Stabilized pesticide composition

Abstract

This disclosure relates to gel emulsion compositions, as well as methods for producing and using them.

Description

Technical Field

[0001] The present invention relates to a stabilized, liquid, chemical composition, the preparation of such a composition, and the use of such a composition, for example, for pest control or as a plant growth regulator.

Background Art

[0002] Gel emulsions, and gel emulsion-like formulations are disclosed, for example, in WO 2019 / 21770, WO 2019 / 21775, WO 2011 / 162944, and WO 2011 / 137170. The design of gel emulsion formulations involves soft, gel-like, ductile polymer matrix microparticles. Although many advantages have been disclosed for such formulations, public research on the use of many possible components and their combinations is generally lacking. The use of different components, and their combinations, can change the properties of the formulation. However, it is not always clear how specific properties will change (improve or deteriorate) when the components are changed. Therefore, there is still a need for gel emulsion formulations with improved properties.

[0003] Furthermore, problems have been seen during the scale-up of the production of gel emulsions. Large batches tend to agglomerate and form larger particle sizes. Such agglomeration can result in an overly viscous composition that cannot be effectively processed. Therefore, new methods are needed to facilitate the large-scale production of gel emulsions.

Summary of the Invention

Means for Solving the Problems

[0004] Embodiments of the present disclosure include a method comprising the steps of: combining a first composition in a second composition to form a third composition, wherein the first composition is substantially immiscible in the second composition, the first composition contains an active pesticide ingredient, and the first composition contains a liquid curable, solidifying, or polymerizable resin; emulsifying the third composition such that the first composition is a dispersed phase and the second composition is a continuous phase of the third composition, optionally having a median diameter of less than 200 μm; adding a dispersant to the emulsified third composition to form a fourth composition; and curing, solidifying, or polymerizing the liquid curable, solidifying, or polymerizable resin in the fourth composition to form polymer matrix microparticles in which the active pesticide ingredient is distributed.

[0005] Additional embodiments include a manufacturing system comprising: a first container having a mixer configured to agitate and / or mix a liquid in the first container, and a heater configured to heat a liquid composition in the first container; a second container in fluid communication with the first container, having a shearing system configured to apply shear to a liquid in the second container; a third container having a mixer configured to agitate and / or mix a liquid in the third container; and a pump system configured to transfer liquid between the first and second containers.

[0006] The manufacturing system comprises the steps of: filling a first composition containing an active pesticide ingredient and a liquid curable, solidifying, or polymerizable resin into a first container and optionally mixing or stirring the first composition; filling a second composition substantially immiscible in the first composition into a second container and optionally mixing or stirring the second composition; pumping the first composition from the first container to a second container containing the second composition to form a third composition; and shearing the third composition using a shearing system to form the first set It can be used in a method comprising: emulsifying a third composition so that the product becomes a dispersed phase; preparing a dispersant composition in a third container; transferring the dispersant composition in the third container to a first container; transferring the sheared third composition to the first container; and, after the transfer of the dispersant composition and the transfer of the third composition, curing, solidifying, or polymerization of a liquid curable, solidifying, or polymerizable resin to form polymer matrix microparticles in which the pesticide active ingredient is distributed.

[0007] The methods described herein can be used to prepare pesticide compositions.

[0008] The compositions of the present disclosure may include liquid dispersion compositions comprising: (a) a continuous phase; (b) at least one dispersed phase comprising polymer matrix microparticles, wherein the polymer matrix microparticles have (1) a hardness of less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an active pesticide component therein; and (c) a dispersant system comprising (c1) a sulfonate dispersant and a polyacrylate copolymer, and / or (c2) alkylated vinylpyrrolidone and a nonionic polyacrylate polymer.

[0009] The compositions of this disclosure can be applied in amounts that are effective in killing pests to plants, plant propagation materials, or habitats of harmful organisms. [Brief explanation of the drawing]

[0010] [Figure 1A] The first step in the manufacturing system according to this disclosure is shown. [Figure 1B] The second step in the manufacturing system according to this disclosure is shown. [Figure 1C] The third step in the manufacturing system described herein is shown. [Figure 1D] The fourth step in the manufacturing system according to this disclosure is shown. [Figure 2A] The graphs show the time course of serum formation for various compositions at different temperatures. [Figure 2B] Helipath results for the composition at various temperatures and storage times are shown. [Figure 2C] This shows the viscosity of various dispersants in the composition. [Figure 2D] This shows the pH of various dispersants in the composition. [Figure 2E] This chart shows a two-dimensional chart of serum formation with various dispersants after storage at various temperatures. [Figure 2F] This shows the helipathy results of various dispersants after storage at various temperatures. [Figure 2G] The helipath and binary sedimentation results for various dispersant combinations in the composition are shown. [Figure 2H] The helipathy and sedimentation results for various dispersant combinations in the composition are shown. [Modes for carrying out the invention]

[0011] This disclosure relates to “gel” or “gel-like” polymer matrix particles containing captured pesticides, wherein the pesticides are distributed uniformly or non-uniformly within such particles or exist in the form of domains within such particles, and herein the outer surface region of the particles comprises a colloidal solid material. The terms “gel” and “gel-like” as used herein are meant as non-limiting general descriptors and do not confer any definition or limitation of “gel” or “gel-like” to polymer particles.

[0012] Therefore, in one embodiment, the liquid dispersion composition of the present invention is (a) Continuous phase and; (b) At least one dispersed phase containing polymer matrix microparticles, wherein the polymer matrix microparticles have (1) a hardness of less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) a pesticidal active ingredient therein; (c) A dispersant system, (c1) A sulfonate dispersant and a polyacrylate copolymer, and / or (c2) An alkylated vinyl pyrrolidone, a nonionic polyacrylate polymer A dispersant system containing; containing.

[0013] In certain embodiments, the polymer matrix particles can also be defined by the polymer content of the polymer matrix particles themselves. The polymer content of the polymer matrix particles can be calculated by taking the amount of polymer in the polymer matrix particles and dividing it by the total content of the polymer matrix particles (or the dispersed / oil phase). The calculations as used herein are weight-based. The polymer content of the polymer matrix particles can be, for example, less than 50 wt / wt%, less than 45 wt / wt%, less than 40 wt / wt%, less than 35 wt / wt%, less than 30 wt / wt%, less than 25 wt / wt%, less than 20 wt / wt%, less than 15 wt / wt%, or even less than 10 wt / wt%, or less than 5 wt / wt%. In certain embodiments, there is at least 1% polymer content.

[0014] As used herein, the term "particle" refers to a minute portion of a substance. The particles can include portions of a substance that are, for example, solid, liquid, or gel.

[0015] In one embodiment, the chemical agent is a pesticidal active ingredient.

[0016] In one embodiment, the colloidal solid material is a Pickering colloid emulsion stabilizer.

[0017] In one embodiment, GE comprises captured pesticides that are distributed uniformly or non-uniformly within such particles, or that exist within such particles in the form of domains.

[0018] In relation to the present invention, the average particle or droplet size exhibits a volume-weighted average, generally referred to as Dv50, which is determined by dynamic light scattering.

[0019] In connection with this invention, particle hardness is measured by nanoindentation technology. Nanoindentation technology has been widely used to characterize the mechanical properties of materials on a surface. It is based on the following standards for instrumentation: ASTM E2546 and ISO 14577. Nanoindentation uses an established method in which an indenter tip with a known shape (typically conical for relatively soft samples) is driven into a specific location in the material by applying an increasing vertical load. Once a preset maximum value is reached, the vertical load is reduced until complete relaxation occurs. During the experiment, the position of the indenter relative to the sample surface is precisely monitored with a high-precision volumetric sensor. The resulting load / displacement curve provides data specific to the mechanical properties 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 allows for testing of local mechanical properties.

[0020] In one embodiment, the active ingredient of the pesticide is either a solid distributed within the dispersed phase or a liquid distributed within the dispersed phase.

[0021] In another embodiment, the dispersion concentrate for use in the liquid pesticide composition of the present invention is formed using a curing agent, monomer, oligomer, prepolymer, or blend thereof, which exhibits a slow curing or polymerization reaction when combined with a curing agent under ambient conditions. Particularly preferred are those curing agents, monomers, oligomers, prepolymers, or blends thereof that, after mixing with a curing agent, do not show a significant increase in viscosity under ambient conditions for at least 15 minutes, more particularly 30 minutes, and most particularly 1 hour.

[0022] According to one embodiment of the present invention, a polymerizable thermosetting resin is understood to include all molecules that can be irreversibly polymerized or cured to form a polymer matrix that does not melt or deform at temperatures below its thermal decomposition point. The polymerization reaction may be initiated thermally by the addition of a chemical curing agent or by suitable irradiation to generate radicals or ions, such as visible, UV, microwave or other electromagnetic irradiation, or electron beam irradiation. Examples include phenolic, urea, melamine, epoxy, polyester, silicone, rubber, polyisocyanate, polyamine, and polyurethane. In addition, bioplastics or biodegradable thermosetting resins may be used, including epoxy or polyester resins derived from natural materials such as vegetable oil, soybean or wood.

[0023] According to another embodiment of the present invention, the polymerizable thermoplastic resin is understood to include all molecules that can be polymerized or cured to form a polymer matrix that can melt or deform at temperatures below its thermal decomposition point. The polymerization reaction may be initiated thermally by the addition of a chemical curing agent or by suitable irradiation to generate radicals or ions, for example by visible, UV or other electromagnetic irradiation, or electron beam irradiation. Examples of suitable ethylenically unsaturated monomers include styrene, vinyl acetate, α-methylstyrene, methyl methacrylate, and those described in U.S. Patent Application Publication No. 2008 / 0171658. Examples of thermoplastic polymers for polymer particles that can be prepared from in-situ miniemulsion polymerization include polymethyl methacrylate, polystyrene, polystyrene-co-butadiene, polystyrene-co-acrylonitrile, polyacrylate, polyalkyl acrylate, polyalkyl acetate, polyacrylonitrile, or copolymers thereof.

[0024] In a further embodiment of the present invention, the solidifiable thermoplastic resin is understood to contain all molecules that can be dissolved in a volatile solvent so that the solvent evaporates upon heating, producing a polymer matrix that can melt or deform at temperatures below its thermal decomposition point. The volatile solvent is selected to be immiscible with the continuous aqueous phase and sufficiently volatile so that it can be conveniently removed from the composition by heating to a temperature below which any significant decomposition occurs. Examples include polymers of the ethylenically unsaturated monomers mentioned above, as well as polymers such as cellulose acetate, polyacrylate, polycaprolactone, and polylactic acid. Other examples include 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 wax. In addition, bioplastics or biodegradable polymers such as thermoplastic starch, polylactic acid, polyhydroxyalkanoates, polycaprolactone, and polyesteramides are also suitable for use in the preparation 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 International Publication No. 2011 / 040956.

[0025] As used herein, the terms “polymer matrix particles” or “polymer matrix microparticles” mean polymer particles in which the density and polymer composition are substantially uniform throughout the particle itself.

[0026] The term "microparticles" is a term commonly used to describe particles whose size is microscopic. The polymer matrix particles of this technology differ from microcapsules, which consist of a separate shell wall and a hollow core. According to the present invention, the polymer matrix microparticles of the dispersed phase have Dv50 particle sizes of 1 to 200 microns, more particularly 1 to 100 microns, and most particularly 1 to 80 microns and 1 to 30 microns.

[0027] In one embodiment, a suitable polymerizable resin and polymer solution is substantially miscible with the liquid used in the continuous phase.

[0028] In relation to the present invention, colloidal solid materials are those whose properties of interest are determined by their surface interactions with other materials. Therefore, colloidal solids inevitably have a high specific surface area, typically 10 m². 2 It has a concentration greater than / g. For example, colloidal solids can stabilize emulsions of immiscible liquids, as described, for example, in International Publication No. 2008 / 030749. When useful for this purpose, such colloidal solids may be called pickering colloids, colloidal emulsion stabilizers, or other equivalent terms. Functional tests for determining whether a colloidal solid can stabilize an emulsion as used herein are known. Not all colloidal solids can stabilize any given pair of emulsions of immiscible liquids, and such functional tests may be used by those skilled in the art to identify suitable colloids.

[0029] In another embodiment, where the continuous phase is aqueous, the affinity of an aqueous liquid suitable for use in continuous phase a) to the pesticide active ingredient distributed in the dispersed phase b) is such that substantially all of the pesticide active ingredient remains in the dispersed solid phase and substantially nothing moves to the continuous phase. Those skilled in the art will be able to easily determine whether a particular aqueous liquid satisfies this criterion for a particular pesticide active ingredient in question by following any standard test procedure for determining the distribution coefficient of the compound (in this case, the pesticide active ingredient in the dispersed phase) between the continuous phase and the dispersed solid phase. Thus, the dispersed phase b) is immiscible with continuous phase a).

[0030] In a further embodiment, an aqueous liquid suitable for use in continuous phase a) is a solution of a water-soluble solute in water.

[0031] Suitable water-soluble solutes for continuous phase use include ammonium and metal halides, nitrates, sulfates, carbonates, phosphates, nitrites, sulfites, nitrides, and sulfides. Other suitable solutes include sugars and osmolites, such as polysaccharides, proteins, betaines, and amino acids.

[0032] In one embodiment, an aqueous liquid suitable for use in continuous phase a) is a mixture of water and a substantially water-miscible non-aqueous liquid. In connection with the present invention, the term “substantially water-miscible” means a non-aqueous liquid that forms a single phase when present in water at a concentration of at least 50% by weight.

[0033] Substantially water-miscible non-aqueous liquids suitable for use in continuous phase a) include, for example, propylene carbonate; water-miscible glycols selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, hexylene glycol and polyethylene glycol having a molecular weight up to about 800; acetylated glycols such as di(propylene glycol)methyl ether acetate or propylene glycol diacetate; triethyl phosphate; ethyl lactate; gamma-butyrolactone; water-miscible alcohols such as propanol or tetrahydrofurfuryl alcohol; N-methylpyrrolidone; dimethyllactamide; and mixtures thereof. In one embodiment, the non-aqueous, substantially water-miscible liquid used in continuous phase a) is a solvent for at least one of any pesticide active ingredients.

[0034] In another embodiment, the aqueous, substantially water-miscible liquid used in continuous phase a) is completely miscible with water in all proportions. Alternatively, the aqueous, substantially water-miscible liquid used in 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 and water is maintained in a liquid state by forming a composition at high temperatures.

[0035] In another embodiment, the continuous liquid phase is a non-aqueous liquid. In another embodiment, the continuous liquid phase is a substantially water-immiscible, non-aqueous liquid. The water-immiscible, non-aqueous liquid may be selected from petroleum distillates, vegetable oils, silicone oils, methylated vegetable oils, refined paraffinic hydrocarbons, alkyl lactates, mineral oils, alkylamides, alkyl acetates, and mixtures thereof.

[0036] In another embodiment, the continuous phase comprises a substantially water-miscible, non-aqueous liquid. The water-miscible, non-aqueous liquid may be selected from the group comprising propylene carbonate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, hexylene glycol, polyethylene glycol having a molecular weight up to about 800, di(propylene glycol) methyl ether acetate, propylene glycol diacetate, triethyl phosphate, ethyl lactate, gamma-butyrolactone, propanol, tetrahydrofurfuryl alcohol, N-methylpyrrolidone, dimethyllactamide, and mixtures thereof.

[0037] Those skilled in the art will understand that the amount of water and the properties and amounts of non-aqueous, water-miscible liquids or water-soluble solutes can be varied to provide a mixed aqueous liquid suitable for use in continuous phase a), and that these amounts can be determined without excessive experimentation. In one embodiment, the aqueous continuous phase contains 5 to 95% by weight, more preferably 30 to 90% by weight of ethylene glycol, with the remainder being water. In another embodiment, the aqueous continuous phase contains 5 to 95% by weight, more preferably 30 to 90% by weight of glycerol, with the remainder being water.

[0038] In one embodiment, the liquid dispersion concentrate composition of the present invention comprises a mixture of GEs, each containing one or more chemical agents (e.g., active ingredients of pesticides). Each of the chemical agents is contained in the same or different dispersed phases GM, and each dispersed phase particle optionally contains a different polymer matrix as described above. Optionally, each dispersed phase may have a different particle size.

[0039] In one embodiment, the liquid dispersion concentrate composition of the present invention comprises a dispersion phase in the form of finely pulverized suspended polymer particles containing a colloidal solid material on their outer surface and containing at least one pesticide active ingredient.

[0040] The advantages of the liquid dispersion concentrate composition (e.g., gel emulsion) of the present invention include: long-term storage stability; the ability to conveniently combine multiple pesticides in different physical states in a dispersion of mutually compatible particles; improved adhesion of the deposit to a surface where it can dry; reduced possibility of crop damage due to the presence of solvents or other plant toxic agents; improved acute toxicity; easy handling for the user, as dilution for the preparation of application mixtures is carried out with water or other liquid carriers; the composition can be easily resuspended or redispersed with only a small amount of stirring and is less susceptible to bonding when dilution is carried out with fertilizer solution for the preparation of 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.

[0041] Active ingredients of pesticides The term “pesticide active ingredient” refers to chemical and biological compositions, such as those described herein (e.g., pesticide active ingredients), that are effective in killing, preventing, or controlling the growth of undesirable pests, such as plants, insects, mice, microorganisms, algae, fungi, bacteria, etc. The term may also be applied to compounds that act as adjuvants to promote the uptake and delivery of other active compounds. The term may also be applied to compounds that control plant growth in a desired manner (e.g., plant growth regulators), compounds that mimic the natural systemic activation-resistance response found in plant species (e.g., plant activators), or compounds that reduce the toxic response of plants to herbicides (e.g., phytotoxicity reducers). If two or more are present, the pesticide active ingredients are present independently in amounts that are biologically effective when the composition is diluted, if necessary, in a suitable volume of liquid carrier, e.g., water, and applied to the intended target, e.g., plant leaves or their habitat.

[0042] Examples of pesticide active ingredients suitable for use in continuous phase a) or dispersed phase b) according to the present invention include, but are not limited to, the following: fungicides such as azoxystrobin, benzovin diflupyr, chlorothalonil, cyproconazole, cyprodinil, difenoconazole, fenpropidine, fludioxonil, mandipropamide, mefenoxam, paclobutrazol, picoxystrobin, propiconazole, pyraclostrobin, sedaxane, tebuconazole, thiabendazole, and trifloxystrobin; acetochlor, arachlor Ametrine, Anirofos, Atrazine, Azaphenidine, Benfluralin, Benfuralate, Benslide, Benzefenizone, Benzofenap, Bicyclopyrone, Bromobutide, Bromophenoxime, Bromoxynil, Butachlor, Butaphenacil, Butamiphos, Butralin, Butyrate, Cafenstrol, Carbetamide, Chloridazone, Chlorpropham, Chlortal-dimethyl, Chlorthiamide, Synidone-ethyl, Symmethilin, Chromazon, Clomeprop, Chloransrum-methyl, Cyanazine, Cycloate, Desmedifam Desmethrin, Diclobenyl, Diflufenican, Dimepiperate, Dimethachlor, Dimethometryn, Dimethenamide, Dimethenamide-P, Dinitramine, Dinoterb, Diphenamide, Dithiopyr, EPTC, Esprocarb, Etalfluralin, Etofmesate, Etobenzanide, Phenoxaprop-ethyl, Phenoxaprop-P-ethyl, Fentrazaamide, Flamprop-methyl, Flamprop-M-isopropyl, Fluazolate, Fluchloralin, Fluphenacet, Flumicrolac-pentyl, Flumioxazine, Fluorochlor Don, Flupoxam, Flurenol, Flulidone, Fluthiaset-methyl, Indanophan, Isoxaben, Isoxaflutol, Renasil, Linulone, Mefenaset, Mesotrione, Metamitron, Metazachlor, Metabenzthiazuron, Methyldimylon, Metobenzuron, Metrachlor, Metoslam, Metoxron, Metrivudine, Morinate, Naproanilide, Napropamide, Nevron, Norflurazone, Olbencarb, Oryzalin, Oxaziargyl, Oxadiazone, Oxyfluorphene, Pebrate, Bendimethalin,Pentanoclor, petoxamide, pentoxazone, fenmedifam, pinoxadene, piperofos, pretilachlor, prodiamine, profluazole, prometon, prometrin, propachlor, propanyl, propazine, profam, propisochlor, propizamide, prosulfocarb, pidflumetofen, pyraflufen-ethyl, pyrazogyl, pyrazolinate, pyrazoxifen, pyributicarb, pyridate, pyriminovac-methyl, quinchlorac, sidurone, simazine, simetrin, S-methrachlor, sulcotrione, sulfentrazone, tebutam, tebutiurone, terbasil, terbumeton, terbutyrazine, terbutrin, tenylchlor, thiazopyr, tidiazimine, thiobencarb, thiocarbasil, triate, trietadine, trifluralin and Herbicides such as vernolate; benoxacol, dichlormid, fenchlorazole-ethyl, fenchlorim, flurazole, fluxofenim, flirazole, isoxadifen-ethyl, mefenpyr; alkali metal, alkaline earth metal, sulfonium or ammonium cations of mefenpyr; herbicide toxicity mitigants such as mefenpyr-diethyl and oxavethrinil; insecticides such as abamectin, clothianidin, cyanthraniliprole, emamectin benzoate, gamma-cyhalothrin, imidacloprid, cyhalothrin and its enantiomers, for example, lambda-cyhalothrin, tefluthrin, permethrin, resmethrin and thiamethoxam; nematicides such as fostiazate, phenamifos and aldicarb.

[0043] The total amount of pesticide active ingredients in polymer matrix particles can be calculated by taking the amount of pesticide active ingredients in polymer matrix particles and dividing it by the total content of the polymer matrix particles. Calculations as used herein are weight-based. The total content of pesticide active ingredients may be, for example, less than 95% by weight, less than 90% by weight, less than 85% by weight, less than 80% by weight, less than 75% by weight, less than 70% by weight, less than 65% by weight, less than 60% by weight, less than 55% by weight, less than 50% by weight, less than 45% by weight, less than 40% by weight, less than 35% by weight, less than 30% by weight, less than 25% by weight, even less than 20% by weight, even less than 15% by weight, even less than 10% by weight, or even less than 5% by weight, depending on the active ingredients of the particular pesticide and the solvent used to dissolve at least one of the pesticide active ingredients in the particles. Generally, the amount of the active ingredient in pesticides is at least 5% by weight of the particles.

[0044] In one embodiment, the active ingredient in the continuous phase may be in the form of a solution, emulsion, microemulsion, microcapsule, or particles or fine particles. In connection with the present invention, fine particles are substantially smaller than the GE of the dispersed phase such that a plurality (at least 10) of active ingredient particles are present within each particle of the dispersed phase, while non-fine particles are slightly smaller than the GE of the dispersed phase such that each polymer particle contains only a small number of active ingredient particles.

[0045] Further embodiments of the present invention include a method for preventing or eliminating pests from invading plant species and regulating plant growth by diluting a certain amount of a concentrated composition with water or a suitable liquid carrier such as a liquid fertilizer and applying it to plants, trees, animals or habitats as needed. The formulations of the present invention may also be combined with water in a continuous flow device or a spray application device so that a holding tank is not required for the dilution product.

[0046] The liquid dispersion concentrate composition can be conveniently stored in a container, from which the composition is poured, pumped, or to which a liquid carrier is added before application.

[0047] If a solid pesticide active ingredient is present, the solid active ingredient may be ground to a desired particle size before being dispersed in a polymerizable resin (monomer, oligomer, and / or prepolymer, etc.) that will form a GE. The solid may be ground in a dry state using an air mill or other suitable apparatus as needed to achieve the desired particle size. The particle size may be a Dv50 particle size of about 0.2 to about 20 microns, preferably about 0.2 to about 15 microns, and more preferably about 0.2 to about 10 microns.

[0048] As used herein, the term “pesticide-effective amount” means the amount of a pesticide-active compound that adversely controls or modulates a target pest or modulates plant growth (PGR). For example, in the case of herbicides, “pesticide-effective amount” is the amount of herbicide sufficient to control or modify plant growth. Controlling or modifying effects include all deviations from natural development, such as death, delay, leaf burn, bleaching, and dwarfing. The term plant refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits. In the case of fungicides, the term “fungicide” means a substance that kills fungi or substantially inhibits their growth, proliferation, division, reproduction, or spread. As used herein, in relation to fungicidal compounds, the term “fungicide-effective amount” or “amount effective to control or reduce fungi” is the amount that would kill a significant number of fungi or substantially inhibit their growth, proliferation, division, reproduction, or spread. As used herein, the terms “insecticide,” “nematicide,” or “acaricide” mean, respectively, a substance that kills or substantially inhibits the growth, proliferation, reproduction, or spread of insects, nematodes, or mites. An “effective dose” of an insecticide, nematicide, or acaricide is the amount that would kill or substantially inhibit the growth, proliferation, reproduction, or spread of a considerable number of insects, nematodes, or mites.

[0049] In one embodiment, as used herein, “(plant) growth regulator,” “plant growth regulator,” PGR, “regulate,” or “regulate” includes the following plant responses: inhibition of cell elongation, e.g., reduction of stem height and internode distance, strengthening of stem walls, and thereby increased lodging resistance; compact growth in ornamental plants for the economical production of plants of improved quality; promotion of better fruit setting; increase in ovary number for the purpose of increasing yield; acceleration of tissue senescence to enable fruit detachment; leaf fall of seedlings and ornamental shrubs and trees for autumn mail order; leaf fall of trees to break the chain of parasitic infection; acceleration of ripening and breaking of the food chain of harmful insects for the purpose of planning harvests by reducing harvests to one or two picks.

[0050] In another embodiment, “(plant) growth regulator,” “plant growth regulator,” “PGR,” “regulate,” or “regulate” also includes the use of compositions as defined in the present invention for increasing yields and / or improving vitality of agricultural plants. According to one embodiment of the present invention, compositions of the present invention are used to improve the tolerance of agricultural plants to stressors such as fungi, bacteria, viruses and / or insects, as well as to stressors such as heat stress, nutrient stress, cold stress, drought stress, UV stress and / or salt stress.

[0051] The selection of application rates related to providing a desired level of pest-killing activity to the compositions of the present invention is commonplace for those skilled in the art. The application rate will depend on factors such as the pest pressure level, plant condition, climate and growth conditions, as well as the activity of the pesticide active ingredient and any applicable label ratio limitations.

[0052] Embodiment The present invention also, a) Optionally, a continuous aqueous liquid phase containing at least one active pesticide ingredient; b) A dispersed phase comprising polymer particles containing a colloidal solid material on their outer surface, prepared from either a curable or polymerizable resin or a solidifying thermoplastic polymer, wherein the particle hardness is greater than 0.001 MPa and less than 6 MPa, and the particles contain at least one pesticide active ingredient distributed therein, and This relates to a gel emulsion pesticide composition containing [a specific ingredient / method].

[0053] A further aspect of the present invention is a dilute aqueous spray composition for controlling pests in a habitat or regulating plant growth, a) A continuous aqueous phase comprising 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) A dispersed phase comprising polymer particles prepared from either a curable or polymerizable resin or a solidifying thermoplastic polymer, wherein the particles have a hardness greater than 0.001 MPa and less than 6 MPa, and the particles contain at least one pesticide active ingredient distributed therein; c) Optionally, at least one pesticide active ingredient dispersed, dissolved, suspended, microemulsified and / or emulsified in a liquid carrier This relates to compositions containing the following:

[0054] In another embodiment, the present invention relates to a dilute pesticide and / or PGR composition for ultra-low volume (ULV) application, a) A continuous phase comprising a carrier solvent having a flash point above 55°C in an amount sufficient to obtain the desired final concentration of each active ingredient in the ULV composition; b) A dispersed phase prepared from either a curable or polymerizable resin or a solidifying thermoplastic resin, comprising polymer particles containing a colloidal solid material on their outer surface, wherein the particle hardness is greater than 0.001 MPa and less than 6 MPa, and the particles contain at least one pesticide active ingredient distributed therein. This relates to compositions containing the following:

[0055] The present invention also relates to a method for controlling or preventing harmful organisms in a useful plant crop, or for regulating the growth of such crop, wherein the method is 1) A desired area such as a plant, a part of a plant, or its habitat, a) A continuous aqueous liquid phase optionally containing at least one active pesticide ingredient and optionally containing at least one acidic or basic component; b) A dispersed phase prepared from either a curable or polymerizable resin or a solidifying thermoplastic resin, comprising polymer particles containing a colloidal solid material on its outer surface, wherein the particle hardness is greater than 0.001 MPa and less than 6 MPa, and the particles contain at least one pesticide active ingredient distributed therein. A step of treating with a concentrated composition containing; or 2) Diluting the concentrated composition in a suitable carrier, 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 active ingredients of the pesticide, if necessary; and then treating a desired area, such as a plant, a part of a plant, or its habitat, with the dilute spray or ULV composition. This includes methods.

[0056] crops The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, flowers, stalks, leaves, and fruits. The term "habitat" refers to the place where a plant is growing or is expected to grow.

[0057] The compositions according to the present invention are suitable for all conventional application methods used in agriculture, such as pre-emergence application, post-emergence application, post-harvest application, and seed coating. The compositions according to the present invention are suitable for pre-emergence or post-emergence application to crop areas.

[0058] Compositions according to the present invention are also suitable for controlling and / or preventing pests in useful plant crops, or for regulating the growth of such plants. In some embodiments, the compositions may be applied by any conventionally used method, including spraying, dripping, and wicking. One advantage of the GE of the formulations is that their small size allows for uniform coverage of plant stems and leaves with small distances between particles of the formulation. Thus, the formulations are more effective in contacting pests that damage plants.

[0059] Preferred crops of useful plants include cereals such as canola, corn, barley, oats, rye, and wheat, as well as cotton, soybeans, sugar beets, fruits, berries, nuts, vegetables, flowers, trees, shrubs, and turfgrass. The components used in the compositions of the present invention can be applied in various concentrations and in a variety of ways known to those skilled in the art. The ratio in which the composition is applied will depend on the specific type of pest to be controlled, the degree of control required, and the timing and method of application.

[0060] Crops should be understood to include crops that have been made resistant to herbicides or types of herbicides (e.g., ALS-, GS-, EPSPS-, PPO-, ACCase-, and HPPD- inhibitors) by conventional breeding methods or genetic engineering. An example of a crop made resistant to imidazolinone, such as imazamox, by conventional breeding methods is Clearfield® summer canola. An example of a crop made resistant to herbicides by genetic engineering is glyphosate- and glufosinate-resistant maize varieties, which are commercially available under the trade names RoundupReady® and LibertyLink®.

[0061] Crops should also be understood as those that have been genetically modified to be resistant to pests, such as Bt maize (resistant to the European corn borer), Bt cotton (resistant to the cotton weevil), and Bt potato (resistant to the Colorado potato beetle). An example of Bt maize is the Bt 176 maize hybrid from NK® (Syngenta Seeds). Bt toxin is a protein naturally formed by the soil bacterium Bacillus thuringiensis. Examples of toxins or genetically modified plants capable of synthesizing such toxins are described in European Patent Publication No. 451 878, European Patent Publication No. 374 753, International Publication No. 93 / 07278, International Publication No. 95 / 34656, International Publication No. 03 / 052073, and European Patent Publication No. 427 529. Examples of genetically modified plants that encode insecticide resistance and contain one or more genes expressing one or more toxins include KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard®, and Protexcta®. Plant crops or their seed materials may exhibit resistance to herbicides and simultaneously resistance to insect feeding ("superimposed" genetic modification events). For example, seeds may have the ability to express the insecticidal Cry3 protein while also exhibiting resistance to glyphosate.

[0062] Crops obtained through conventional breeding methods or genetic engineering should also be understood to include those that possess so-called output traits (e.g., improved storage stability, higher nutritional value, and improved flavor).

[0063] Other useful plants include, for example, turfgrass for golf courses, lawns, parks and roadsides, or turfgrass commercially cultivated for turfing, as well as ornamental plants such as flowers or shrubs.

[0064] A crop area is an area of ​​land where cultivated plants are already growing or where the seeds of those cultivated plants have been sown, and also an area of ​​land where those cultivated plants are intended to be grown.

[0065] Compounding additives Other active ingredients such as herbicides, plant growth regulators, algaecides, fungicides, fungicides, virucidates, insecticides, acaricides, nematicides, or molluscicides may be present in the formulation of the present invention or added to the formulation as tank mixing partners.

[0066] The compositions of the present invention may further contain other inert additives. Such additives include thickeners, fluidity enhancers, dispersants, emulsifiers, wetting agents, defoamers, biocides, lubricants, fillers, drift control agents, adhesion enhancers, auxiliary agents, evaporation retarders, freeze-protective agents, insect-attracting odorants, UV-protective agents, fragrances, and the like. Thickeners may be compounds that are soluble in water or can swell, such as xanthan gum (e.g., anionic heteropolysaccharides such as RHODOPOL® 23 (xanthan gum) (Rhodia, Cranbury, NJ)), alginates, guar or cellulose polysaccharides; modified cellulose polymers, polycarboxylates, bentonite, montmorillonite, hectonite, or synthetic macromolecules such as attapulgite. Freezing agents may be, for example, water-soluble salts such as ethylene glycol, propylene glycol, glycerol, diethylene glycol, saccharose, and sodium chloride, sorbitol, triethylene glycol, tetraethylene glycol, urea, or mixtures thereof. Typical defoamers are silicone oils, polydialkylsiloxanes, especially polydimethylsiloxanes, fluoroaliphatic esters, or perfluoroalkylphosphonic acids / perfluoroalkylphosphonic acids or their salts and mixtures thereof. A preferred defoamer is polydimethylsiloxane, e.g., Dow Corning® Antifoam A, Antifoam B, or Antifoam MSA. Typical biocides include 1,2-benzoisothiazolin-3-one, available as PROXEL® GXL (Arch Chemicals). Conventional surfactants may only be present at low concentrations due to their ability to form micelles in the aqueous phase, because these micelles extract solvents, plasticizers, and / or active ingredients from GE. Therefore, while conventional surfactants are useful for controlling the viscosity of GE dispersions, at higher concentrations they can extract components from the particles, potentially undermining their advantages. Hence, the compositions of this technology may not contain conventional surfactants at concentrations above the concentration at which they form micelles, a concentration referred to as the critical micelle concentration (CMC).For this reason, non-micelle polymer dispersants are preferred to control the viscosity of GE dispersions. Examples of conventional surfactants that form micelles include linear and branched alcohol ethoxylates and their acid esters, tristyryl-phenol ethoxylates and their acid esters, alkyl-phenol ethoxylates and their acid esters, linear and branched alkyl-aryl sulfonates such as dodecyl-benzenesulfonate, fatty acid ethoxylates, alkylamine ethoxylates, and block copolymers of ethylene oxide and higher alkylene (propylene-,butylene-) oxides. Examples of non-micelle polymer dispersants include polyvinylpyrrolidone homopolymers having molecular weights of 15-120 kDa, polyvinylpyrrolidone-vinyl acetate random copolymers, lignosulfonates, sulfonated urea-formaldehyde condensates, styrene-acrylic copolymers, comb-type polymers having alkyl backbones and polyacrylic acid side chains, alkylated polyvinylpyrrolidone, and other common non-emulsifying dispersants.

[0067] The compositions of the present invention can be mixed with fertilizers and still maintain their stability.

[0068] Dispersant (DPA) Dispersants are well known in the art, and the selection of such dispersants can involve various factors depending on a given formulation. Preferred dispersants include, without limitation, polyvinylpyrrolidone homopolymers having molecular weights of 15 to 120 kDa, polyvinylpyrrolidone-vinyl acetate random copolymers, alkylated polyvinylpyrrolidone, lignosulfonates, sulfonated urea-formaldehyde condensates, styrene-acrylic copolymers, comb-type polymers having an alkyl backbone and polyacrylic acid side chains, alkylated polyvinylpyrrolidone, and other common, non-emulsifying dispersants.

[0069] Generally, the total amount of the dispersant system in the composition may be 0.1 to 25% by weight, preferably 0.5 to 10% by weight, and most preferably 0.5 to 5% by weight. For example, the dispersant system may include a mixed dispersant: a first dispersant, a second dispersant, and a third dispersant. The total amount (by weight) of each dispersant may vary depending on the specific dispersant selected, but a typical amount of each dispersant (e.g., the first dispersant or the second or third dispersant) is 0.1 to 25% by weight, preferably 0.5 to 10% by weight, and most preferably 0.5 to 5% by weight.

[0070] Accordingly, the compositions of the present disclosure include a dispersant system having at least one dispersant, at least two dispersants, at least three dispersants, or even at least four dispersants.

[0071] The ratio (weight / weight) of any two dispersants may include 5:1 to 1:5, 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2, or approximately 1:1, or mixtures of such ratios. The ratio of any three dispersants may include 5 to 0.2:5 to 0.2:5 to 0.2, 4 to 0.25:4 to 0.25, 3 to 0.3:3 to 0.3, 2 to 0.5:2 to 0.5, or approximately 1:1:1, or mixtures of such ratios. Any ratio of the four dispersants may include 5-0.2:5-0.2:5-0.2:5-0.2; 4-0.25:4-0.25:4-0.25:4-0.25; 3-0.3:3-0.3:3-0.3:3-0.3; 2-0.5:2-0.5:2-0.5:2-0.5; or a mixture of approximately 1:1:1:1 or such ratios.

[0072] In embodiments comprising at least two dispersants, the weight / weight % of each dispersant may be 0.1 to 25 weight / weight, preferably 0.5 to 10 weight / weight, and most preferably 0.5 to 5 weight / weight.

[0073] Nevertheless, it has now been found that, in certain embodiments, nonionic alkylated vinylpyrrolidone and polyacrylate polymers are surprisingly preferable.

[0074] Alkylated vinylpyrrolidone and polyacrylate polymers are generally produced by random grafting of alpha-olefins onto the vinylpyrrolidone polymer backbone and lactam rings. These products can have a "comb-like" structure. The alkylating group is C4-C 20 It could be from C4 (butane), C 16 (Hexadexene), or C 20 It may be (ercosene). In certain embodiments, the vinylpyrrolidone / alkylation ratio is 90 / 10, 20 / 80, 50 / 50, or 30 / 70, or a combination thereof. The average molecular weight of such polymers may be 12,000–22,000, 11,000–17,000, or 14,000–20,000. Their alkylation components induce lipophilicity, while the vinylpyrrolidone sections in such polymers contribute to hydrophilicity; the presence of both lipophilic and hydrophilic elements in a single molecule makes them surfactant. Such surfactant of these polymers promotes a reduction in the particle size of GE droplets.

[0075] Furthermore, nonionic alkylated vinylpyrrolidone and polyacrylate polymers appear to be remarkably effective in GE's manufacturing processes.

[0076] Examples of commercially available alkylated vinylpyrrolidone polyacrylate polymers include Agrimer® AL, Agrimer® AL 10LC, Agrimer® AL 22, Agrimer® AL 25, Agrimer® AL 30, and Agrimer® AL 22D.

[0077] In addition, a mixture of nonionic alkylated vinylpyrrolidone, polyacrylate polymer, and highly charged ligninsulfonated lignosulfonate and nonionic comb-type polyacrylate polymer can also improve the resuspendability of GE droplets in very hard water.

[0078] A sulfonate dispersant is a dispersant containing a sulfonate group. In preferred embodiments, the sulfonate dispersant is a sodium salt or a calcium salt. Examples of sulfonate dispersants include naphthalene sulfonate, lignosulfonate, kraft lignin sulfonate, dodecyl sulfonate (SDS), and dodecylbenzene sulfonate (SDBS). In preferred embodiments, the sulfonate dispersant contains kraft lignin to increase water solubility. In addition, preferred sulfonate dispersants induce strengthening and increase the glass transition temperature. An increase in the glass transition temperature is desirable for producing GE.

[0079] Examples of commercially available sulfonate dispersants include REAX®, Polyfon, Kraftsperse, Indulin, Borresperse, NAXAN® products, and Vultamol® NN 9104.

[0080] Polyacrylate copolymers are known in the art. These polymers are prepared using an acrylic acid monomer and a second monomer. In preferred embodiments, the copolymer is a graft polymer in which the first monomer forms the main chain of the polymer and the second monomer forms branches thereon. A desirable comb-type polymer stabilizer structure consists of randomly incorporated side chains having affinity for the dispersion medium, which are chemically bonded to the anchor polymer. These comb-type polymers induce dispersion properties based on a steric hindrance stabilization mechanism.

[0081] Examples of commercially available polyacrylate copolymers include Dispersive PSL 100, Atlox 4913, Atlox 4917, and Agrilan 755.

[0082] Application method The compositions of the present invention can be used in conventional farming methods. For example, the compositions of the present invention can be mixed with water and / or fertilizer and applied to a desired habitat before and / or after sprouting by any means such as aircraft spray tanks, irrigation systems, direct injection sprayers, backpack spray tanks, cattle immersion tanks, and agricultural equipment used for ground spraying (e.g., boom sprayers, hand sprayers). The desired habitat may be soil, plants, etc.

[0083] The technology further includes a method for treating seeds or bulbils, comprising contacting the seeds or bulbils with the composition of the present invention. The technology can be applied to seeds or bulbils in any physiological state at any time between seed harvesting and seed sowing; during or after sowing; and / or after germination. Preferably, the seeds or bulbils are in a sufficiently durable state in which they suffer no or minimal damage, including physical or biological damage, during the treatment process. The formulation can be applied to seeds or bulbils using conventional coating or pelletizing techniques and machinery, e.g., fluidized bed techniques, roller mills, rotary stationary seed processing machines, and drum coaters. Seeds or bulbils can be pre-classified before coating. After coating, the seeds or bulbils are typically dried and then transferred to a classifier for classification. Such procedures are known in the art. In some embodiments, the composition of the present invention is applied as one component of a seed or bulbil coating. The treated seeds may also be wrapped in a thin film overcoating to protect the coating. Such overcoatings are known in the art and can be applied, for example, using conventional fluidized bed and drum thin-film coating techniques.

[0084] manufacturing Various methods for producing a dispersed phase GE containing a chemical agent are within the scope of the present invention, and these are described in a manner in which the chemical agent is an agrochemical active ingredient.

[0085] A method for producing a dispersed phase GE may include the following steps: a step of combining a first composition in a second composition to form a third composition, wherein the first composition is substantially immiscible in the second composition, the first composition contains an active pesticide ingredient, and the first composition contains a liquid curable, solidifying, or polymerizable resin; a step of emulsifying the third composition such that the first composition is a dispersed phase and the second composition is a continuous phase of the third composition, optionally having a median diameter of less than 200 μm of the dispersed phase; a step of adding a dispersant to the emulsified third composition to form a fourth composition; and a step of curing, solidifying, or polymerizing the liquid curable, solidifying, or polymerizable resin in the fourth composition to form polymer matrix microparticles in which the active pesticide ingredient is distributed.

[0086] Such a method may also optionally include preparing a dispersion concentrate (e.g., Composition 1) by dissolving or suspending at least one pesticide active ingredient in a non-aqueous curable liquid mixture containing at least one suitable crosslinkable resin (including monomers, oligomers, prepolymers, or blends thereof), if the resin optionally contains hydrophilic groups, optionally suitable curing agents, catalysts, plasticizers, or initiators. The dispersion concentrate can then be emulsified in an aqueous liquid to an average droplet size of 1 to 200 microns, where the liquid contains a colloidal solid as an emulsifying stabilizer, optionally a plasticizer, and optionally a specific suitable curing agent, catalyst, or initiator that can diffuse into the dispersed uncured resin droplets.

[0087] Embodiments of the above method may include modifications, except that the dispersion concentrate contains a polymerizable resin instead of a crosslinkable resin as a non-aqueous liquid. Instead of a curing reaction, the dispersed phase particles are formed by a polymerization reaction, and as a result, the resulting dispersed phase contains thermoplastic polymer particles rather than thermosetting polymer particles.

[0088] Additional steps applicable to the above method are: 1. Dissolving or suspending at least one active ingredient of a pesticide in a non-aqueous liquid mixture containing at least one suitable solidifying polymer dissolved in a volatile solvent and one or more optional plasticizers; 2. A step of emulsifying the solution in an aqueous liquid to an average droplet size of 1 to 200 microns, wherein the liquid contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; 3. A process to produce thermoplastic polymer particles having a hardness of less than 6 MPa, in which at least one agricultural active ingredient is distributed, by heating the emulsion to a temperature of approximately 30 to 120°C for approximately 0.1 to 10 hours to cause evaporation of the volatile solvent, and optionally subsequently absorbing a plasticizer, thereby producing a colloidal solid material on the surface of the particles. Includes.

[0089] The above disclosure method utilizing curing involves the following steps: 1. A step of preparing a dispersion concentrate by dissolving or suspending at least one pesticide active ingredient in a non-aqueous curable liquid mixture containing at least one suitable solidifying thermoplastic polymer molten and optionally a plasticizer; 2. A step of emulsifying the dispersed concentrate into an aqueous liquid with an average droplet size of 1 to 200 microns, wherein the liquid contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; 3. A step of cooling the emulsion and optionally subsequently absorbing a plasticizer to produce thermoplastic polymer particles having a hardness of less than 6 MPa, in which at least one agricultural active ingredient is distributed, and a colloidal solid material on the surface of the particles. It can include...

[0090] In situations where the active ingredient is soluble or miscible with the plasticizer, the above method can be modified so that the active ingredient is added after a step of curing, solidifying, or extracting the solvent from a liquid emulsion droplet, resulting in the active ingredient being absorbed or dissolved into the GE after formation rather than initially being present in the dispersion concentrate.

[0091] Therefore, the method disclosed herein involves the following steps: a. A step of dissolving or suspending at least one pesticide active ingredient in a non-aqueous liquid mixture (premix) comprising at least one suitable curable or polymerizable resin (including monomers, oligomers, prepolymers or blends thereof), and optionally a suitable curing agent, plasticizer, catalyst or initiator; b. A step of emulsifying the solution or suspension in an aqueous liquid to an average droplet size of 1 to 200 microns, wherein the liquid also contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer, a specific preferred curing agent, a catalyst or initiator that can diffuse into dispersed uncured or unpolymerized resin droplets; c. A step of crosslinking, curing, or polymerization of a resin mixture, optionally thereafter absorbing a plasticizer, to produce cured thermoset or polymerized thermoplastic resin polymer particles having a hardness of less than 6 MPa in which at least one agricultural active ingredient is distributed, and a colloidal solid material on the surface of the particles, wherein after curing, it is dispersed in an aqueous liquid. Includes.

[0092] The method may include adding a curing agent through a continuous phase after a Pickering emulsion has formed, so that the dispersed phase premix cannot be cured. Alternatively, a first very slow-reactive curing agent may be used in the dispersed concentrate, and then a second fast-curing curing agent, accelerator, or catalyst may be added through the continuous phase. These second agents are added to the continuous phase after the dispersed phase has been emulsified, and therefore they must be selected to be miscible in the continuous phase. Suitable fast-curing water-miscible curing agents include diethylenetriamine, triethylenetetramine, xylenediamine, polyethylene glycol diamine, isophorone diamine, and polyoxypropylenediamine. Mixtures of curing agents may also be used for additional flexibility.

[0093] The premix in the above method can be prepared as follows: 1) The premix of the dispersed phase is prepared using a high-shear mixer by blending, if necessary, at least one agricultural active ingredient, at least one suitable curable or polymerizable resin monomer, oligomer, prepolymer or blend thereof, a suitable curing agent, catalyst or initiator; 2) The continuous phase premix is ​​prepared by blending an aqueous liquid having a colloidal solid as an emulsion stabilizer using a low-shear mixer.

[0094] The resulting mixture of the dispersed phase premix and the continuous phase premix is ​​stirred for a suitable time under high shear conditions to form a Pickering emulsion, and then, if necessary, is heated or exposed to light or other electromagnetic radiation conditions (UV, microwave) to polymerize the dispersed phase. The shear rate and duration of emulsification can be readily determined by those skilled in the art, which are derived from the following observations: if the shear rate is too low, the emulsion and the resulting polymer matrix particles may be relatively coarse and larger than desired; if the shear rate is instead too high or the duration is too long, the emulsion-stabilizing colloid will eventually be depleted from the continuous phase so that no new interface surface between the dispersed phase and the continuous phase is effectively protected, at which point rapid coalescence or heterogeneous aggregation of the dispersed phase occurs, and the Pickering emulsion becomes heterogeneous.

[0095] In one embodiment, a mixture of a dispersed phase premix and a continuous phase premix is ​​stirred 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 induce a curing reaction.

[0096] In one embodiment, the dispersed concentrate is a. A step of dissolving or suspending at least one pesticide active ingredient in a non-aqueous liquid mixture containing at least one suitable polymer dissolved in a volatile solvent; b. A step of emulsifying the solution in an aqueous liquid to an average droplet size of 1 to 200 microns, wherein the liquid also contains a colloidal solid as a (Pickering) emulsion stabilizer; c. A step of generating thermoplastic particles having a hardness of less than 6 MPa, in which at least one agricultural active ingredient is distributed, and a colloidal solid material on the surface of the particles, wherein the emulsion is dispersed in an aqueous liquid, thereby causing evaporation of the volatile solvent. It is prepared by [method]. If necessary, more liquid may be added to the continuous phase to replace any liquid lost during the evaporation process.

[0097] One system for implementing the above method is shown in Figures 2A to 2D.

[0098] The first step in preparing GE according to the system shown in Figures 2A to 2D is shown in Figure 2A. The first step in preparing GE may include preparing various premixes.

[0099] The first premix can be prepared in the first container 101. Generally, the first premix will be a dispersed phase of the pesticide composition as described above. The first container 101 may have a mixer 109 configured to stir and / or mix the liquid in the first container 101, and a heater 107 configured to heat the liquid composition in the first container 101. In certain embodiments, the heater 109 may additionally function as a chiller to remove heat from the first container 101. In preferred embodiments, the heater 107 is located outside the first container 101 and surrounds its outer periphery. In alternative embodiments, the heater is located inside the first container 101 and is in contact with the liquid in the first container. Mixers or agitation systems include ribbon systems, tumble systems, planetary mixers, centrifugal mixers, or ResonantAcoustic® Mixing (RAM) (RAM uses low-frequency energy to generate unique material movement and sound-induced (acoustic) interactions within a container without the use of internal mechanical drive components such as impellers).

[0100] The size of the first container 101 is not particularly limited. The first container may have a volume greater than 10 gallons, for example, 10 to 1,000,000 gallons, or 100 to 500,000 gallons.

[0101] A second premix can be prepared in a second container 103. Generally, the second premix will be a continuous phase of the pesticide composition as described above. The second container 103 has a shearing system configured to apply shear to the liquid in the second container 103. In a preferred embodiment, the shearing system includes a first mixer 111 and a second mixer 113. The mixers may be the same as or different from the mixer in the first container 101. Generally, the shearing system can generate a forcing force greater than 500 rpm, for example, 1000 rpm to 25,000 rpm, 1500 rpm to 10000 rpm, or 2000 rpm to 5000 rpm.

[0102] The size of the second container 103 is not particularly limited. The second container may have a volume greater than 10 gallons, for example, 10 to 1,000,000 or 100 to 500,000.

[0103] A third premix can be prepared in the third container 105. Generally, the third premix will be a dispersant added after emulsification but before curing, solidification, or polymerization. The third container 105 may have a mixer 115 configured to stir and / or mix the liquids within the third container. Alternatively, the third container 105 may be stirred or mixed manually. The size of the third container 105 is not particularly limited. The third container 105 may have a volume greater than 1 gallon, for example, 1 to 1,000 or 1 to 500.

[0104] The second step in preparing the GE according to the system in Figures 2A to 2D is shown in Figure 2B. The second step in preparing the GE may include emulsification from the contents of the first container 101 and the second container 103. The system may include a pump 117 configured to transfer liquid between the first container 101 and the second container 103, and vice versa. The first container 101 and the second container 103 may be in fluid communication such that the bottom of the first container 101 is in fluid communication with the top of the second container 103. Fluid communication can be achieved through a conduit or piping with the pump 117 in between.

[0105] Once the first premix from the first container 101 is transferred to the second premix in the second container 103, the shearing system of the second container 103 can be used to emulsify its contents.

[0106] A third step in preparing the GE according to the system shown in Figures 2A to 2D is shown in Figure 2C. The third step in preparing the GE may include adding a dispersant and subsequently causing the dispersed phase of the emulsified composition to harden, solidify, or polymerize in the second container 103.

[0107] The system may use the same or a different pump 117 as the one used to transfer the first premix in the first container 101 to the second container 103. The fluid connection used to facilitate the transfer of the liquid from the second container 103 to the first container 101 may be the same as or different from the conduit or piping used to transfer the first premix in the first container 101 to the second container 103. For example, a different fluid communication system may connect the base of the second container 103 to the base of the first container 101.

[0108] The third premix in the third container 115 can be added to the first container 101 before the emulsion liquid is transferred from the second container 103 to the first container 101. Alternatively, the third premix can be added after the emulsion liquid is transferred from the second container 103 to the first container 101. In some embodiments, the third premix is ​​added to the second container 103 before being transferred to the first container 101. In a preferred embodiment, the third premix is ​​mixed into the emulsion liquid using the mixer 109 in the first container 101.

[0109] When the third premix is ​​incorporated into the emulsion liquid, polymerization, curing, or solidification of the emulsion liquid can occur. In a preferred embodiment, polymerization is facilitated by the heater 107 of the first container, and the mixer 109 circulates the contents of the first container.

[0110] The fourth step in preparing GE according to the system shown in Figures 2A to 2D is shown in Figure 2F. The fourth step in preparing GE may include the addition of a diluent (e.g., water) and an auxiliary agent (co-formulate), as well as packaging the product for distribution.

[0111] Once the GE is finally formed, the addition of diluents (e.g., water) and auxiliary agents is added to the first container 101 by conventional means, such as pouring them through the opening of the first container 101. A mixer 109 can be used to ensure homogeneity of the composition in the first container 101.

[0112] A liquid transfer system, including pipes or piping, which may be the same as or different from the system used to transfer liquid from the first container 101 to the second container 103, can be used to transfer the compound composition in the first container 101 to the package 127 for distribution.

[0113] The liquid transfer system can use the pump 119 to deliver the compounded product through the mesh 121. Once the compounded product has been transferred through the mesh 121, it can be temporarily stored in totes 123 and 125 before being transferred to packages 127 for distribution.

[0114] polymer Preferred polymerizable resins for use in the preparation of polymer particles of the dispersed phase include thermosetting resins such as epoxy resins, phenolic resins, aminoplast resins, polyester resins, polyacrylates, biodegradable polymers, polyurethanes, and polyureas. Epoxy resins are particularly preferred. Combinations of these resins may also be used to achieve miscibility with other components of the dispersed phase and to control the polymerization reaction kinetics.

[0115] Other suitable polymerizable resins for use in the preparation of polymer particles of the dispersed phase include thermoplastic resins such as styrene, methyl methacrylate, and acrylic. Combinations of these resins may also be used to achieve miscibility with other components of the dispersed phase.

[0116] Preferred thermoplastic polymers include the thermoplastic resin polymers mentioned above, as well as polymers such as cellulose acetate, polyacrylate, polycaprolactone, and polylactic acid.

[0117] Polymerization reactions can be initiated thermally by adding chemical curing agents and / or catalysts, or by suitable irradiation such as visible, UV, microwave or other electromagnetic irradiation, electron beam irradiation, or sonication, in order to generate reactive species such as radicals or ions.

[0118] Suitable monomers for the present invention include vinyl aromatic monomers such as styrene, α-methylstyrene, and divinylbenzene; esters of α,β-monoethylenically unsaturated mono- and dicarboxylic acids, particularly esters of acrylic acid, such as ethyl acrylate, n-butyl acrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate; and esters of methacrylic acid, such as ethyl methacrylate, n-butyl methacrylate, and n-hexyl methacrylate. Further suitable monomers are conjugated diolefins such as vinyl esters and allyl esters of aliphatic carboxylic acids, such as vinyl acetate and vinyl propionate; vinyl halides such as vinyl chloride and vinylidene chloride; and butadiene and isoprene. Examples of suitable unsaturated monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, N-vinylformamide, and N-vinylpyrrolidone, as well as acrylic acid, methacrylic acid, styrene sulfonic acid, and vinylphosphonic acid.

[0119] Additional examples of polymers suitable for use in the preparation of GE of the present invention include phenolic, urea, melamine, epoxy, silicone, polyisocyanate, polyamine and polyurethane, polycarbonate, polyalkylene terephthalate, polyphenylene oxide, polysulfone, polyimide, polyetherimide, polyhydroxyalkanoate, polycaprolactone, polyesteramide, and polylactic acid. In addition, biopolymers or biodegradable resins derived from natural materials such as plants, algae, microorganisms or animals, including vegetable oil or algal oil, lignin, humic acid, glycoprotein, protein, polypeptide, polysaccharide, cellulose or hemicellulose, may be used.

[0120] With respect to epoxy, all conventional mono-, di-, and polyepoxide monomers, prepolymers, or blends thereof are suitable epoxy resins for the implementation of the present invention. In one embodiment, the suitable epoxy resin is one that is liquid at ambient temperature. The diepoxides and polyepoxides may be aliphatic, alicyclic, or aromatic compounds. Typical examples of such compounds include diglycidyl ethers of bisphenol A, glycerol or resorcinol; hydrogenated bisphenol A; ethylene glycol; 1,2-propanediol; 1,3-propanediol; 1,4-butanediol; diethylene glycol; polyethylene glycol; polypropylene glycol; glycerol; trimethylolpropane or 1,4-dimethylolcyclohexane or 2,2-bis(4-hydroxycyclohexyl)propane; diglycidyl ethers of aliphatic or alicyclic diols or polyols; and β-methylglycidyl ethers of di- and polyphenols; di- and polyphenols, typically resorcinol, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl-2,2-propane, novolac, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; and glycidyl ethers of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Further examples include N-glycidyl compounds, such as diglycidyl compounds of ethylene urea, 1,3-propylene urea, or 5-dimethyl hydantoin, or 4,4'-methylene-5,5'-tetramethyldihydantoin, or triglycidyl isocyanurates, or biodegradable / bio-derived epoxy (vegetable oil-based).

[0121] Further glycidyl compounds of technical importance are glycidyl esters of carboxylic acids, particularly 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.

[0122] Examples of polyepoxides different from glycidyl compounds include vinylcyclohexene and dicyclopentadiene diepsides, 3-(3',4'-epoxycyclohexyl)-8,9-epoxy-2,4-dioxaspiro[5.5]undecane, 3',4'-epoxycyclohexylmethyl ester of 3,4-epoxycyclohexanecarboxylic acid, butadiene diepsides or isoprene epoxides, epoxidized linoleic acid derivatives, or epoxidized polybutadienes.

[0123] Other suitable epoxy resins include diglycidyl ethers or highly diglycidyl ethers of divalent phenols or divalent aliphatic alcohols with 2 to 4 carbon atoms, preferably diglycidyl ethers or highly diglycidyl ethers of 2,2-bis(4-hydroxyphenyl)propane and bis(4-hydroxyphenyl)methane, or mixtures thereof of these epoxy resins.

[0124] Suitable epoxy resin curing agents for carrying out the present invention are typically any suitable epoxy resin curing agent selected from primary and secondary amines and their adducts, cyanamides, dicyandiamides, polycarboxylic acids, polycarboxylic acid anhydrides, polyamines, polyaminoamides, and polyadducts of amines, polyepoxides, and polyols.

[0125] Various amine compounds (mono, di, or polyamines), such as aliphatic amines (e.g., diethylenetriamine, polyoxypropylenetriamine), alicyclic amines (e.g., isophoronediamine, aminoethylpiperazine, or diaminocyclohexane), or aromatic amines (e.g., diaminodiphenylmethane, xylenediamine, phenylenediamine), can be used as curing agents. Primary and secondary amines can broadly function as curing agents, while tertiary amines generally function as catalysts.

[0126] Epoxy curing agents are typically amines, but other options exist that may provide special flexibility to accommodate chemicals that may be unstable or soluble in the presence of amines, or that may allow for the achievement of a wider range of curing rates.

[0127] For example, other suitable curing agents include polycarboxylic acid anhydrides, typically phthalic anhydride, nadic anhydride, methylnadic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and in addition, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.

[0128] For the present invention, certain epoxy polymers are preferred. Preferred epoxy polymers are polymerization products from one or more preferred epoxy monomers and one or more preferred amine curing agents. 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-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, diglycidyl 1,2-cyclohexanedicarboxylate, isosorbide diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Preferred amine curing agents include polyoxypropylenediamine, polyoxypropylenetriamine, polyoxyethylenediamine, N-aminoethyl-piperazine, trimethyl-1,6-hexanediamine, isophoronediamine, N,N-dimethyl-1,3-diaminopropane, diethylenetriamine, N,N'-dimethylethylenediamine, and hexamethylenediamine.

[0129] Suitable catalysts such as tertiary amines, boron trifluoride, monoethylamines, imidazoles, triethanolamine, aminoethylpiperazine, tri(dimethylaminomethyl)phenol, bis(dimethylaminomethyl)phenol, and dicyandiamide can optionally be used to accelerate the epoxy curing reaction.

[0130] Colloidal solid According to the present invention, when the dispersed phase contains a chemical agent such as an active ingredient in a pesticide, any type of Pickering colloid emulsion stabilizer may be used to stabilize the emulsion before the step of solidifying the dispersed phase into the polymer matrix, regardless of the polymer matrix type.

[0131] More specifically, solids such as silica and clay are taught in the literature for use as viscosity modifiers in agrochemical formulations to inhibit gravity-driven sedimentation or cream separation by forming networks or gels throughout the continuous phase, thereby increasing low shear viscosity and slowing the movement of small particles, surfactant micelles, or emulsion droplets. The colloidal solids of the present invention, on the other hand, adsorb to transient liquid-liquid interfaces, thereby stabilizing droplets containing resin monomers during curing by forming a barrier around the curable droplets to prevent contact or adjacent curable droplets from accreting, regardless of whether the curable droplets have accumulated in a deposit layer or cream layer. The colloidal solids also play a role in preventing GE aggregation under stress conditions, such as those observed when plasticizers are absorbed into conventional latex dispersions. Two different functional-rheological modifications or emulsion and dispersion stabilizations can be distinguished by functional tests such as those described below. The effectiveness of colloidal solids in stabilizing emulsions of curable polymer droplets depends on particle size, particle shape, particle concentration, particle wetting properties, and inter-particle interactions. The colloidal solids must be small enough to coat the surface of dispersed curable liquid polymer droplets, and the curable droplets must be small enough for use with conventional application equipment. The final polymer particles (and therefore colloidal solids) will also need to be small enough to provide an acceptablely uniform product distribution at the target site. The colloidal solids must also have sufficient affinity for both the dispersed and continuous phases of the liquid so that they can adsorb to transient liquid-liquid interfaces, thereby stabilizing the emulsion during curing. These wetting properties, particle shape, and pickering-type emulsion stabilization can be easily evaluated by preparing control formulations lacking colloidal solids as emulsion stabilizers. In such cases, the curable liquid polymer droplets coalesce, forming unified clumps instead of a dispersion of polymer particles.

[0132] In one embodiment, the colloidal solid has a number-weighted median particle size diameter such that it is measured by scanning electron microscopy, with a diameter of 0.001 to 2.0 microns, particularly 0.5 microns or less, and more particularly 0.1 microns or less.

[0133] A wide variety of solid materials, such as carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica, mica, and clay, can be used as colloidal stabilizers for preparing the dispersions of the present invention. A suitable colloidal stabilizer is insoluble in any of the liquid phases present in the preparation of the concentrate formulation. If the pesticide active ingredient has preferably low solubility, less than about 100 ppm at room temperature, in any liquid used to dilute the final composition, and in both continuous and (transient) dispersion liquid phases, can be prepared with a suitable particle size, and has suitable wetting properties for such transient liquid-liquid interfaces, then this active ingredient can also function as a colloidal stabilizer. Examples of particulate inorganic materials are oxy compounds (or derivatives thereof) of at least one of calcium, magnesium, aluminum, and silicon, such as silica, silicates, marble, clay, and talc. Particulate inorganic materials may be naturally occurring or synthesized in a reactor. The particulate inorganic materials may be, but are not limited to, minerals selected from kaolin, bentonite, alumina, limestone, bauxite, gypsum, magnesium carbonate, calcium carbonate (either crushed or precipitated), perlite, dolomite, diatomaceous earth, hanthite, magnesite, boehmite, sepiolite, palygorskite, mica, vermiculite, illite, hydrotalcite, hectorite, halloysite, and gibbsite. More suitable clays (e.g., aluminosilicates) include those containing the clay minerals kaolinite, montmorillonite, or illite groups. Other specific examples are attapulgite, laponite, and sepiolite. Polymers that aggregate colloids (such as xanthan gum in the case of colloidal kaolin) can also improve the stability of the Pickering emulsion.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].

[0134] The type and amount of colloidal solid are selected to provide acceptable physical stability of the composition during curing, polymerization, solvent evaporation, or other polymer solidification processes. The colloidal solid should also be present in an amount sufficient to provide a stably dispersed composition. The term “stably dispersed” as used herein means that the particles are substantially circular spheres (in suspension) under optical microscopy and are visually distinguishable from one another when diluted. This can be readily determined by those skilled in the art by a predetermined evaluation of various compositions having different amounts of this component. For example, the ability of a colloidal solid to stabilize a composition can be verified by preparing a test sample with the colloidal solid, confirming that the droplet emulsion is stable and does not exhibit coalescence. Coalescence is evident by the formation of visible large droplets and ultimately by the formation of layers of liquid monomer, polymer melt, or polymer solution within the formulation. The physical stability of the composition during and after curing, polymerization, solvent evaporation, or other polymer solidification is acceptable if no significant coalescence is evident and the GE is present as a dispersed system. For example, in one embodiment, the colloidal solid is used in an amount of 1 to 80% by weight, particularly 4 to 50% by weight, of the dispersed phase. A mixture of colloidal solids may be used.

[0135] plasticizer The required mechanical properties of the present invention can be achieved by one or a combination of means. In some embodiments, plasticizers are used. Plasticizers are relatively small, non-reactive molecules (less than 1000 Da) that partially solubilize polymer molecules to allow segment movement, thereby imparting flexibility and reducing the rigidity of the overall polymer matrix. Plasticizers are chemically diverse and vary depending on the polymer matrix in question, and are necessarily miscible with any monomer and final polymer matrix. Plasticizers can be added to the monomer or polymer before the formation of the GM, or they can be added to the continuous phase after the polymer matrix particles have been formed. In other embodiments, the type of polymer used for the formulation can impart the desired mechanical properties. The selection of polymers with relatively long segments (more than about 5 bond lengths) between potential intermolecular crosslinking sites is such that these segments have a low tendency to form short persistence lengths (less than segment length) and organized crystalline domains, thereby imparting flexibility to the overall polymer matrix. In other embodiments, some or all of the monomers or copolymers used may be polyfunctional, enabling branching or crosslinking of the polymer matrix, or they may have a lower degree of functionality, so that during the curing reaction, these monomers reduce the overall crosslinking density, thereby producing polymer matrix microparticles with hardness of 0.001 MPa to 6 MPa. In the case of crosslinked thermosetting epoxy polymer matrices, preferred means for reducing the crosslinking density include mixing monoglycidyl ethers with conventional polyglycidyl ethers and / or mixing one or more monoprimary, mono, or disecondary amines with conventional difunctional, trifunctional, or more functional primary amine curing agents. Specific preferred monoepoxides are butyl glycidyl ether, 2-ethylhexyl glycidyl ether, t-butyl glycidyl ether, phenyl glycidyl ether, o-cresyl glycidyl ether, C12-C14 alkyl glycidyl ether, octylene oxide, allyl glycidyl ether, styrene oxide, pentadecylphenol glycidyl ether, and epoxidized soybean oil.

[0136] In certain embodiments of this technology, the inclusion of specific plasticizers may not be necessary to obtain the desired hardness of the particles. For example, and without limitation, pesticide active ingredients may possess chemical and physical properties that would make the inclusion of plasticizers unnecessary, or that would allow the active ingredient to function as a plasticizer itself. Other components of polymer particles may also produce this same effect / function.

[0137] Embodiment Embodiment 1. A step of forming a third composition by combining a first composition with a second composition, wherein the first composition is substantially immiscible with the second composition, the first composition contains an active pesticide ingredient, and the second composition contains a liquid curable, solidifying, or polymerizable resin; A step of emulsifying a third composition such that the first composition is a dispersed phase and the second composition is a continuous phase of the third composition, wherein optionally the median diameter of the dispersed phase is less than 200 μm; A step of adding a dispersant to the emulsified third composition to form a fourth composition; A fourth step involves curing, solidifying, or polymerizing a liquid in the composition to form polymer matrix fine particles in which the pesticide active ingredient is distributed. Methods that include...

[0138] Embodiment 2. The method according to Embodiment 1, wherein the dispersant is selected from a sulfonated dispersant, a substituted or unsubstituted polyvinylpyrrolidone, and / or a nonionic comb-type polyacrylate polymer.

[0139] Embodiment 3. The method according to Embodiment 2, wherein the dispersant is a sulfonated dispersant selected from lignosulfonate and / or naphthalene sulfonate, and optionally the dispersant is present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, or most preferably 0.1 to 2% by weight.

[0140] Embodiment 4. The method according to Embodiment 2, wherein the dispersant is substituted or unsubstituted polyvinylpyrrolidone, and optionally the dispersant is present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, or most preferably 0.2 to 2% by weight.

[0141] Embodiment 5. The method according to Embodiment 2, wherein the dispersant is polyvinylpyrrolidone, and optionally the dispersant is present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, or most preferably 0.1 to 2% by weight.

[0142] Embodiment 6. The method according to Embodiment 5, wherein the polyvinylpyrrolidone is alkylated.

[0143] Embodiment 7. The method according to Embodiment 5, wherein the dispersant is unsubstituted.

[0144] Embodiment 8. The method according to Embodiment 7, wherein the dispersant is a mixture of lignin sulfonated lignosulfonate, polyvinylpyrrolidone, and a nonionic comb-type polyacrylate polymer, and is optionally present in an amount of 0.1 to 20% by weight, preferably 0.2 to 15% by weight, or most preferably 0.5 to 10% by weight.

[0145] Embodiment 9. The method according to any one of Embodiments 1 to 8, wherein the second composition comprises a colloidal solid emulsion stabilizer, optionally present in an amount of 0.1 to 25% by weight, preferably 0.5 to 15% by weight, or most preferably 1 to 12% by weight.

[0146] Embodiment 10. The method according to any one of Embodiments 1 to 9, wherein at least one of the first or second composition contains a plasticizer, and optionally the plasticizer is present in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, or most preferably 1 to 8% by weight.

[0147] Embodiment 11. The method according to any one of Embodiments 1 to 10, wherein the first composition contains a chemical curing agent, and optionally the chemical curing agent is present in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, or most preferably 1 to 5% by weight.

[0148] Embodiment 12. The method according to any one of Embodiments 1 to 11, wherein the liquid curable, solidifying, or polymerizable resin is selected from epoxy, polyisocyanate, polyamine, aminoplast, phenolic, and polyester.

[0149] Embodiment 13. The method according to Embodiment 11, wherein the resin is a thermosetting epoxy resin.

[0150] Embodiment 14. The method according to any one of Embodiments 1 to 13, wherein the second composition is more than 50% by weight of water or a mixture of water and a substantially water-miscible non-aqueous liquid, the non-aqueous liquid forming a single phase when present in water at a concentration of at least 50% by weight.

[0151] Embodiment 15. The method according to any one of Embodiments 1 to 14, wherein the first composition further comprises a solvent for dissolving the active ingredient of the pesticide, and optionally the solvent is present in an amount of 5 to 75% by weight, preferably 10 to 50% by weight, or most preferably 15 to 30% by weight.

[0152] Embodiment 16. The method according to any one of Embodiments 1 to 15, wherein the hardness of the polymer matrix microparticles is less than 6 MPa, for example, less than 5 MPa, less than 1 MPa, less than 0.1 MPa, less than 0.001 MPa, or 6 MPa, 0.001 MPa and less than 1 MPa, 0.001 MPa and less than 0.1 MPa, or 0.001 MPa and less than 0.01 MPa.

[0153] Embodiment 17. The method according to any one of Embodiments 1 to 16, wherein the polymer matrix microparticles have a median diameter of less than 200 μm, for example, 1 to 200 μm, 1 to 100 μm, 1 to 50 μm, 1 to 20 μm, or 8 to 18 μm.

[0154] Embodiment 18. The method according to any one of Embodiments 1 to 17, wherein the viscosity of the fourth composition during the curing, solidification, or polymerization of the liquid curable, solidifying, or polymerizable resin remains below 2000 cP, for example, 100 cP to 1000 cP or 300 to 600 cP.

[0155] Embodiment 19. A method according to any one of Embodiments 1 to 18, further comprising the step of shear mixing a fourth composition while the first composition is curing, solidifying, or polymerizing, wherein the shear mixing is optionally at a speed greater than 500 rpm, for example, 1000 rpm to 25,000 rpm, 1500 rpm to 10,000 rpm, or 2000 rpm to 5000 rpm.

[0156] Embodiment 20. The method according to any one of Embodiments 1 to 19, wherein the third composition is more than 90% by weight of the fourth composition, for example, 90% by weight to 99.9% by weight, or 95% to 99.9% by weight.

[0157] Embodiment 21. The first container, A mixer configured to stir and / or mix a liquid in a first container, A heater configured to heat a liquid composition in a first container. A first container containing; A second container that is in fluid communication with the first container, A shearing system configured to apply shear to a liquid in a second container. A second container containing; A third container, A mixer configured to stir and / or mix liquids in a third container. A third container, including; A pump system configured to transfer liquid between a first container and a second container. A manufacturing system that includes this.

[0158] Embodiment 22. The first container has a volume greater than 10 gallons, for example, 10 to 1,000,000 or 100 to 500,000; The second container has a volume greater than 10 gallons, for example, 10 to 1,000,000 or 100 to 500,000; and / or The third container has a volume greater than 1 gallon, for example, 1 to 1,000 or 1 to 500. The system described in Embodiment 21.

[0159] Embodiment 23. The system according to either Embodiment 21 or 22, further comprising at least one bulk storage tote in fluid communication with the first container, wherein optionally, at least one bulk storage tote has a volume greater than 100 gallons, for example, 275 to 330 gallons.

[0160] Embodiment 24. The system according to Embodiment 23, further comprising a mesh filter between at least one bulk storage tote and the first container, wherein the mesh filter is optionally 100 mesh.

[0161] Embodiment 25. A system according to either Embodiment 23 or 24, further comprising a plurality of end-use product containers, wherein the plurality of end-use product containers optionally have a volume of less than 5 gallons, for example, 2 gallons, 1 gallon, 1 liter, or 0.5 liters.

[0162] Embodiment 26. A method for preparing a pesticide composition comprising the system described in any one of Embodiments 22 to 25, The process involves filling a first composition containing a liquid curable, solidifying, or polymerizable resin with an active ingredient for pesticides into a first container, and optionally mixing or stirring the first composition; The steps include: filling a second composition, which is substantially immiscible in the first composition, into a second container, and optionally mixing or stirring the first composition; The process involves pumping the first composition from a first container to a second container containing the second composition to form a third composition; A step of shearing the third composition with a shearing system to emulsify the third composition so that the first composition becomes a dispersed phase; The process involves preparing a dispersant composition in a third container; The process involves transferring the dispersant composition from the third container to the first container; The steps include transferring the third composition after shearing to the first container; The process involves transferring the dispersant composition and the third composition, followed by curing, solidifying, or polymerizing a liquid curable, solidifying, or polymerizable resin to form polymer matrix fine particles in which the pesticide active ingredient is distributed. Methods that include...

[0163] Embodiment 27. A pesticide composition prepared by the method described in any one of Embodiments 1 to 21 and 26.

[0164] Embodiment 28. A liquid pesticide composition, (a) Continuous phase and; (b) at least one dispersed phase comprising polymer matrix microparticles, wherein the polymer matrix microparticles (1) have a hardness of less than 6 MPa, (2) are colloidal solid materials present at the interface with the continuous phase, and (3) contain pesticide active ingredients; (c) Dispersant system, (c1) Sulfonate dispersants and polyacrylate copolymers, and / or (c2) Alkylated vinylpyrrolidone, nonionic polyacrylate polymer Dispersant system including A liquid dispersion composition containing the following:

[0165] Embodiment 29. The composition according to Embodiment 28, wherein the polyacrylate copolymer is present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, or most preferably 0.2 to 2% by weight.

[0166] Embodiment 30. The composition according to either claim 28 or 29, wherein the sulfonate dispersant is present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, or most preferably 0.1 to 2% by weight.

[0167] Embodiment 31. The composition according to any one of Embodiments 28 to 30, wherein the alkylated vinylpyrrolidone, nonionic polyacrylate polymer is present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, or most preferably 0.1 to 2% by weight.

[0168] Embodiment 32. The composition according to any one of Embodiments 28 to 31, wherein the sulfonate dispersant is a sodium salt.

[0169] Embodiment 33. The composition according to any one of Embodiments 28 to 32, wherein the sulfonate dispersant is naphthalene sulfonate.

[0170] Embodiment 34. The composition according to any one of Embodiments 28 to 33, wherein the sulfonate dispersant is a lignosulfonate.

[0171] Embodiment 35. The composition according to any one of Embodiments 29 to 34, wherein the pesticide active ingredient is selected from azoxystrobin, benzovin diflupyr, fludioxonil, propiconazole, pidflumetofen, and tefluthrin.

[0172] Embodiment 36. The composition according to Embodiment 35, wherein the active pesticide ingredient is tefluthrin.

[0173] Embodiment 37. The composition according to Embodiment 35, further comprising a second pesticide active ingredient distributed in polymer matrix microparticles, wherein the pesticide active ingredient is benzovindiflupyr and the second pesticide active ingredient is fludioxonil.

[0174] Embodiment 38. A liquid pesticide composition, (a) Continuous phase and; (b) at least one dispersed phase comprising polymer matrix microparticles, wherein the polymer matrix microparticles (1) have a hardness of less than 6 MPa, (2) are colloidal solid materials present at the interface with the continuous phase, and (3) contain pesticide active ingredients; (c) at least one dispersant and A liquid dispersion composition comprising, A composition in which serum formation remains below 10% after 2 months of storage at 23°C or 54°C, and / or helipath maximum remains below 120 after 2 months of storage at 23°C or 54°C.

[0175] Embodiment 39. The composition according to Embodiment 38, wherein each dispersant may be 0.1 to 25% by weight, preferably 0.5 to 10% by weight, most preferably 0.5 to 5% by weight, and optionally the total amount of dispersants is 0.1 to 25% by weight, preferably 0.5 to 10% by weight, most preferably 0.5 to 5% by weight.

[0176] Embodiment 40. The composition according to Embodiment 38 or 39, comprising at least two dispersants.

[0177] Embodiment 41. The composition according to Embodiment 38 or 39, comprising at least three dispersants.

[0178] Embodiment 42. The composition according to Embodiment 38 or 39, comprising at least four dispersants.

[0179] Embodiment 43. The composition according to any one of Embodiments 38 to 42, wherein at least one dispersant is selected from polyvinylpyrrolidone homopolymer, sulfonate dispersant, polyvinylpyrrolidone-vinyl acetate random copolymer, alkylated polyvinylpyrrolidone, lignosulfonate, sulfonated urea-formaldehyde condensate, styrene acrylic copolymer, comb-type polymer having alkyl main chains and side chains of polyacrylic acid, and alkylated polyvinylpyrrolidone.

[0180] Embodiment 44. A method for controlling pests, comprising applying a pesticidal amount of a composition described in any one of Embodiments 28 to 43 to a plant, plant propagation material, or habitat of a pest.

[0181] Embodiment 45. The method of Embodiment 44, further comprising identifying plants, plant propagation materials, or habitats of pests that are susceptible to attack by pests.

[0182] Embodiment 46. The method according to either Embodiment 44 or 45, further comprising diluting the composition before application. [Examples]

[0183] The following embodiments illustrate some further aspects of the present invention, but are not intended to limit its scope. Unless otherwise specified throughout this specification and the claims, percentages are by weight.

[0184] The products and product names used in the following examples are listed in the table below.

[0185] [Table 1]

[0186] manufacturing Example 1 The first composition was prepared by producing a mixture of water (about 80% by weight) and glycerin (about 20% by weight).

[0187] The second composition was prepared by mixing fludioxonil (about 19% by weight) and benzobindiflupy (about 2% by weight) in Hallcomid® M-8-10 (about 64% by weight) until the fludioxonil and benzobindiflupy were dissolved. Triisophosphate and resorcinol diglycidyl ether were then mixed into the second composition.

[0188] A third composition was formed by combining the first composition, the second composition, and Jeffamine® D230, and the mixture was mixed at high shear for 15 minutes. A premix of water (approximately 40% by weight) and aluminum silicate (approximately 40% by weight) was added to the third composition, and the mixture was sheared until the desired particle size was reached.

[0189] Next, the composition was heated at 70°C for 4 hours. The resulting mixture was extremely viscous, making further processing difficult.

[0190] The batch was further processed by adding Agrimer® AL 10 LC, followed by XIAMETER® ACP-1500, Acticide CT, Proxel GXL, and water to obtain the following composition.

[0191] Example 2 A third composition was prepared using the procedure of Example 1, but without triisophosphate. After shearing the third composition to the desired particle size, a premix of water (about 80% by weight) and Agrimer® AL 10LC (about 20% by weight) was added and mixed with gentle stirring for 15 minutes.

[0192] Next, the third composition was heated at 70°C for 4 hours. The resulting mixture remained fluid.

[0193] The batch was further treated by adding Dispersogen® PSL100; lignosulfonic acid, sodium salt, sulfomethylated; XIAMETER® ACP-1500, biocidal agent, water, and 75% phosphoric acid.

[0194] Dispersant test The formulation blank was designed as shown in the table below.

[0195] [Table 2]

[0196] The formulation (Example 1) was prepared using a variety of dispersants V1, with Reax® 100M at a concentration of 0.56% by weight / volume. The formulations were tested for storage stability at various temperatures for up to 6 months. Serum formation (Figure 2A) and viscosity were measured and recorded via helipath (Figure 2B).

[0197] Using the above compound blank, the post-curing process was modified with the following dispersants.

[0198] [Table 3]

[0199] The differences between various Reax® products are summarized in the table below.

[0200] [Table 4]

[0201] The effects of the dispersant on viscosity and pH are shown in Figures 2C and 2D, respectively.

[0202] The above formulations were further re-examined for sedimentation and helipass at -18°C, 23°C, and 54°C after two weeks of storage. The sedimentation test was performed as a binary re-examination, with 0 indicating no sedimentation (less than 10%) and 1 indicating sedimentation (greater than 10%). The results are shown in Figures 2E and 2F, respectively.

[0203] The formulation blank was modified to include Attagel® 50 (0.5 wt / wt%), and the binary and ternary combinations of dispersants that yield the following formulation blanks were re-examined.

[0204] [Table 5]

[0205] The following combinations were tested.

[0206] [Table 6]

[0207] These formulations were tested for sedimentation and helipass maxima as discussed above. Surprisingly, only Terperse® 2020 and Agrilan® 788 (1:1); Atlox® 4913 and Agrilan® 788 (1:1); and Dispersogen® PSL100 and Agrilan® 788 (1:1) showed sedimentation at 23°C and 54°C. The other combinations did not show sedimentation after two weeks. A summary of the helipass results and sedimentation is shown in Figure 2G. The experiments for the above formulations were extended to two months, and the helipass and sedimentation results are shown in Figure 2H.

[0208] Resuspension in hard water The following two formulations were prepared according to the method described herein.

[0209] [Table 7]

[0210] Both formulations were diluted in 1000 ppm hard water and allowed to stand for 24 hours. The compositions were then passed through 50 and 100 mesh sieves. The results for Example 1 are shown in Figure 2A. The results for Example 2 are shown in Figure 2B. As shown, significant residue was produced in Example 1, but no residue was observed in Example 2.

[0211] Although only a few exemplary embodiments of the present invention have been described in detail above, those skilled in the art will readily recognize that many modifications are possible in the exemplary embodiments without substantially departing from the novel teachings and advantages of the present invention. Accordingly, all such modifications are intended to fall within the scope of the present invention as defined in the following claims.

Claims

1. A step of forming a third composition by combining a first composition with a second composition, wherein the first composition is substantially immiscible with the second composition, the first composition contains an active ingredient for pesticides, and the first composition contains a liquid curable, solidifying, or polymerizable resin; A step of emulsifying the third composition such that the first composition is a dispersed phase and the second composition is a continuous phase of the third composition, wherein optionally the median diameter of the dispersed phase is less than 200 μm; A step of adding a dispersant to the emulsified third composition to form a fourth composition; The steps include: curing, solidifying, or polymerization of the liquid in the fourth composition to form polymer matrix fine particles in which the pesticide active ingredient is distributed; Methods that include...

2. The method according to claim 1, wherein the dispersant is selected from a sulfonated dispersant, a substituted or unsubstituted polyvinylpyrrolidone, and / or a nonionic comb-type polyacrylate polymer.

3. The method according to claim 2, wherein the dispersant is a sulfonated dispersant selected from lignosulfonate and / or naphthalene sulfonate, and optionally the dispersant is present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, or most preferably 0.1 to 2% by weight.

4. The method according to claim 2, wherein the dispersant is the substituted or unsubstituted polyvinylpyrrolidone, and optionally the dispersant is present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, or most preferably 0.1 to 2% by weight.

5. The method according to any one of claims 1 to 4, wherein the second composition comprises a colloidal solid emulsion stabilizer, optionally present in an amount of 0.1 to 25% by weight, preferably 0.5 to 15% by weight, or most preferably 1 to 12% by weight.

6. The method according to any one of claims 1 to 5, wherein the viscosity of the fourth composition during the curing, solidification, or polymerization of the liquid and the polymerizable resin remains less than 2000 cP, for example, 100 cP to 1000 cP or 300 to 600 cP.

7. The method according to any one of claims 1 to 6, further comprising shearing the fourth composition while the first composition is curing, solidifying, or polymerizing, wherein the shearing is optionally performed at a speed greater than 500 rpm, for example, 1,000 rpm to 25,000 rpm, 1,500 rpm to 10,000 rpm, or 2,000 rpm to 5,000 rpm.

8. The method according to any one of claims 1 to 7, wherein the third composition is more than 90% by weight of the fourth composition, for example, 90% by weight to 99.9% by weight, or 95% by weight to 99.9% by weight.

9. A manufacturing system suitable for carrying out the method according to any one of claims 1 to 8, The first container, A mixer configured to stir and / or mix a liquid in the first container, A heater configured to heat the liquid composition in the first container. A first container including; A second container that is in fluid communication with the first container, A shearing system configured to apply shear to a liquid in the second container. A second container containing; A third container, A mixer configured to stir and / or mix the liquid in the third container. A third container including; A pump system configured to transfer liquid between the first container and the second container. A manufacturing system that includes this.

10. A method for preparing a pesticide composition comprising the system described in claim 9, A step of filling a first composition containing an active ingredient in a pesticide and a liquid curable, solidifying, or polymerizable resin into the first container, and optionally mixing or stirring the first composition; A step of filling a second composition, which is substantially immiscible in the first composition, into the second container, and optionally mixing or stirring the second composition; The process involves pumping the first composition from the first container to the second container containing the second composition to form a third composition; A step of shearing the third composition using the shearing system to emulsify the third composition so that the first composition becomes a dispersed phase; The steps include: preparing a dispersant composition in the third container; The steps include: transferring the dispersant composition from the third container to the first container; The steps include transferring the third composition after shearing to the first container; The process involves, after the transfer of the dispersant composition and the transfer of the third composition, curing, solidifying, or polymerization of the liquid's curable, solidifying, or polymerizable resin to form polymer matrix fine particles in which the pesticide active ingredient is distributed; Methods that include...

11. A pesticide composition prepared by the method described in any one of claims 1 to 8 and claim 10.

12. (a) with the continuous phase; (b) at least one dispersed phase comprising polymer matrix fine particles, wherein the polymer matrix fine particles (1) have a hardness of less than 6 MPa, (2) are colloidal solid materials present at the interface with the continuous phase, and (3) contain an active ingredient for the pesticide; (c) Dispersant system, (c1) Sulfonate dispersants and polyacrylate copolymers, and / or (c2) Alkylated vinylpyrrolidone, nonionic polyacrylate polymer Dispersant system including A liquid dispersion composition containing the following:

13. The polyacrylate copolymer is present in an amount of 0.01 to 100% by weight, preferably 0.1 to 5% by weight, or most preferably 0.2 to 2% by weight; and / or The sulfonate dispersant is selected from naphthalene sulfonate and / or lignosulfonate and is optionally present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, or most preferably 0.1 to 2% by weight; and / or The alkylated vinylpyrrolidone and nonionic polyacrylate polymer are present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, or most preferably 0.1 to 2% by weight. The composition according to claim 12.

14. A method for controlling harmful organisms, comprising applying a composition according to any one of claims 12 to 13 in an amount effective in killing harmful organisms to a plant, plant propagation material, or the habitat of the harmful organism.

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