WO2024126624A1

WO2024126624A1 - Stabilized agrochemical composition

Info

Publication number: WO2024126624A1
Application number: PCT/EP2023/085698
Authority: WO
Inventors: Anne-Laure BREMONT VERNET; Natalia Lebedeva; Jeffrey David Fowler; Jelena NARSALE; Rene Rolf Bircher; Sejong Kim
Original assignee: Syngenta Crop Protection AG Switzerland
Current assignee: Syngenta Crop Protection AG Switzerland
Priority date: 2022-12-16
Filing date: 2023-12-13
Publication date: 2024-06-20
Anticipated expiration: 2025-06-16

Abstract

Stabilized liquid agrochemical compositions are provided that comprise flowable, liquid dispersion concentrates comprising a) a continuous liquid phase; and b) a dispersed phase comprising a dispersion of gel-like polymer matrix particles having a hardness greater than 0.01 MPa and less than 6 MPa, and where the outside surfaces of the particles comprise a colloidal solid material and the particles have an agrochemically active ingredient dissolved in a solvent in the particle.

Description

STABILIZED AGROCHEMICAL COMPOSITION [0001] The present invention relates to stabilized, liquid, chemical compositions, the preparation of such compositions and a method of using such compositions, for example, to combat pests or as plant growth regulators. BACKGROUND [0002] Gel emulsion (“GE”), and gel emulsion like, formulations are disclosed in, e.g., WO2019217770A1, WO2019217775A1, WO2011/162944, and WO2011/137170. The design of gel emulsion formulations contain soft, gel-like, ductile polymer matrix microparticles. While many advantages have been disclosed for such formulations, there has been a general lack of public study for using the plethora of possible components and their combinations. Using different components, and combinations thereof, can change the properties of the formulation. However, it is not always clear how a specific property will change (improve or worsen) when components are altered. Accordingly, there remains a need for gel emulsion formulations which have improved properties. SUMMARY [0003] Embodiments are directed to liquid dispersion concentrate compositions having (a) a continuous phase, and at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has: (1) a hardness greater than 0.001 MPa and less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient dissolved in a benzoate based solvent therein. [0004] Further embodiments are directed to liquid dispersion concentrate compositions having (a) a continuous phase; (b) at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has: (1) a hardness greater than 0.001 MPa and less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient dissolved in a solvent therein; wherein the solvent has a logP of 0.5-9.5 and a vapor pressure of below 1.3x10-5 bar at 20°C. [0005] Additional embodiments are directed to liquid dispersion concentrate compositions having (a) a continuous phase; and (b) at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has: (1) a hardness greater than 0.001 MPa and less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient dissolved in a solvent therein; wherein the solvent is an aromatic solvent with carbon numbers primarily greater than C16. [0006] As well as methods of use of such compositions including methods for controlling pests and applying to propagation materials. BRIEF DESCRIPTION OF DRAWINGS [0007] FIG.1A shows an image of a seed treatment containing tefluthrin and a close-up thereof. [0008] FIG.1B shows an image of a seed treatment containing tefluthrin and Aromatic 200 and a close-up thereof. [0009] FIG.1C shows an image of a seed treatment containing tefluthrin and benzyl benzoate as a solvent and a close-up thereof. DETAILED DESCRIPTION OF THE INVENTION [0010] The present disclosure relates to GEs. GEs are compositions where the dispersed phase is a polymer matrix gel particle in a continuous phase. In general GEs comprise an entrapped agrochemical that is either homogeneously or non-homogeneously distributed within such particle or present in the form of domains within such particle and wherein the outside surface regions of the particles comprise a colloidal solid material. The term “gel” and “gel-like” as used herein is meant as non-limiting common descriptor and not to impart a definition or limitation of “gel” or “gel-like” on to the polymer particle. [0011] Accordingly, in one embodiment, the liquid dispersion concentrate compositions of the present invention comprise: a) a continuous liquid phase, optionally comprising at least one chemical agent and optionally a polymeric dispersant; and b) at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has a hardness greater than 0.001 MPa and less than 6 MPa, and wherein the outside surfaces of the particle comprise a colloidal solid material, and optionally comprises a plasticizer, and wherein the polymer particles have at least one chemical agent distributed therein. [0012] In certain embodiments, the polymer matrix particles can also be defined by the polymer content of the polymer matrix particle itself. The polymer content of a polymer matrix particle can be calculated by taking the amount of polymer in the polymer matrix particle and dividing it by the total content of the polymer matrix particle (or the dispersed/oil phase). The calculation as used herein is based on weight. The polymer content of the polymer matrix particles can be, for example, less than 50% w/w, less than 45% w/w, less than 40% w/w, less than 35% w/w, less than 30% w/w, less than 25% w/w, less than 20% w/w, less than 15% w/w, or less than 10% w/w, or even less than 5% w/w. In specific embodiments, there is at least 1% polymer content. [0013] In one embodiment, the chemical agents are agrochemically active ingredients. [0014] In one embodiment, the colloidal solid material is a Pickering colloid emulsion stabilizer. [0015] In one embodiment, the GE comprise an entrapped agrochemical that is either homogeneously on non-homogeneously distributed within such particles or present in the form of domains within such particles. Embodiments herein preferably have at least one agrochemically active ingredient dissolved in a solvent within the particle. [0016] In the context of the present invention, mean particle or droplet size indicates the volume-weighted mean, commonly designated Dv50 as determined by dynamic light scattering. [0017] In the context of the present invention, particle hardness is measured by the nanoindenter technique. The nanoindentation technique has been widely used to characterize the mechanical properties of materials at a surface. It is based on the following standards for instrumentation: ASTM E2546 and ISO 14577. Nanoindentation uses an established methodology where an indenter tip (typically conical for relatively soft samples) with a known geometry is driven into a specific site of the material, by applying an increasing normal load. Once a pre-set maximum value has been reached, the normal 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 capacitive sensor. The resulting load/displacement curves provide data specific to the mechanical nature of the material. Established physical models are used to calculate the hardness, the elastic modulus, and other mechanical properties of the material. The high spatial resolution of nanoindentation allows for tests of local mechanical properties. [0018] In another embodiment, the dispersion concentrates for use in the liquid agrochemical compositions of the present invention are those that are formed using curing agents, monomers, oligomers, prepolymers or blends thereof that exhibit a slow curing or polymerization reaction when combined with the curing agents at ambient conditions. Particularly suitable are those curing agents, monomers, oligomers, prepolymers or blends thereof that exhibit no significant increase in viscosity under ambient conditions for a period of at least 15 minutes, more particularly 30 minutes, most particularly 1 hour, after mixing with the curing agent. [0019] In accordance with one embodiment of the invention, polymerizable thermoset resins are understood to include all molecules that may be irreversibly polymerized or cured to form a polymeric matrix that does not melt or deform at elevated temperatures below the point of thermal decomposition. The polymerization reaction may be initiated thermally, by addition of chemical curing agents or by suitable irradiation to create radicals or ions such as by visible, UV, microwave or other electromagnetic irradiation, or electron beam irradiation. Examples include the phenolics, ureas, melamines, epoxies, polyesters, silicones, rubbers, polyisocyanates, polyamines and polyurethanes. In addition, bioplastic or biodegradable thermoset resins may be used including epoxy or polyester resins derived from natural materials such as vegetable oil, soy or wood and the like. [0020] In accordance with another embodiment of the invention, polymerizable thermoplastic resins are understood to include all molecules that may be polymerized or cured to form a polymeric matrix that can melt or deform at elevated temperatures below the point of thermal decomposition. The polymerization reaction may be initiated thermally, by addition of chemical curing agents or by suitable irradiation to create radicals or ions such as 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, those described in US 2008/0171658 and the like. Examples of thermoplastic polymers for polymer particles that can be prepared from in-situ mini-emulsion polymerization include polymethylmethacrylate, polystyrene, polystyrene-co-butadiene, polystyrene-co- acrylonitrile, polyacrylate, polyalkyl acrylate, polyalkyl acetate, polyacrylonitrile or their copolymers. [0021] In accordance with yet another embodiment of the invention, solidifiable thermoplastic resins are understood to include all molecules that may be dissolved in a volatile solvent such that the solvent may be evaporated by heating to create a polymeric matrix that can melt or deform at elevated temperatures below the point of thermal decomposition. The volatile solvent is chosen to be immiscible with the continuous aqueous phase and sufficiently volatile that it can be conveniently removed from the composition by heating to a temperature below that where any significant decomposition occurs. Examples include polymers of the ethylenically unsaturated monomers described above, as well as polymers such as cellulose acetate, polyacrylates, polycaprolactone and polylactic acid. There may also be mentioned polymethylmethacrylate, polystyrene, polyethylvinyl acetate, cellulose acetate, polyacrylate, polyacrylonitrile, polyamide, polyalkyleneterephthalate, polycarbonate, polyester, polyphenylene oxide, polysulfone, polyimide, polyetherimide, polyurethane, polyvinylidene chloride, polyvinyl chloride, polypropylene and waxes, etc. In addition, bioplastic or biodegradable polymers such as thermoplastic starch, polylactic acid, polyhydroxy alkanoate, polycaprolactone, polyesteramide are also suitable for use in preparing 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 dicholoromethane and trichloromethane. Other examples of suitable polymers and solvents are described in WO2011/040956A1. [0022] The term “polymer matrix particle” or “polymer matrix microparticle” as used herein means a polymer particle that is substantially uniform in density and polymer compositional make-up throughout the particle itself. [0023] The term “microparticle” is a term that is generally used to describe particles that are microscopic in size. The polymer matrix particles of the present technology differ from microcapsules, which are composed of a distinct shell wall and hollow core. In accordance with the invention, the polymer matrix microparticles of the dispersed phase have a Dv50 particle size of from 1 to 200 microns, more particularly from 1 to 100 microns and most particularly, from 1 to 80 microns and 1-30 microns. [0024] In one embodiment, suitable polymerizable resins and polymer solutions are those which are substantially immiscible with the liquid used in the continuous phase. [0025] In the context of the present invention, a colloidal solid material is one whose properties of interest are determined by its surface interactions with other materials. Colloidal solids are therefore necessarily those with high specific surface area, typically above 10 m2/g. For example, colloidal solids are able to stabilize emulsions of immiscible liquids, as described for instance in WO 2008/030749. When serving for this purpose, such colloidal solids may be called Pickering colloids, colloidal emulsion stabilizers, or other equivalent terms. Functional tests are known for whether a colloidal solid can stabilize an emulsion as used herein. Not all colloidal solids are able to stabilize an emulsion of any given pair of immiscible liquids, and such a functional test may be used by those skilled in the art to identify a suitable colloid. [0026] In another embodiment, where the continuous phase is aqueous, the affinity of the aqueous liquids suitable for use in the continuous phase a) for the agrochemically active ingredient distributed in the dispersed phase b) is such that substantially all of the agrochemically active ingredient remains in the dispersed solid phase and substantially none migrates to the continuous phase. Those skilled in the art will readily be able to determine whether a particular aqueous liquid meets this criterion for a specific agrochemically active ingredient in question by following any standard test procedure for determining the partition coefficient of a compound (in this case, the agrochemically active ingredient of the dispersed phase) between the continuous phase and the dispersed solid phase. Accordingly, the dispersed phase b) is immiscible with the continuous phase a). [0027] In a further embodiment, the aqueous liquids suitable for use in the continuous phase a) are solutions of water-soluble solutes in water. [0028] Water-soluble solutes suitable for use in the continuous phase include salts such as halides, nitrates, sulfates, carbonates, phosphates, nitrites, sulfites, nitrides and sulfides of ammonium and of metals such as those of groups 1 to 12 of the periodic table. Other suitable solutes include sugars and osmolytes such as polysaccharides, proteins, betaines and amino acids. [0029] In one embodiment, the aqueous liquids suitable for use in the continuous phase a) are mixtures of water and a substantially water-miscible non-aqueous liquid. In the context of the invention, the term "substantially water-miscible” means a non-aqueous liquid that forms a single phase when present in water at a concentration up to at least 50 wt%. [0030] Substantially water-miscible non-aqueous liquids suitable for use in the continuous phase a) include, for example, propylene carbonate; a water-miscible glycol selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having a molecular weight of up to about 800; an acetylated glycol such as di(propylene glycol) methyl ether acetate or propylene glycol diacetate; triethyl phosphate; ethyl lactate; gamma-butyrolactone; a water-miscible alcohol such as propanol or tetrahydrofurfuryl alcohol; N-methyl pyrrolidone; dimethyl lactamide; and mixtures thereof. In one embodiment, the non-aqueous, substantially water-miscible liquid used in the continuous phase a) is a solvent for at least one optional agrochemically active ingredient. [0031] In another embodiment, the aqueous, substantially water-miscible liquid used in the continuous phase a) is fully miscible with water in all proportions. Alternatively, the aqueous, substantially water-miscible liquid used in the continuous phase a) is a waxy solid such as polyethylene glycol having a molecular weight above about 1000 and the mixture of this waxy solid with water is maintained in the liquid state by forming the composition at an elevated temperature. [0032] 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, alkyl amides, alkyl acetates, and mixtures thereof. [0033] 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 glycols having a molecular weight of up to about 800, di(propylene glycol) methyl ether acetate, propylene glycol diacetate, triethyl phosphate, ethyl lactate, gamma-butyrolactone, propanol, tetrahydrofurfuryl alcohol, N- methyl pyrrolidone, dimethyl lactamide, and mixtures thereof. [0034] Those skilled in the art will appreciate that the quantities of water and the nature and quantity of the non-aqueous, water-miscible liquid or water-soluble solute can be varied to provide mixed aqueous liquids suitable for use in the continuous phase a) and these quantities can be determined without undue experimentation. In one embodiment, the aqueous continuous phase comprises 5 to 95 wt%, more preferably 30 to 90 wt%, ethylene glycol with the balance being water. In another embodiment, the aqueous continuous phase comprises 5 to 95 wt%, more preferably 30 to 90 wt%, glycerol with the balance being water. [0035] In one embodiment, the liquid dispersion concentrate compositions of the present invention comprise a mixture of GE each containing one or more than one chemical agents (such as an agrochemically active ingredient). Each one of the chemical agent(s) is contained within the same or different dispersed phase GE, and each respective dispersed phase particle optionally includes a different polymer matrix as described above. Optionally each respective dispersed phase may have different particle sizes. [0036] In one embodiment, the liquid dispersion concentrate compositions of the present invention comprise a dispersed phase in the form of finely divided, suspended polymer particles comprising a colloidal solid material at their outside surface and containing at least one agrochemically active ingredient. Agrochemically Active Ingredients [0037] The term “agrochemically active ingredient” refers to chemicals and biological compositions, such as those described herein, which are effective in killing, preventing, or controlling the growth of undesirable pests, such as, plants, insects, mice, microorganism, algae, fungi, bacteria, and the like (such as pesticidally active ingredients). The term may also apply to compounds that act as adjuvants to promote the uptake and delivery of other active compounds. The term may also apply to compounds that control the growth of plants in a desired fashion (e.g., plant growth regulators), to a compound which mimics the natural systemic activated resistance response found in plant species (e.g., plant activator) or to a compound that reduces the phytotoxic response to a herbicide (e.g., safener). If more than one is present, the agrochemically active ingredients are independently present in an amount that is 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., the foliage of a plant or locus thereof. [0038] Examples of agrochemical active ingredients suitable for use within the continuous phase a) or disperse phase b) in accordance with the present invention include, but are not limited to: fungicides such as azoxystrobin, benzovindiflupyr, chlorothalonil, cyproconazole, cyprodinil, difenoconazole, fenpropidin, fludioxonil, mandipropamid, mefenoxam, paclobutrazole, picoxystrobin, propiconazole, pyraclostrobin, sedaxane, tebuconazole, thiabendazole and trifloxystrobin; herbicides such as acetochlor, alachlor, ametryn, anilofos, atrazine, azafenidin, benfluralin, benfuresate, bensulide, benzfendizone, benzofenap, bicyclopyrone, bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil, butamifos, butralin, butylate, cafenstrole, carbetamide, chloridazon, chlorpropham, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, clomazone, clomeprop, cloransulam-methyl, cyanazine, cycloate, desmedipham, desmetryn, dichlobenil, diflufenican, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dinitramine, dinoterb, diphenamid, dithiopyr, EPTC, esprocarb, ethalfluralin, ethofumesate, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, flamprop-methyl, flamprop-M- isopropyl, fluazolate, fluchloralin, flufenacet, flumiclorac-pentyl, flumioxazin, fluorochloridone, flupoxam, flurenol, fluridone, flurtamone, fluthiacet-methyl, indanofan, isoxaben, isoxaflutole, lenacil, linuron, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, methyldymron, metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, molinate, naproanilide, napropamide, neburon, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxyfluorfen, pebulate, pendimethalin, pentanochlor, pethoxamid, pentoxazone, phenmedipham, pinoxaden, piperophos, pretilachlor, prodiamine, profluazol, prometon, prometryn, propachlor, propanil, propazine, propham, propisochlor, propyzamide, prosulfocarb, pydiflumetofen, pyraflufen-ethyl, pyrazogyl, pyrazolynate, pyrazoxyfen, pyributicarb, pyridate, pyriminobac-methyl, quinclorac, siduron, simazine, simetryn, S-metolachlor, sulcotrione, sulfentrazone, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thidiazimin, thiobencarb, tiocarbazil, triallate, trietazine, trifluralin, and vernolate; herbicide safeners such as benoxacor, dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr; alkali metal, alkaline earth metal, sulfonium or ammonium cation of mefenpyr; mefenpyr-diethyl and oxabetrinil; insecticides such as abamectin, clothianidin, cyantraniliprole, cyanthraniliprole, emamectin benzoate, gamma cyhalothrin, imidacloprid, cyhalothrin and its enantiomers such as lambda cyhalothrin, tefluthrin, permethrin, resmethrin and thiamethoxam; nematicides such as fosthiazate, fenamiphos and aldicarb. [0039] The total amount of agrochemical active ingredients in the polymer matrix particles can be calculated by taking the amount of agrochemical active ingredients in the polymer matrix particle and dividing it by the total content of the polymer matrix particle. The calculation as used herein is based on weight. The total content of agrochemical active ingredients can be, for example, less than 95% w/w, less than 90% w/w, less than 85% w/w, less than 80% w/w, less than 75% w/w, less than 70% w/w, less than 65% w/w, less than 60% w/w, less than 55% w/w, less than 50% w/w, less than 45% w/w, less than 40% w/w, less than 35% w/w, less than 30% w/w, less than 25% w/w, even less than 20% w/w, even less than 15% w/w, even less than 10% w/w, or about 5% w/w, depending on the specific agrochemical active ingredients and the solvent used to dissolve at least one agrochemical active ingredient within the particle. In general, the amount of agrochemical active ingredients is at least 5% w/w of the particle. [0040] In one embodiment, the active ingredients in the continuous phase may be in the state of a solution, an emulsion, a microemulsion, a microcapsule or a particle or fine particle. In the context of the present invention, a fine particle is one substantially smaller than the dimensions of the GE of the dispersed phase, such that a plurality (at least 10) of active ingredient particles are within each particle of the dispersed phase, whereas a non- fine particle is one only slightly smaller than the dimensions of the GE of the dispersed phase, such that each polymeric particle contains only a few active ingredient particles. [0041] Further aspects of the invention include a method of preventing or combating infestation of plant species by pests, and regulating plant growth by diluting an amount of concentrate composition with a suitable liquid carrier, such as water or liquid fertilizer, and applying to the plant, tree, animal or locus as desired. The formulations of the present invention may also be combined in a continuous flow apparatus with water in spray application equipment, such that no holding tank is required for the diluted product. [0042] The liquid dispersion concentrate compositions can be stored conveniently in a container from which they are poured, or pumped, or into which a liquid carrier is added prior to application. [0043] If a solid agrochemically active material is present, the solid active ingredient may be milled to the desired particle size prior to dispersion within the polymerizable resin (monomers, oligomers, and/or prepolymers, etc.) that will form the GE. The solid may be milled in a dry state using an air-mill or other suitable equipment as necessary, to achieve the desired particle size. The particle size may be a Dv50 particle size of about 0.2 to about 20 microns, suitably about 0.2 to about 15 microns, more suitably about 0.2 to about 10 microns. [0044] As used herein, the term “agrochemically effective amount” means the amount of an agrochemical active compound which adversely controls or modifies target pests or regulates the growth of plants (PGR). For example, in the case of herbicides, a “herbicidally effective amount” is that amount of herbicide sufficient for controlling or modifying plant growth. Controlling or modifying effects include all deviation from natural development, for example, killing, retardation, leaf burn, albinism, dwarfing and the like. The term plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage and fruits. In the case of fungicides, the term “fungicide” shall mean a material that kills or materially inhibits the growth, proliferation, division, reproduction, or spread of fungi. As used herein, the term “fungicidally effective amount" or “amount effective to control or reduce fungi” in relation to the fungicidal compound is that amount that will kill or materially inhibit the growth, proliferation, division, reproduction, or spread of a significant number of fungi. As used herein, the terms "insecticide”, “nematicide” or “acaricide" shall mean a material that kills or materially inhibits the growth, proliferation, reproduction, or spread of insects, nematodes or acarids, respectively. An "effective amount" of the insecticide, nematicide or acaricide is that amount that will kill or materially inhibit the growth, proliferation, reproduction or spread of a significant number of insects, nematodes or acarids. [0045] In one aspect, as used herein, “regulating (plant) growth”, "plant growth regulator", PGR, “regulating” or "regulation" includes the following plant responses; inhibition of cell elongation, for example reduction in stem height and internodal distance, strengthening of the stem wall, thus increasing the resistance to lodging; compact growth in ornamentals for the economic production of improved quality plants; promotion of better fruiting; increasing the number of ovaries with a view to stepping up yield; promotion of senescence of the formation of tissue enabling fruit to absciss; defoliation of nursery and ornamental bushes and trees for mail-order business in the fall; defoliation of trees to interrupt parasitic chains of infection; hastening of ripening, with a view to programming the harvest by reducing the harvest to one to two pickings and interrupting the food-chain for injurious insects. [0046] In another aspect, “regulating (plant) growth”, "plant growth regulator", “PGR”, “regulating” or "regulation" also includes the use of a composition as defined according to the present invention for increasing the yield and/or improving the vigor of an agricultural plant. According to one embodiment of the present invention, the inventive compositions are used for improved tolerance against stress factors such as fungi, bacteria, viruses and/or insects and stress factors such as heat stress, nutrient stress, cold stress, drought stress, UV stress and/or salt stress of an agricultural plant. [0047] The selection of application rates relative to providing a desired level of pesticidal activity for a composition of the invention is routine for one of ordinary skill in the art. Application rates will depend on factors such as level of pest pressure, plant conditions, weather and growing conditions as well as the activity of the agrochemically active ingredients and any applicable label rate restrictions. Solvents [0048] Embodiments of the disclosure are particularly related to agrochemically active ingredients which are dissolved in a solvent in the polymer matrix particle. In general, a person of ordinary skill in the art can select a particular solvent based on the agrochemically active ingredient which is to be dissolved and vice versa. [0049] The total amount of solvent in the polymer matrix particles can be calculated by taking the amount of solvent in the polymer matrix particle and dividing it by the total content of the polymer matrix particle. The calculation as used herein is based on weight. The total content of solvent can be, for example, less than 80% w/w, less than 75% w/w, less than 70% w/w, less than 65% w/w, less than 60% w/w, less than 55% w/w, less than 50% w/w, less than 45% w/w, less than 40% w/w, less than 35% w/w, less than 30% w/w, less than 25% w/w, even less than 20% w/w, even less than 15% w/w, even less than 10% w/w, or even less than even less than 5% w/w depending on the specific agrochemical active ingredients and the solvent used to dissolve at least one agrochemical active ingredient within the particle. [0050] Specific solvents of the disclosure have the solvent has a logP of about 0.5 to 9.5, preferably about 1 to 9, and most preferably about 5 to 8 and/or a vapor pressure of below 1.3x10^-5 bar at 20°C, preferably below 1x10^-6 bar at 20°C, and most preferably 5x10^-7. [0051] Aspects of the disclosure are also related to benzoate based solvents, for example, benzoic acid, benzyl benzoate, methyl benzoate, and butyl benzoate. [0052] Specific solvents applicable include aromatic solvents with carbon numbers primarily greater than C16, greater than C17, greater than C18, greater than C19, greater than C20, greater than C21, greater than C22, greater than C23, greater than C24, greater than C25, or even greater than C26. Specific aromatic solvents can be those listed above, +1C, for example, a C16 solvent can be primarily composed of C15-17, and C17 can be primarily composed of C16-18, etc. These solvents can be combined with solvents having lower carbon numbers, for example Aromatic 200 and Aromatic 150. [0053] In specific embodiments, solvent excludes aromatic hydrocarbons having carbon numbers primarily in the range of C12-15 such as Aromatic 200. Alternative, embodiments can exclude aromatic solvents that are primarily made up of C9-C11 aromatic hydrocarbons, such as Aromatic 150. Crops [0054] The term plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, flowers, stalks, foliage and fruits. The term locus refers to where the plant is growing or is expected to grow. [0055] The composition according to the invention is suitable for all methods of application conventionally used in agriculture, e.g. pre-emergence application, post- emergence application, post-harvest and seed dressing. The compositions according to the invention are suitable for pre- or post-emergence applications to crop areas. [0056] The compositions according to the invention are also suitable for combating and/or preventing pests in crops of useful plants or for regulating the growth of such plants. In some embodiments, the compositions may be applied by any method that is conventionally used, including spraying, dripping, and wicking. One advantage of the GE of the present formulations is that their small size permits an even coverage of plant stems and leaves where the distance between particles of the formulation is small. Thus, the formulation is more effective in contacting pests that damage the plant. [0057] Preferred crops of useful plants include canola, cereals such as maize, barley, oats, rye and wheat, cotton, soya, sugar beets, fruits, berries, nuts, vegetables, flowers, trees, shrubs and turf. The components used in the composition of the invention can be applied in a variety of ways known to those skilled in the art, at various concentrations. The rate at which the compositions are applied will depend upon the particular type of pests to be controlled, the degree of control required, and the timing and method of application. [0058] Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®. [0059] Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-451878, EP-A-374753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut ^ (maize), Yield Gard ^ (maize), NuCOTIN33B ^ (cotton), Bollgard ^ (cotton), NewLeaf ^ (potatoes), NatureGard ^ and Protexcta ^. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate. [0060] Crops are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour). [0061] Other useful plants include turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod, and ornamental plants such as flowers or bushes. [0062] Crop areas are areas of land on which the cultivated plants are already growing or in which the seeds of those cultivated plants have been sown, and also areas of land on which it is intended to grow those cultivated plants. Formulation Additives [0063] Other active ingredients such as herbicide, plant growth regulator, algaecide, fungicide, bactericide, viricide, insecticide, acaricide, nematicide or molluscicide may be present in the formulations of the present invention or may be added as a tank-mix partner with the formulations. [0064] The compositions of the invention may further comprise other inert additives. Such additives include thickeners, flow enhancers, dispersants, emulsifiers, wetting agents, antifoaming agents, biocides, lubricants, fillers, drift control agents, deposition enhancers, adjuvants, evaporation retardants, freeze protecting agents, insect attracting odor agents, UV protecting agents, fragrances, and the like. The thickener may be a compound that is soluble or able to swell in water, such as, for example, polysaccharides of xanthans (e.g., anionic heteropolysaccharides such as RHODOPOL® 23 (Xanthan Gum)(Rhodia, Cranbury, NJ)), alginates, guars or celluloses; synthetic macromolecules, such as modified cellulose-based polymers, polycarboxylates, bentonites, montmorillonites, hectonites, or attapulgites. The freeze protecting agent may be, for example, ethylene glycol, propylene glycol, glycerol, diethylene glycol, saccharose, water-soluble salts such as sodium chloride, sorbitol, triethylene glycol, tetraethylene glycol, urea, or mixtures thereof. Representative anti-foam agents are silicone oils, polydialkylsiloxanes, in particular polydimethylsiloxanes, fluoroaliphatic esters or perfluoroalkylphosphonic/perfluoroalkylphosphonic acids or the salts thereof and mixtures thereof. Suitable antifoams are polydimethylsiloxanes, such as Dow Corning® Antifoam A, Antifoam B or Antifoam MSA. Representative biocides include 1,2- benzisothiazolin-3-one, available as PROXEL® GXL (Arch Chemicals). Conventional surfactants may only be present at low concentrations because of their ability to form micelles in the aqueous phase, because these micelles extract solvent, plasticizer and/or active ingredient from the GE. Thus although conventional surfactants are useful to control the viscosity of dispersions of GE, at higher concentrations they have the potential to extract components from the particles and obviate their advantages. Therefore, compositions of the present technology may not contain conventional surfactants at concentrations above that at which they form micelles, which concentration is termed the critical micelle concentration (CMC). For this reason non-micellar polymeric dispersants are preferred to control the viscosity of dispersions of GE. Examples of conventional surfactants that form micelles are linear and branched alcohol ethoxylates and their acid esters, tristyryl-phenol ethoxylates and their acid esters, alkyl- phenol ethoxylates and their acid esters, linear or branched alkyl-aryl sulfonates such as dodecyl-benzene sulfonate, fatty acid ethoxylates, alkyl amine ethoxylates, block copolymers of ethylene oxide and higher alkylene (propylene-, butylene-) oxides. Examples of non-micellar polymeric dispersants include polyvinylpyrrolidone homopolymer with a molecular weight between 15-120kDa, polyvinylpyrrolidone-vinyl acetate random copolymer, lignosulfonates, sulfonated urea-formaldehyde condensates, styrene acrylic copolymers, comb polymers with an alkyl backbone and side chains of polyacrylic acid, alkylated polyvinylpyrrolidone, and other general, non-emulsifying dispersants. [0065] Dispersants are well known in the art and selection of such will have various factors dependent on a given formulation. Preferred dispersants, as noted above, include, without limitation, polyvinylpyrrolidone homopolymer with a molecular weight between 15-120kDa, polyvinylpyrrolidone-vinyl acetate random copolymer, lignosulfonates, sulfonated urea-formaldehyde condensates, styrene acrylic copolymers, comb polymers with alkyl backbone and side chains of polyacrylic acid, alkylated polyvinylpyrrolidone, and other general, non-emulsifying dispersants. [0066] The compositions of the invention may be mixed with fertilizers and still maintain their stability. [0067] The compositions of the invention may be used in conventional agricultural methods. For example, the compositions of the invention may be mixed with water and/or fertilizers and may be applied preemergence and/or postemergence to a desired locus by any means, such as airplane spray tanks, irrigation equipment, direct injection spray equipment, knapsack spray tanks, cattle dipping vats, farm equipment used in ground spraying (e.g., boom sprayers, hand sprayers), and the like. The desired locus may be soil, plants, and the like. Propagation Material Treatments [0068] The present technology further includes a method for treating seeds or plant propagules, comprising contacting said seeds or plant propagules with a composition of the present invention. The present technology can be applied to a seed or plant propagule in any physiological state, at any time between harvest of the seed and sowing of the seed; during or after sowing; and/or after sprouting. It is preferred that the seed or plant propagule be in a sufficiently durable state that it incurs no or minimal damage, including physical damage or biological damage, during the treatment process. A formulation may be applied to the seeds or plant propagules using conventional coating or pelleting techniques and machines, such as: fluidized bed techniques, the roller mill method, rotostatic seed treaters, and drum coaters. The seeds or plant propagules may be pre- sized before coating. After coating, the seeds or plant propagules are typically dried and then transferred to a sizing machine for sizing. Such procedures are known in the art. In some embodiments, a composition of the present invention is applied as one ingredient of a seed or plant propagule coating. The treated seeds may also be enveloped with a film over-coating to protect the coating. Such over-coatings are known in the art and may be applied using conventional fluidized bed and drum film coating techniques, for example. Method of Making [0069] In one embodiment, the dispersion concentrate is prepared by adding the hardener through the continuous phase, after the Pickering emulsion is formed, so that the dispersed phase premix is incapable of curing. Alternatively a first very slow-reacting hardener can be used in the dispersion concentrate, and then a second fast-curing hardener, an accelerator or catalyst can be added through the continuous phase. These second agents are added to the continuous phase after the dispersed phase is emulsified, so they must be chosen to be miscible in the continuous phase. Suitable fast cure water- miscible hardeners include diethylene triamine, triethylene tetramine, xylene diamine, polyethylene glycol diamine, isophorone diamine and polyoxypropylene diamine. Mixtures of hardeners may also be employed for extra flexibility. [0070] In one embodiment, the dispersion concentrate is prepared by adding a premix of the dispersed phase to a premix of the continuous phase, wherein: 1) the premix of the dispersed phase is prepared by blending with a high shear mixer: at least one agriculturally active ingredient, at least one suitable curable or polymerizable resin monomer, oligomer, prepolymer or blend thereof, a suitable hardener, catalyst or initiator; 2) the premix of the continuous phase is prepared by blending with low shear mixer: an aqueous liquid with a colloidal solid as an emulsion stabilizer. [0071] The resulting mixtures of the dispersed phase premix and the continuous phase premix are stirred under high shear conditions for a suitable time to form a Pickering emulsion and then heated or exposed to light or other electromagnetic radiation conditions (UV, microwave), as needed, in order to polymerize the dispersed phase. The shear rate and duration of the emulsification may be readily determined by one skilled in the art, guided by the following observations: if the shear rate is too low, the emulsion and resulting polymer matrix particles are relatively coarse and may be larger than desired; if the shear rate is instead too high or of too long a duration, the emulsion stabilizing colloid eventually becomes so depleted from the continuous phase that any new interfacial surface between the dispersed and continuous phases is effectively unprotected, at which point rapid coalescence or heteroflocculation of the dispersed phase occurs and the Pickering emulsion becomes inhomogeneous. [0072] In one embodiment, the mixture of the dispersed phase premix and the continuous phase premix is stirred under high shear conditions for 5-10 min and heated to a temperature of about 30-120 ^C for about 0.1- 10 hr in order to effect the curing reaction. [0073] In one embodiment, the dispersion concentrate is prepared by: a. dissolving or suspending at least one agrochemically active ingredient in a non- aqueous liquid mixture comprising at least one suitable polymer dissolved in a volatile solvent; b. emulsifying said solution in to an aqueous liquid to a mean droplet size of 1 – 200 microns, which liquid also contains a colloidal solid as (Pickering) emulsion stabilizer; and c. effecting evaporation of the volatile solvent by heating the emulsion to a temperature of about 30-120 ^C for about 0.1- 10 hr to produce thermoplastic particles having a hardness greater than 0.001 MPa and less than 6 MPa with at least one agriculturally active ingredient distributed therein and a colloidal solid material at the surface of the particle, and which are dispersed in the aqueous liquid. If necessary more liquid may be added to the continuous phase to replace any liquid lost during the evaporation process. [0074] Preferred polymerizable resins for use in preparing the polymer particles of the dispersed phase include thermosets such as epoxy resins, phenolic resins, aminoplast resins, polyester resins, polyacrylate, biodegradable polymer, polyurethane, and polyurea. Epoxy resins are particularly preferred. Combinations of these resins may also be used to achieve miscibility with the other components of the disperse phase and to control the polymerization kinetics. [0075] Other suitable polymerizable resins for use in preparing the polymer particles of the dispersed phase include thermoplastics resins such as styrenes, methyl methacrylates, and acrylics. Combinations of these resins may also be used to achieve miscibility with the other components of the disperse phase. [0076] Preferred thermoplastic polymers include polymers of the thermoplastic resins described above, as well as polymers such as cellulose acetate, polyacrylates, polycaprolactone and polylactic acid. [0077] The polymerization reaction may be initiated thermally, by addition of chemical curing agents and/or catalysts or by suitable irradiation such as by visible, UV, microwave or other electromagnetic irradiation, electron beam irradiation, or ultrasonication to produce reactive species such as radicals or ions. [0078] Suitable monomers for the present invention comprise vinylaromatic monomers, such as styrene, α-methylstyrene, divinylbenzene and the like, esters of α,β- monoethylenically unsaturated mono- and dicarboxylic acids, in particular the esters of acrylic acid, such as ethyl acrylate, n-butyl acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and the esters of methacrylic acid, such as ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate and the like. Suitable monomers are furthermore vinyl esters and allyl esters of aliphatic carboxylic acids, for example vinyl acetate and vinyl propionate, vinyl halides, such as vinyl chloride and vinylidene chloride, conjugated diolefins, such as butadiene and isoprene. Examples of suitable unsaturated monomers also include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, N-vinylformamide and N-vinylpyrrolidone, and also acrylic acid, methacrylic acid, styrenesulfonic acid, and vinylphosphonic acid. [0079] Additional examples of polymers suitable for use in preparing the GE of the present invention include the phenolics, ureas, melamines, epoxies, silicones, polyisocyanates, polyamines and polyurethanes, polycarbonate, polyalkyleneterephthalate, polyphenylene oxide, polysulfone, polyimide, polyetherimide, polyhydroxy alkanoate, polycaprolactone, polyesteramide, and polylactic acid. In addition, biopolymer or biodegradable resins may be used derived from natural materials such as plants, algae, microbes or animals, including vegetable or algal oils, lignin, humic acid, glycoproteins, proteins, polypeptides, polysaccharides, cellulose or hemicellulose, and the like. [0080] With respect to the epoxies, all customary mono-, di-, and polyepoxide monomers, prepolymers or blends thereof are suitable epoxy resins for the practice of this invention. In one embodiment, suitable epoxy resins are those that are liquid at ambient temperature. The di- and polyepoxides may be aliphatic, cycloaliphatic or aromatic compounds. Typical examples of such compounds are the diglycidyl ethers of bisphenol A, glycerol or resorcinol, the glycidyl ethers and β-methylglycidyl ethers of aliphatic or cycloaliphatic diols or polyols, including those of hydrogenated bisphenol A, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane or 1,4-dimethylolcyclohexane or of 2,2-bis(4-hydroxycyclohexyl)propane, the glycidyl ethers of di- and polyphenols, typically resorcinol, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl-2,2- propane, novolaks and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, Further examples are N- glycidyl compounds, including diglycidyl compounds of ethylene urea, 1,3-propylene urea or 5-dimethylhydantoin or of 4,4'-methylene-5,5'-tetramethyldihydantoin, or those such as triglycidyl isocyanurate, or biodegradable/bio-derived epoxies (vegetable oil- based). [0081] Further glycidyl compounds of technical importance are the glycidyl esters of carboxylic acids, especially di-and polycarboxylic acids. Typical examples are the 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 of partially polymerized, e.g. dimerised, fatty acids. [0082] Exemplary of polyepoxides that differ from glycidyl compounds are the diepoxides of vinylcyclohexene and dicyclopentadiene, 3-(3',4'-epoxycyclohexyl)-8,9- epoxy-2,4-dioxaspiro[5.5]undecane, the 3',4'-epoxycyclohexylmethyl ester of 3,4- epoxycyclohexanecarboxylic acid, butadiene diepoxide or isoprene diepoxide, epoxidized linoleic derivatives or epoxidized polybutadiene. [0083] Other suitable epoxy resins are diglycidyl ethers or advanced diglycidyl ethers of dihydric phenols or dihydric aliphatic alcohols of 2 to 4 carbon atoms, preferably the diglycidyl ethers or advanced diglycidyl ethers of 2,2-bis(4-hydroxyphenyl)propane and bis(4-hydroxyphenyl)methane or a mixture of these epoxy resins. [0084] Suitable epoxy resin hardeners for the practice of this invention may be any suitable epoxy resin hardener, typically selected from primary and secondary amines and their adducts, cyanamide, dicyandiamide, polycarboxylic acids, anhydrides of polycarboxylic acids, polyamines, polyamino-amides, polyadducts of amines and polyepoxides and polyols. [0085] A variety of amine compounds (mono, di or polyamines) can be used as a hardener such as aliphatic amines (diethylene triamine, polyoxypropylene triamine etc), cycloaliphatic amines (isophorone diamine, aminoethyl piperazine or diaminocyclohexane etc), or aromatic amines (diamino diphenyl methane, xylene diamine, phenylene diamine etc). Primary and secondary amines broadly can serve as hardening agents while tertiary amines generally act as catalysts. [0086] Although epoxy hardeners are typically amines, other options exist and these will give extra flexibility to accommodate chemical agents that might be unstable or soluble in the presence of amine, or allow a broader range of cure rates to be achieved. [0087] For example, other suitable hardeners are anhydrides of polycarboxylic acids, typically phthalic anhydride, nadic anhydride, methylnadic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and, in addition, tetrahydrophthalic anhydride and hexahydrophthalic anhydride. [0088] For the present invention, certain epoxy polymers are preferred. Preferred epoxy polymers are the polymerized products from one or more preferred epoxy monomers and one or more preferred amine hardeners. Preferred epoxy monomers include: cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, bisphenol A diglycidyl ether, resorcinol diglycidyl ether, glycerol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropyleneglycol diglycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, diglycidyl 1,2-cyclohexanedicarboxylate, isosorbide diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Preferred amine hardeners include: Polyoxypropylene diamine, polyoxypropylene triamine, polyoxyethylene diamine, N-aminoethyl-piperazine, trimethyl-1,6-hexanediamine, isophorone diamine, N,N-dimethyl-1,3-diaminopropane, diethylene triamine, N,N′-dimethylethylenediamine, and hexamethylenediamine. [0089] Suitable catalysts such as tertiary amines, borontrifluoride, monoethylamine, imidazoles, triethanolamine, aminoethylpiperazine, tri(dimethylaminomethyl)phenol, bis(dimethylaminomethyl) phenol and dicyandiamides can be optionally used to accelerate the epoxy curing reaction. Colloidal Solids [0090] In accordance with the invention, Pickering colloidal emulsion stabilizers of any type may be used to stabilize emulsions prior to the step of solidifying the dispersed phase into a polymer matrix, regardless of polymer matrix type, where the dispersed phase contains a chemical agent such as an agrochemical active ingredient. [0091] More specifically, solids, such as silicas and clays, have been taught in the literature for use as viscosity modifiers in agrochemical formulations to inhibit gravity- driven sedimentation or cream separation by forming a network or gel throughout the continuous phase, thereby increasing the low-shear viscosity, and slowing the movement of small particles, surfactant micelles or emulsion droplets. The colloidal solids of the present invention instead serve to stabilize the droplets containing the resin monomers during cure by adsorbing to the transient liquid-liquid interface, thereby forming a barrier around the curing droplets so that contacting or neighbouring curing droplets are not able to coalesce, irrespective of whether or not the curing droplets have collected in a sediment or a cream layer. The colloidal solids also serve to prevent the GE’s from congealing under stress conditions as is observed when plasticizers are imbibed into conventional latex dispersions. It is possible to distinguish the two different functions - rheological modification or emulsion and dispersion stabilization, by a functional test such as described below. The effectiveness of the colloidal solid in stabilizing the emulsions of curing polymer droplets depends on particle size, particle shape, particle concentration, particle wettability and the interactions between particles. The colloidal solids must be small enough so that they can coat the surfaces of the dispersed curing liquid polymer droplets, and the curing liquid droplets must be sufficiently small for use in conventional application equipment. The final polymer particles (and hence, the colloidal solids) will also need to be small enough to provide an acceptably even product distribution at the target site. The colloidal solid also must have sufficient affinity for both the liquids forming the dispersed and continuous phases so that they are able to adsorb to the transient liquid-liquid interface and thereby stabilize the emulsion during cure. This wetting characteristic, particle shape and suitability for Pickering-type emulsion stabilization may be readily assessed by preparing a control formulation lacking the colloidal solid as emulsion stabilizer. In such a case the curing liquid polymer droplets coalesce and form a consolidated mass instead of a dispersion of polymer particles. [0092] In one embodiment, the colloidal solids have a number-weighted median particle size diameter as measured by scanning electron microscopy of 0.001 - 2.0 microns, particularly 0.5 microns or less, more particularly 0.1 microns or less. [0093] A wide variety of solid materials may be used as colloidal stabilizers for preparing the dispersions of the present invention including carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica, mica and clays. Suitable colloidal stabilizers are insoluble in any of the liquid phases present in preparation of the concentrate formulation. If an agrochemical active ingredient has suitably low solubility in any liquid used to dilute the final composition, and in both the continuous and (transient) dispersed liquid phases, that is below about 100 ppm at room temperature, and can be prepared at a suitable particle size, and has suitable wetting properties for the transient liquid-liquid interface as described above, then it is also possible that this active ingredient can serve as the colloidal stabilizer. Examples of particulate inorganic materials are oxy compounds of at least one of calcium, magnesium, aluminium and silicon (or derivatives of such materials), such as silica, silicate, marble, clays and talc. Particulate inorganic materials may be either naturally occurring or synthesized in reactors. The particulate inorganic material may be a mineral chosen from, but not limited to, kaolin, bentonite, alumina, limestone, bauxite, gypsum, magnesium carbonate, calcium carbonate (either ground or precipitated), perlite, dolomite, diatomite, huntite, magnesite, boehmite, sepiolite, palygorskite, mica, vermiculite, illite, hydrotalcite, hectorite, halloysite and gibbsite. Further suitable clays (for example aluminosilicates) include those comprising the kaolinite, montmorillonite or illite groups of clay mineral. Other specific examples are attapulgite, laponite and sepiolite. Polymers that flocculate the colloids (such as xanthan in the case of colloidal kaolin) can also improve the stability of Pickering emulsions. Other polymers suitable as colloid 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]. [0094] The type and amount of colloidal solid is selected so as to provide acceptable physical stability of the composition during cure, polymerization, solvent evaporation or other polymer solidification processes. The colloidal solid should also be present in an amount to provide for a stably-dispersed composition. The term “stably-dispersed” as used herein means that under optical microscopy the particles are substantially round spheres (in suspension) and on dilution are visibly identifiable from each other. This can readily be determined by one of skill in the art by routine evaluation of a range of compositions having different amounts of this component. For example, the ability of the colloidal solids to stabilize the composition can be verified by preparing a test sample with the colloidal solid and it can be confirmed that the emulsion of droplets is stable and does not exhibit coalescence. Coalescence is apparent by the formation of large droplets visible to the eye, and ultimately by the formation of a layer of liquid monomers, polymer melt or polymer solution within the formulation. Physical stability of the composition during and after cure, polymerization, solvent evaporation or other polymer solidification is acceptable if no significant coalescence is evident and the GE are present as a dispersion. [0095] For example, in one embodiment the colloidal solids are employed in an amount of from 1 to 80%, particularly from 4 to 50% by weight of the dispersed phase. Mixtures of colloidal solids may be employed. Plasticizers [0096] The required mechanical properties of the present invention can be achieved by one or a combination of means. In some embodiments, a plasticizer is used. Plasticizers are relatively small, non-reactive molecules (below 1000 Da) that partially solubilize the polymer molecules to allow movement of segments, thereby conferring flexibility and reducing the rigidity of the overall polymer matrix. Plasticizers are chemically diverse and vary according to the polymer matrix in question, being of necessity miscible with any monomers and the final polymer matrix. Plasticizers may be added to the monomers or polymers prior to formation of the GE, or they may be added to the continuous phase after the polymer matrix particles are formed. In other embodiments, the kind of polymer used for formulation can confer the desired mechanical properties. The selection of polymers with relatively long (more than about 5 bond lengths) segments between sites of potential inter-molecular cross-links, such that these segments have a short persistence length (less than the segment length) and a low tendency to form organized crystal-like domains thereby confer flexibility on the overall polymer matrix. In other embodiments, some or all of the monomers or copolymers used may instead of being multi-functional to allow branching or cross-linking of the polymer matrix, have a lower degree of functionality such that during the curing reaction these monomers reduce the overall cross-link density, thereby producing a polymer matrix microparticle of a hardness between 0.001 MPa and 6 MPa. In the case of cross-linked thermoset epoxy polymer matrices, a preferred means to reduce cross-link density includes mixing mono-glycidyl- ethers with the conventional poly-glycidyl-ethers, and/or mixing one or more mono- primary, mono- or di-secondary amines with the conventional di-, tri- or higher- functional primary amine hardeners. Specific preferred mono-epoxides 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, pentadecyl phenol glycidyl ether and epoxidized soybean oil. [0097] In certain embodiments of the technology, the inclusion of a specific plasticizer will not be need to obtain the desired hardness of the particle. By way of example, and without limitation, the agrochemical active ingredient itself may have chemical and physical properties which would make the inclusion of a plasticizer unnecessary, or allow the active ingredient itself to function as a plasticizer. Other components of the polymer particle may also cause this same effect/function. Embodiments [0098] Embodiment 1.A liquid dispersion concentrate composition comprising: (a) a continuous phase; (b) at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has: (1) a hardness greater than 0.001 MPa and less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient dissolved in a benzoate based solvent therein and optionally wherein the solvent has a logP of 0.5-9.5 and a vapor pressure of below 1.3x10-5 bar at 20°C and/or the solvent is an aromatic solvent with carbon numbers primarily greater than C16. [0099] Embodiment 2. A liquid dispersion concentrate composition comprising: (a) a continuous phase; (b) at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has: (1) a hardness greater than 0.001 MPa and less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient dissolved in a solvent therein; wherein the solvent is an aromatic solvent with carbon numbers primarily greater than C16, and optionally wherein the solvent has a logP of 0.5-9.5 and a vapor pressure of below 1.3x10-5 bar at 20°C and/or benzoate based solvent. [0100] Embodiment 3. A liquid dispersion concentrate composition comprising: (a) a continuous phase; (b) at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has: (1) a hardness greater than 0.001 MPa and less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient dissolved in a solvent therein; wherein the solvent has a logP of 0.5-9.5 and a vapor pressure of below 1.3x10^-5 bar at 20°C, and optionally wherein the solvent is an aromatic solvent with carbon numbers primarily greater than C16 and/or benzoate based solvent. [0101] Embodiment 4. The liquid dispersion of any one of embodiments 1-3, wherein the solvent is benzyl benzoate, methyl benzoate, and butyl benzoate. [0102] Embodiment 5. The liquid dispersion of any one of embodiments 1-4, wherein the solvent is benzyl benzoate. [0103] Embodiment 6. The liquid dispersion of any one of embodiments 1-5, wherein the agrochemical active is an insecticide or fungicide. [0104] Embodiment 7. The liquid dispersion of any one of embodiments 1-6, wherein the agrochemical active is a pyrethroid. [0105] Embodiment 8. The liquid dispersion of any one of embodiments 1-7, wherein the agrochemical active is tefluthrin. [0106] Embodiment 9. The liquid dispersion of any one of embodiments 1-8, wherein the solvent is aromatic. [0107] Embodiment 10. The liquid dispersion of any one of embodiments 1-9, wherein the solvent is an aromatic ester. [0108] Embodiment 11. The liquid dispersion of any one of embodiments 1-10, wherein the dissolved agrochemical active ingredient does not substantially crystalize after application to a plant propagation material. [0109] Embodiment 12. The liquid dispersion of any one of embodiments 1-11, wherein the solvent is about 10-50% w/w of the liquid dispersion. [0110] Embodiment 13.The liquid dispersion of any one of embodiments 1-12, wherein the dissolved agrochemical active ingredient is present in about 1-50% w/w of the liquid dispersion. [0111] Embodiment 14. The composition of any one of embodiments 1-13, wherein the dust produced by the formulation after application to a propagation material is less than 1320 ug per 100,000 seeds with a dust-off Heubach test. [0112] Embodiment 15. The composition of any one of embodiments 1-14, wherein the dust produced by the formulation to a propagation material is between 400-1320 ug per 100,000 seeds with a dust-off Heubach test. [0113] Embodiment 16. A seed coated with a diluted composition of any one of embodiments 1-15. [0114] Embodiment 17. A method of controlling pests, comprising: diluting the composition of any one of embodiments 1-15; and applying the diluted composition to a propagation material, the locus of a pest, or a plant. EXAMPLES [0115] The following examples illustrate further some of the aspects of the invention but are not intended to limit its scope. Where not otherwise specified throughout this specification and claims, percentages are by weight. [0116] The following formulations were prepared: Sample 1 Ingredients gram oil phase Tefluthrin 13.81 Benzyl benzoate 19.6 Huntsman DY-N 6.14 ( Neopentyl diglycidyl ether CAS 17557- 23-2) Huntsman Aradur21 1.86 (Trimethyl hexane diamine CAS 25620-58- 0) aqueous water 41.3 phase universal gel 2 Infilm939 4 Propylene glycol 5 Post-cure neutralizer Phosphoric acid ~ 0.5 (pH 7.5) dispersant Reax 100M 1 thickener Universal gel 2 WATER 2 Sample 2 Ingredients gram oil phase Tefluthrin 13.81 Benzyl benzoate 15.90 Huntsman DY-N 8.10 ( Neopentyl diglycidyl ether CAS 17557-23-2) Huntsman Aradur21 (Trimethyl hexane diamine CAS 25620-58-0) 1.7 Jeffamine D400 1.7 aqueous water 41.3 phase universal gel 2 Infilm939 4 Propylene glycol 5 Post-cure neutralizer Phosphoric acid ~ 0.5 (pH 7.5) dispersant Reax 100M 1 thickener Universal gel 2 WATER 2 Sample 3 Ingredients gram oil phase Tefluthrin 13.81 Benzyl benzoate 15.90 Huntsman DY-N 8.30 ( Neopentyl diglycidyl ether CAS 17557-23-2) Huntsman Aradur21 (Trimethyl hexane diamine CAS 25620-58-0) 1.6 Jeffamine D400 1.6 aqueous water 41.3 phase universal gel 2 Infilm939 4 Propylene glycol 5 Post-cure neutralizer Phosphoric acid ~ 0.5 (pH 7.5) dispersant Reax 100M 1 thickener Universal gel 2 WATER 2 Sample 4 Ingredients gram oil phase Tefluthrin 13.81 Benzyl benzoate 17.00 Huntsman DY-N 7.30 ( Neopentyl diglycidyl ether CAS 17557-23-2) Huntsman Aradur21 (Trimethyl hexane diamine CAS 25620-58-0) 1.5 Jeffamine D400 1.5 aqueous water 41.3 phase universal gel 2 Infilm939 4 Propylene glycol 5 Post-cure neutralizer Phosphoric acid ~ 0.5 (pH 7.5) dispersant Reax 100M 1 thickener Universal gel 2 WATER 2 Sample 5 Ingredients gram oil phase Tefluthrin 11.90 Benzyl benzoate 17.90 Huntsman DY-N 8.10 ( Neopentyl diglycidyl ether CAS 17557-23-2) Huntsman Aradur21 (Trimethyl hexane diamine CAS 25620-58-0) 1.7 Jeffamine D400 1.7 aqueous water 41.3 phase universal gel 2 Infilm939 4 Propylene glycol 5 Post-cure neutralizer Phosphoric acid ~ 0.5 (pH 7.5) dispersant Reax 100M 1 thickener Universal gel 2 WATER 2 Sample 6 Ingredients gram oil phase Tefluthrin 16.3 Benzyl benzoate 19.13 reaction products of hexane-1,6-diol with 3.7 2-(chloromethyl)oxirane (1:2) Isophorone-diamine 1.40 diaminopolypropylene glycol 0.79 aqueous water 54.92 phase Infilm939 (kaolin clay) 4.42 Propylene glycol 4.92 Post-cure poly[1-(2-oxo-1-pyrrolidinyl)ethylene] 0.49 polyacrylate copolymer 1.3 neutralizer Phosphoric acid ~ 0.1 (pH 7.5) dispersant lignosulfonic acid, sodium salt, 1.49 thickener sulfomethylated Universal gel (xanthan gum) 0.08 attapulgite clay 0.49 bactericide 0.26 Sample 7 Ingredients gram oil phase Tefluthrin 13.81 Benzyl benzoate 15.90 Huntsman DY-N 7.70 ( Neopentyl diglycidyl ether CAS 17557-23-2) Huntsman Aradur21 (Trimethyl hexane diamine CAS 25620-58-0) 1.9 Jeffamine D400 0.9 aqueous water 41.3 phase universal gel 2 Infilm939 4 Propylene glycol 5 Post-cure neutralizer Phosphoric acid ~ 0.5 (pH 7.5) dispersant Reax 100M 1 thickener Universal gel 2 WATER 2 Sample 8 oil phase Tefluthrin 13.81 Benzyl benzoate 15.90 Huntsman DY-N 8.00 ( Neopentyl diglycidyl ether CAS 17557-23-2) Huntsman Aradur21 (Trimethyl hexane diamine CAS 25620-58-0) 2.1 Jeffamine D400 0.7 aqueous water 41.3 phase universal gel 2 Infilm939 4 Propylene glycol 5 Post-cure neutralizer Phosphoric acid ~ 0.5 (pH 7.5) dispersant Reax 100M 1 thickener Universal gel 2 WATER 2 - Values have been rounded to the nearest hundredth [0117] The formulations were prepared by loading all the ingredients of the oil phase as listed in the above Tables into a beaker, followed by mixing with gentle shear until a homogeneous and transparent oil phase was formed. [0118] In a separate beaker, all components of the aqueous phase were loaded, followed by shear with a sawtooth mixer. Then the hardeners were added followed by gentle mix. [0119] The premixed oil phase was added into the aqueous phase, followed by shearing with a high shear mixer (UltraTurrax 0.5 inch head, 8k rpm 3min for 100g batch, 6min for 200g batch), until the target particle size (Dv50 < 13µ, Dv95< 20, preferred size is Dv95 < 15µm) was obtained. An ice bath was used to cool down the formulation while shearing. [0120] Cure (polymerization) of the formulation was at 60-70°C for 7 to 15hrs. [0121] Post-cure coformulants (acid, dispersant, pregel) are added to the cured formulation, and mixed with a sawtooth mixer until a homogeneous flowable liquid is formed. Acid was added to achieve target pH (7.5). [0122] During testing of the formulation, it was discovered that the tefluthrin did not crystalize as readily as previous formulations, as illustrated in FIGs 1A-1C. [0123] Fig.1A illustrates the crystallization of Force® CS 200 after being applied to corn seeds. Force® CS 200 is a capsule suspension type formulation with tefluthrin as the only active ingredient. The seed treatment utilized thiamethoxam/tefluthrin at rates of 0.8/0.4 mg/seed, Maxim Quattro, and red colorant polymerfloRite 1197 at 1mg/seed rate. [0124] FIG. 1B illustrates the results in the tefluthrin formulation from WO2019217770A1 and WO2019217775A1 using Aromatic 200. [0125] The formulation of the composition shown in FIG. 1C utilized benzyl benzoate (Sample 6) as a solvent. [0126] As illustrated by FIGs. 1A-1C, the composition of FIG. 1C surprisingly resulted in smaller crystals, if not non-observable crystals as compared to both the formulations used in FIG. 1A and FIG. 1B. These smaller crystals provide additional dust-off safety to workers in the field. [0127] Using a dust-off Heubach test, tefluthrin results were: 1.8mg /100k seed for Force® CS 200 and 0.4-0.8 mg /100k seed for formulations utilizing benzyl benzoate. [0128] Although only a few exemplary embodiments of this invention have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the following claims.

Claims

Claims 1. A liquid dispersion concentrate composition comprising: (a) a continuous phase; (b) at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has: (1) a hardness greater than 0.001 MPa and less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient dissolved in a benzoate based solvent therein and optionally wherein the solvent has a logP of 0.5-9.5 and a vapor pressure of below 1.3x10^-5 bar at 20°C and/or the solvent is an aromatic solvent with carbon numbers primarily greater than C16.

2. A liquid dispersion concentrate composition comprising: (a) a continuous phase; (b) at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has: (1) a hardness greater than 0.001 MPa and less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient dissolved in a solvent therein; wherein the solvent is an aromatic solvent with carbon numbers primarily greater than C16, and optionally wherein the solvent has a logP of 0.5-9.5 and a vapor pressure of below 1.3x10^-5 bar at 20°C and/or benzoate based solvent.

3. A liquid dispersion concentrate composition comprising: (a) a continuous phase; (b) at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has: (1) a hardness greater than 0.001 MPa and less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient dissolved in a solvent therein; wherein the solvent has a logP of 0.5-9.5 and a vapor pressure of below 1.3x10-5 bar at 20°C, and optionally wherein the solvent is an aromatic solvent with carbon numbers primarily greater than C16 and/or benzoate based solvent.

4. The liquid dispersion of any one of claims 1-3, wherein the solvent is benzyl benzoate, methyl benzoate, and butyl benzoate.

5. The liquid dispersion of any one of claims 1-4, wherein the solvent is benzyl benzoate.

6. The liquid dispersion of any one of claims 1-5, wherein the agrochemical active is an insecticide or fungicide.

7. The liquid dispersion of any one of claims 1-6, wherein the agrochemical active is a pyrethroid.

8. The liquid dispersion of any one of claims 1-7, wherein the agrochemical active is tefluthrin.

9. The liquid dispersion of any one of claims 1-8, wherein the solvent is aromatic.

10. The liquid dispersion of any one of claims 1-9, wherein the solvent is an aromatic ester.

11. The liquid dispersion of any one of claims 1-10, wherein the dissolved agrochemical active ingredient does not substantially crystalize after application to a plant propagation material.

12. The liquid dispersion of any one of claims 1-11, wherein the solvent is about 10-50% w/w of the liquid dispersion.

13. The liquid dispersion of any one of embodiments 1-12, wherein the dissolved agrochemical active ingredient is present in about 1-50% w/w of the liquid dispersion.

14. The composition of any one of claims 1-13, wherein the dust produced by the formulation after application to a propagation material is less than 1320 ug per 100,000 seeds with a dust-off Heubach test.

15. The composition of any one of claims 1-14, wherein the dust produced by the formulation to a propagation material is between 400-1320 ug per 100,000 seeds with a dust-off Heubach test.

16. A seed coated with a diluted composition of any one of claims 1-15.

17. A method of controlling pests, comprising: diluting the composition of any one of claims 1-15; and applying the diluted composition to a propagation material, the locus of a pest, or a plant.