa, with the agriculturally active ingredient or ingredients dispersed therein. 9. The method according to any one of paragraphs. 1-8, where the polymer matrix microparticle has a hardness of more than 0.001 MPa and less than 5 MPa. 10. The method according to paragraphs. 1-8, where the microparticle of the polymer matrix has a hardness of more than 0.01 MPa and less than 5 MPa. 11. The method according to paragraphs. 1, 2, 5, 6, 9 or claim 10, where the resin is an epoxy resin. 12. The method according to any one of paragraphs. 1-11, where each dispersed phase contains polymer matrix microparticles with a median diameter of 1 to 100 microns. 13. The method according to any one of paragraphs. 1-11, where the dispersed phase contains polymer matrix microparticles with a median diameter of 1 to 50 microns. 14. The method according to paragraphs. 1-11, where the dispersed phase contains polymer matrix microparticles with a median diameter of 1 to 30 microns. 15. The method of claim 11, wherein the epoxy resin is bisphenol A diglycidyl ether, glycerin, polypropylene oxide, neopentyl, resorcinol, cyclohexanedimethanol, butanediol, polyethylene oxide, or polyalkylene oxide, or a mixture of two or more of these esters. 16. The method of claim 15, wherein the epoxy resin is cured using an amine curing agent. 17. The method according to any one of paragraphs. 1-11 wherein the colloidal solid as emulsion stabilizer is selected from carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica, mica, modified hydrophobic silica, a mixture of silica and alumina, and types of clay . 18. The method according to any one of paragraphs. 1-11 wherein the continuous phase is water and the colloidal solid is kaolin clay, alumina, or hydrophilic fumed silica. 19. The method according to any one of paragraphs. 1-11 wherein the continuous phase contains water and a substantially water-miscible non-aqueous liquid, and the colloidal solid is hydrophilic fumed silica or kaolin clay.