EP4680023A1

EP4680023A1 - Stabilized agrochemical composition

Info

Publication number: EP4680023A1
Application number: EP24708485.8A
Authority: EP
Inventors: Manoj Varshney; Anne-Laure BREMONT VERNET; Natalia Lebedeva; Warren Schmidt; Jeffrey David Fowler; Leanna ROBBINS; Jelena NARSALE; Rene Rolf Bircher
Original assignee: Syngenta Crop Protection AG Switzerland
Current assignee: Syngenta Crop Protection AG Switzerland
Priority date: 2023-03-13
Filing date: 2024-03-06
Publication date: 2026-01-21
Also published as: CN120857862A; WO2024188742A1; AU2024234335A1; JP2026510856A; AR132101A1; KR20250160492A; PY2416713A; UY40669A

Abstract

The present disclosure relates to gel emulsion compositions and their methods of manufacture and use.

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, 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 changed. Accordingly, there remains a need for gel emulsion formulations which have improved properties.

[0003] Furthermore, during the preparation of gel emulsions, challenges have been seen in the scale up of production. Large batches tend to flocculate and form larger particle sizes. Such flocculation can result in overly viscous compositions which cannot be effectively processed. Accordingly, new methods are needed to facilitate large scale production of gel emulsions.

SUMMARY

[0004] Embodiments of the disclosure include a method, involving 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 comprises an agrochemical active ingredient, and the first composition comprises a liquid curable, solidifiable or polymerizable resin, emulsifying the third composition such that the first composition is the dispersed phase and the second composition is the continuous phase of the third composition, optionally wherein the median diameter of the dispersed phase is less than 200 pm, adding a dispersant to the third composition after the emulsifying to form a fourth composition, and effecting cure, solidification, or polymerization of the liquid curable, solidifiable or polymerizable resin in the fourth composition to form polymer matrix microparticles having the agrochemical active ingredient distributed therein.

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

[0006] The manufacturing system can be used in a method involving: loading the first vessel with a first composition comprising an agrochemical active ingredient and a liquid curable, solidifiable or polymerizable resin, optionally mixing or agitating the first composition; loading the second vessel with a second composition that is substantially immiscible in the first composition, optionally mixing or agitating the second composition; pumping the first composition from the first vessel into the second vessel containing the second composition to form a third composition; shearing the third composition with the shearing system to emulsify the third composition such that the first composition is a dispersed phase; preparing a dispersant composition in the third vessel; transferring the dispersant composition in the third vessel to first vessel; transferring the third composition after shearing to the first vessel; effecting cure, solidification, or polymerization of the liquid curable, solidifiable or polymerizable resin after the transferring of the dispersant composition and the transferring of the third composition to form polymer matrix microparticles having the agrochemical active ingredient distributed therein.

[0007] The methods herein can be used to prepared agrochemical compositions.

[0008] Compositions of the disclosure can include a liquid dispersion 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 less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient therein; and (c) a dispersant system, comprising: (cl) a sulfonate dispersing agent and a polyacrylate copolymer, and/or (c2) an alkylated vinyl pyrrolidone, non-ionic polyacrylate polymer.

[0009] The compositions of the disclosure can be applied in a pesticidally effective amount to a plant, a plant propagation material, or a locus of the pest.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] FIG. 1A shows a first step in a manufacturing system according to the present disclosure.

[0011] FIG. IB shows a second step in a manufacturing system according to the present disclosure.

[0012] FIG. 1C shows a third step in a manufacturing system according to the present disclosure.

[0013] FIG. ID shows a fourth step in a manufacturing system according to the present disclosure.

[0014] FIG. 2A shows a graph of serum formation over time for a composition at a variety of temperatures.

[0015] FIG. 2B shows helipath results for a composition at a variety of temperatures and storage times.

[0016] FIG. 2C shows viscosity of various dispersants in compositions.

[0017] FIG. 2D shows pH of various dispersants in compositions.

[0018] FIG. 2E shows a binary chart of serum formation of various dispersants after storage at various temperatures.

[0019] FIG. 2F shows a helipath results of various dispersants after storage at various temperatures.

[0020] FIG. 2G shows a helipath and binary sedimentation results of various dispersants combinations in compositions. [0021] FIG. 2H shows a helipath and sedimentation results of various dispersants combinations in compositions.

DETAILED DESCRIPTION OF THE INVENTION

[0022] The present disclosure relates to “gel” or “gel-like” polymer matrix particles comprising 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.

[0023] Accordingly, in one embodiment, a liquid dispersion composition of the present invention comprises:

(a) a continuous phase;

(b) at least one dispersed phase comprising a polymer matrix microparticle, wherein the polymer matrix microparticle has: (1) a hardness less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemical active ingredient therein; and

(c) a dispersant system, comprising:

(cl) a sulfonate dispersing agent and a polyacrylate copolymer, and/or

(c2) an alkylated vinyl pyrrolidone, non-ionic polyacrylate polymer.

[0024] 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. [0025] As used herein the term “particle” refers to a minute portion of matter. Particles can include portions of matter which are, e.g., solids, liquids, or gels.

[0026] In one embodiment, the chemical agents are agrochemically active ingredients.

[0027] In one embodiment, the colloidal solid material is a Pickering colloid emulsion stabilizer.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] In one embodiment, the agrochemically active ingredient is a solid and is distributed within the dispersed phase or is a liquid and is distributed within the dispersed phase. [0032] 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.

[0033] 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.

[0034] 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, a-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.

[0035] 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, poly caprolactone 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 W02011/040956A1.

[0036] 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.

[0037] 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.

[0038] In one embodiment, suitable polymerizable resins and polymer solutions are those which are substantially immiscible with the liquid used in the continuous phase.

[0039] 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.

[0040] 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).

[0041] In a further embodiment, the aqueous liquids suitable for use in the continuous phase a) are solutions of water-soluble solutes in water.

[0042] 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.

[0043] 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%.

[0044] 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.

[0045] 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.

[0046] 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. [0047] 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.

[0048] 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.

[0049] 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 GM, 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.

[0050] 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.

[0051] The advantages of the liquid dispersion concentrate compositions (e.g. gel emulsions) of the present invention include: storage-stability for extended periods, multiple agrochemicals of different physical states may be conveniently combined in dispersions of mutually compatible particles; improved adhesion to surfaces where deposits are able to dry; reduced potential for crop injury due to the presence of solvents or other phytotoxic agents; improved acute toxicity; simple handling is made possible for users because dilution is made with water, or other liquid carrier, for preparation of application mixtures; the compositions can easily be resuspended or redispersed with only a minor amount of agitation and are not susceptible to coalescence when dilution is made with fertilizer solutions for preparation of application mixtures. The term “storagestable” as used herein means that a given composition has a Dv50 that changes by less than about 20% over a period of 6 months at 70°F.

Agrochemically Active Ingredients

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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 nonfine 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.

[0056] 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.

[0057] 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.

[0058] 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. [0059] 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.

[0060] 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. [0061] 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.

[0062] 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.

Embodiments

[0063] The invention relates also to gel emulsion agrochemical compositions comprising a) a continuous, aqueous liquid phase, optionally comprising at least one agrochemically active ingredient; and b) at least one dispersed phase comprising polymer particles prepared from either a curable or polymerizable resin or a solidifiable thermoplastic polymer and comprising a colloidal solid material at their outside surface, wherein the hardness of the particles is greater than 0.001 MPa and less than 6 MPa, and wherein the particles have at least one agrochemically active ingredient distributed therein.

[0064] A further aspect of the invention relates to a dilute aqueous spray composition for combating pests or regulating the growth of plants at a locus comprising a) a continuous aqueous phase comprising a suitable liquid carrier, such as water or a liquid fertilizer, in an amount sufficient to obtain the desired final concentration of each of the active ingredients in the spray composition; b) at least one dispersed phase comprising polymer particles prepared from either a cureable or a polymerizable resin or a solidifiable thermoplastic polymer and comprising a colloidal solid material at their outside surface, wherein the hardness of the particles is greater than 0.001 MPa and less than 6 MPa, and wherein the particles have at least one agrochemically active ingredient distributed therein; and c) optionally, at least one agrochemically active ingredient dispersed, dissolved, suspended, microemulsified and/or emulsified in the liquid carrier.

[0065] In another embodiment, the invention relates to a dilute pesticidal and/or PGR composition for ultra-low volume (ULV) application comprising: 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 of the active ingredients in the ULV composition; b) at least one dispersed phase comprising polymer particles prepared from either a cureable or a polymerizable resin or a solidifiable thermoplastic and and comprising a colloidal solid material at their outside surface, wherein the hardness of the particles is greater than 0.001 MPa and less than 6 MPa and wherein the particles have at least one agrochemically active ingredient distributed therein.

[0066] The invention relates also to a method for combating or preventing pests in crops of useful plants or regulating the growth of such crops, said method comprising:

1) treating the desired area, such as plants, the plant parts or the locus thereof with a concentrate composition comprising: a) a continuous aqueous liquid phase, optionally comprising at least one agrochemically active ingredient, and also optionally comprising at least one acidic or basic component; b) at least one dispersed phase comprising polymer particles prepared from either a cureable or a polymerizable resin or a solidifiable thermoplastic and comprising a colloidal solid material at their outside surface, wherein the hardness of the particles is greater than 0.001 MPa and less than 6 MPa and wherein the particles have at least one agrochemically active ingredient distributed therein; or

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

Crops

[0067] 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.

[0068] The composition according to the invention is suitable for all methods of application conventionally used in agriculture, e.g. pre-emergence application, postemergence application, post-harvest and seed dressing. The compositions according to the invention are suitable for pre- or post-emergence applications to crop areas.

[0069] 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.

[0070] 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.

[0071] 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®.

[0072] 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-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. 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.

[0073] 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).

[0074] 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.

[0075] 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 [0076] 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.

[0077] 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, poly dialkylsiloxanes, in particular poly dimethylsiloxanes, fluoroaliphatic esters or perfluoroalkylphosphonic/perfluoroalkylphosphonic acids or the salts thereof and mixtures thereof. Suitable antifoams are polydimethylsiloxanes, such as Dow Coming® 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, alkylphenol 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.

[0078] The compositions of the invention may be mixed with fertilizers and still maintain their stability.

Dispersants (DP As)

[0079] Dispersants are well known in the art and selection of such will have various factors dependent on a given formulation. Preferred dispersants, include, without limitation, polyvinylpyrrolidone homopolymer with a molecular weight between 15- 120kDa, polyvinylpyrrolidone-vinyl acetate random copolymer, alkylated polyvinylpyrrolidone, 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.

[0080] In general, the total amount of dispersant system in the composition can be from 0.1 to 25 % w/w, preferably 0.5 to 10 % w/w, and most preferably 0.5 to 5% w/w. For example, the dispersant system can comprise mixture dispersants: a first dispersant, second and third dispersant. While the total amount (w/w) of each dispersant may vary depending on the specific dispersants selected, typical amounts of for each dispersant (e.g., the first dispersant or second or third dispersant) is 0.1 to 25% w/w, preferably 0.5 to 10 % w/w, and most preferably 0.5 to 5 % w/w. [0081] Accordingly, the compositions of the disclosure include dispersant systems with at least one dispersant, at least two dispersants, at least three dispersant, or even at least four dispersants.

[0082] Ratios (w/w) of any two dispersants can include 5:1 to 1:5, 4:1 to 1:4; 3:1 to 1:3; 2: 1 to 1 :2; or about 1: 1, or a mixture of such ratios. Ratios of any three dispersants can include 5-0.2 : 5-0.2 : 5-0.2; include 4-0.25 : 4-0.25 : 4-0.25; include 3-0.3 : 3-0.3 : 3-0.3; include 2-0.5 : 2-0.5 : 2-0.5; or about l: l: l:or a mixture of such ratios. Ratios of any four dispersants can include 5-0.2 : 5-0.2 : 5-0.2 : 5-0.2; include 4-0.25 : 4-0.25 : 4-0.25 : 4- 0.25; include 3-0.3 : 3-0.3 : 3-0.3 : 3-0.3; include 2-0.5 : 2-0.5 : 2-0.5 : 2-0.5; or about 1 : 1 : 1 : 1 or a mixture of such ratios.

[0083] In embodiments comprising at least two dispersants, the w/w % of each dispersant can be 0.1 to 25 % w/w, preferably 0.5 to 10 % w/w, and most preferably 0.5 to 5 % w/w.

[0084] Nevertheless, it has now been found that in certain embodiments non-ionic alkylated vinyl pyrrolidone, polyacrylate polymers are surprisingly preferred.

[0085] Alkylated vinyl pyrrolidone, polyacrylate polymers are generally produced by random grafting of alpha olefins onto a vinyl pyrrolidone polymer backbone and lactam ring. These products can have “comb-like” structures. Alkylation groups can be from C4- C20. For example, the alkylation group can be C4 (butane), Ci6 (hexadexene), or C20 (elcosene). In certain embodiments, the vinyl pyrrolidone/alkylation ratio is 90/10, 20/80, 50/50, or 30/70, or combinations thereof. The average molecular weight of such polymers can be from 12,000-22,000, 11,000-17,000, or 14,000-20,000. Their alkylated component induces lipophilicity, while vinyl pyrrolidone section in such polymer aids hydrophilicity; presence of both lipophilic and hydrophilic elements in one molecule makes them surface active. Such surface activity of these polymer facilitates reduction of the particle size of GE droplets.

[0086] Furthermore, non-ionic alkylated vinyl pyrrolidone, polyacrylate polymers appear surprisingly effective in the manufacturing process of GEs. [0087] Examples of commercially available alkylated vinyl pyrrolidone, polyacrylate polymers include: Agrimer™ AL, Agrimer™ AL 10LC, Agrimer™ AL 22, Agrimer™ AL 25, Agrimer™ AL 30, Agrimer™ AL 22D.

[0088] In addition, mixing non-ionic alkylated vinyl pyrrolidone, polyacrylate polymers with highly charged lignin sulfonated lignosulfonate and non-ionic comb shaped polyacrylate polymers can also improve re-suspensibility of GE droplets in very hard water.

[0089] Sulfonate dispersing agents are dispersing agents which contain a sulfonate group. In preferred embodiments, the sulfonate dispersing agent is a sodium or calcium salt. Examples of sulfonate dispersing agents include naphthalene sulfonates, lignosulfonates, kraft lignin sulfonate, dodecyl sulfonate (SDS), and dodecyl benzene sulfonate (SDBS). In preferred embodiments, the sulfonate dispersing agents contain kraft lignin to increase water solubility. In addition, preferred sulfonate dispersing agent induce reinforcement and increase glass transition temperature. Increased glass transition temperature is preferable for manufacturing GEs.

[0090] Examples of commercially available sulfonate dispersing agents include: REAX®, Polyfon, Kraftsperse, Indulin, Borresperse, NAXAN® products, Vultamol® NN 9104 .

[0091] Polyacrylate copolymers are known in the art. These polymers are prepared using acrylic acid monomer and a second monomer. In preferred embodiments, the copolymers are graft polymers, wherein a first monomer forms a backbone of the polymer and a second monomer forms branches thereon. A desirable comb-polymer stabilizer architecture consists of randomly incorporated side chain having affinity for dispersion medium, which are chemically attached to an anchor polymer. These comb-polymers induce dispersion properties based on steric hinderance stabilizing mechanisms.

[0092] Examples of commercially available polyacrylate copolymers are: Dispersive PSL 100, Atlox 4913, Atlox 4917 and Agrilan 755.

Application Methods [0093] 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.

[0094] 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 presized 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.

Manufacture

[0095] Within the scope of the present invention are different methods of producing dispersed phase GE containing chemical agents, which are described in a manner wherein the chemical agents are agriculturally active ingredients.

[0096] A method producing dispersed phase GEs can include the following steps: 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 comprises an agrochemical active ingredient, and the first composition comprises a liquid curable, solidifiable or polymerizable resin; emulsifying the third composition such that the first composition is the dispersed phase and the second composition is the continuous phase of the third composition, optionally wherein the median diameter of the dispersed phase is less than 200 pm; adding a dispersant to the third composition after the emulsifying to form a fourth composition; effecting cure, solidification, or polymerization of the liquid curable, solidifiable or polymerizable resin in the fourth composition to form polymer matrix microparticles having the agrochemical active ingredient distributed therein.

[0097] Such methods can also include, preparing a dispersion concentrate (e.g. composition 1) by dissolving or suspending at least one agrochemically active ingredient in a non-aqueous curable liquid mixture comprising at least one suitable cross-linkable resin (comprising monomers, oligomers, prepolymers or blends thereof), optionally where the resin contains hydrophilic groups, optionally a suitable hardener, catalyst, plasticizer or initiator. The dispersion concentrate can then me emulsified into an aqueous liquid to a mean droplet size of 1 - 200 microns, where the liquid contains a colloidal solid as an emulsion stabilizer, optionally contains a plasticizer, and, optionally, certain suitable hardener, catalyst or initiator capable of diffusing into the dispersed uncured resin droplets.

[0098] Embodiments of the above methods can include variation where except that the dispersion concentrate comprises as non-aqueous liquid a polymerizable resin instead of a cross-linkable resin. Instead of a curing reaction, the dispersed phase particles are formed by a polymerization reaction, so that the resulting dispersed phase comprises thermoplastic polymeric particles rather than thermoset polymeric particles.

[0099] Additional steps applicable to the above method include

1. dissolving or suspending at least one agrochemically active ingredient in a nonaqueous liquid mixture comprising at least one suitable solidifiable polymer dissolved in a volatile solvent, and one or more optional plasticizers; 2. emulsifying said solution into an aqueous liquid to a mean droplet size of 1 - 200 microns, where the liquid contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer; and

3. effecting evaporation of the volatile solvent by heating the emulsion to a temperature of about 30-120°C for about 0.1-10 hr, and optionally thereafter imbibing a plasticizer, to produce thermoplastic polymer particles having a hardness less than 6 MPa with at least one agriculturally active ingredient distributed therein, and a colloidal solid material at the surface of the particle.

[0100] Methods of the above disclosure where curing is utilized, can include the following steps:

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

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

3. cooling the emulsion, and optionally thereafter imbibing a plasticizer, to produce thermoplastic polymeric particles having a hardness less than 6 MPa with at least one agriculturally active ingredient distributed therein, and a colloidal solid material at the surface of the particle.

[0101] In situations where the active ingredient is soluble or miscible with the plasticizer, the above method can be modified so that an active ingredient is added after the step of curing, solidifying or extracting solvent from the liquid emulsion droplets, so that the active ingredient is imbibed or dissolved into the GE’s after formation rather than being present in the dispersion concentrate initially.

[0102] Accordingly, the method of the disclosure can include the following steps: a. dissolving or suspending at least one agrochemically active ingredient in a nonaqueous liquid mixture (premix) comprising at least one suitable curable or polymerizable resin (comprising monomers, oligomers, prepolymers or blends thereof), optionally a suitable hardener, plasticizer, catalyst or initiator; b. emulsifying said solution or suspension into an aqueous liquid to a mean droplet size of 1 - 200 microns, which liquid also contains a colloidal solid as an emulsion stabilizer and optionally contains a plasticizer, certain suitable hardener, catalyst or initiators capable of diffusing into the dispersed uncured or unpolymerized resin droplets; and c. effecting crosslinking, cure or polymerization of the resin mixture, and optionally thereafter imbibing a plasticizer, to produce cured thermoset or polymerized thermoplastic resin polymer particles having a hardness 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 after curing are dispersed in the aqueous liquid.

[0103] Methods can include 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 poly oxypropylene diamine. Mixtures of hardeners may also be employed for extra flexibility.

[0104] Premixes in the above methods can be prepared as follows:

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 as needed; 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.

[0105] 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.

[0106] 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.

[0107] In one embodiment, the dispersion concentrate is prepared by: a. dissolving or suspending at least one agrochemically active ingredient in a nonaqueous 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 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.

[0108] One system for implementing the above methods is shown in FIGs. 2A-2D.

[0109] A first step in preparing GEs according to the system of FIGs. 2A-2D is shown in FIG. 2 A. The first step of preparing GEs can include preparing various premixes.

[0110] A first premix can be prepared in a first vessel 101. In general, the first premix will be the dispersed phase of the agrochemical composition as described above. The first vessel 101 can have a mixer 109 configured to agitate and/or mix to liquids within the first vessel 101 and a heater 107 configured to heat the liquid composition within the first vessel 101. In certain embodiments, the heater 109 can additionally function as a chiller to remove heat from the first vessel 101. In preferred embodiments the heater 107 is exterior to the first vessel 101 and surrounds the perimeter of the first vessel 101. In alternative embodiments the heater is interior to the first vessel 101 and in contact with the liquid in the first vessel. Mixers or agitating systems include ribbon systems, tumble systems, planetary mixers, centrifugal mixers, or ResonantAcoustic® Mixing (RAM)(RAM employs low-frequency energy to generate unique material movement and sound-induced (acoustic) interaction within the vessel without the use of internal, mechanically-driven parts such as an impeller.)

[0111] The size of the first vessel 101 is not particularly limited. The first vessel can have a volume of greater than 10 gallons, for example 10 to 1,000,000, or 100 to 500,000.

[0112] A second premix can be prepared in a second vessel 103. In general, the second premix will be the continuous phase of the agrochemical composition as described above. The second vessel 103 has a shearing system configured to apply shearing to liquids within the second vessel 103. In preferred embodiments, the shearing system include a first mixer 111 and a second mixer 113. The mixers can be the same or different from the mixers in the first vessel 101. In general, the shearing system can produce forced above 500rpm, for example lOOOrpm to 25,000rpm 1500rpm to lOOOOrpm, or 2000rpm to 5000rpm. [0113] The size of the second vessel 103 is not particularly limited. The second vessel can have a volume of greater than 10 gallons, for example 10 to 1,000,000, or 100 to 500,000.

[0114] A third premix can be prepared in a third vessel 105. In general, the third premix will be the dispersant added after emulsification but before cure, solidification, or polymerization. The third vessel 105 can have a mixer 115 configured to agitate and/or mix to liquids within the third vessel. Alternatively, the third vessel 105 can be agitated or mixed by hand. The size of the third vessel 105 is not particularly limited. The third vessel 105 can have a volume of greater than 1 gallon, for example 1 to 1,000 or 1 to 500.

[0115] A second step in preparing GEs according to the system of FIGs. 2A-2D is shown in FIG. 2B. The second step of preparing GEs can include an emulsification from the contents of the first vessel 101 and the second vessel 103. The system can include a pump 117 configured to transfer liquids between the first vessel 101 and the second vessel 103, and vice versa. The first vessel 101 and the second vessel 103 can be in fluid communication such that the bottom of first vessel 101 is in fluid communication with the top of the second vessel 103. The fluid communication can be achieved through piping or tubing with a pump 117 in-between.

[0116] Once the first premix from the first vessel 101 is transferred into the second premix in the second vessel 103, the shearing system of the second vessel 103 can be used to emulsify the contents therein.

[0117] A third step in preparing GEs according to the system of FIGs. 2A-2D is shown in FIG. 2C. The third step of preparing GEs can include the addition of a dispersant followed by effecting cure, solidification, or polymerization of the dispersed phase of the composition emulsified in the second vessel 103.

[0118] The system can use a pump 117 which is the same or different than the pump 117 used to move the first premix in the first vessel 101 to the second vessel 103. The fluid connection used to facilitate transfer of liquid from the second vessel 103 to the first vessel 101 can be the same or different from the piping or tubing used to move the first premix in the first vessel 101 to the second vessel 103. For example, a different fluid communication system can connect the base of the second vessel 103 to the base of the first vessel 101.

[0119] The third premix in the third vessel 115 can be added into the first vessel 101 prior to the transfer of the emulsified liquid from the second vessel 103 to the first vessel 101. Alternatively, the third premix can be added after the transfer of the emulsified liquid from the second vessel 103 to the first vessel 101. In some embodiments, the third premix is added into the second vessel 103 prior to transfer to the first vessel 101. In preferred embodiments, the third premix is mixed into the emulsified liquid using the mixer 109 of the first vessel 101.

[0120] Once the third premix is incorporated into the emulsified liquid, then polymerization, cure, or solidification of the emulsified liquid can occur. In preferred embodiments, polymerization is facilitated by the heater 107 of the first vessel, and the mixer 109 is circulates the contents of the first vessel.

[0121] A fourth step in preparing GEs according to the system of FIGs. 2A-2D is shown in FIG. 2F. The fourth step of preparing GEs can include the addition dilutants (e.g., water) and co-formulates and packaging of the product for distribution.

[0122] Once the GE is finally formed the addition dilutants (e.g., water) and coformulates are added into the first vessel 101 through conventional means such a pouring through an opening in the first vessel 101. The mixer 109 can be used to ensure homogeneity of the composition in the first vessel 101.

[0123] A liquid transfer system, including pipes or tubing, which can be the same or different from the system used to transfer liquids from the first vessel 101 to the second vessel 103, can be used to transfer the formulated composition in the first vessel 101 to a package 127 for distribution.

[0124] The liquid transfer system can utilize a pump 119 to deliver the formulated product through a mesh 121. Once the formulated product is transferred through the mesh 121, the formulated product can be temporarily stored in totes 123, 125 prior to transfer to the package 127 for distribution.

Polymers [0125] 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.

[0126] 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.

[0127] Preferred thermoplastic polymers include polymers of the thermoplastic resins described above, as well as polymers such as cellulose acetate, polyacrylates, poly caprolactone and polylactic acid.

[0128] 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.

[0129] Suitable monomers for the present invention comprise vinylaromatic monomers, such as styrene, a-methylstyrene, divinylbenzene and the like, esters of a, [3- 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. [0130] 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.

[0131] 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 [3-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 l,l,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 oilbased).

[0132] 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. [0133] Exemplary of poly epoxides that differ from glycidyl compounds are the di epoxides of vinylcyclohexene and di cyclopentadiene, 3-(3',4'-epoxycyclohexyl)-8,9- epoxy-2,4-dioxaspiro[5.5]undecane, the 3 ',4'-epoxy cyclohexylmethyl ester of 3,4- epoxycyclohexanecarboxylic acid, butadiene diepoxide or isoprene diepoxide, epoxidized linoleic derivatives or epoxidized polybutadiene.

[0134] 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.

[0135] 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 poly epoxides and polyols.

[0136] 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.

[0137] 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.

[0138] For example, other suitable hardeners are anhydrides of poly carboxy lie acids, typically phthalic anhydride, nadic anhydride, methylnadic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and, in addition, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.

[0139] 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- epoxy cyclohexanecarboxylate, 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-l,6-hexanediamine, isophorone diamine, /V,/V-dimethyl-l,3-diaminopropane, diethylene triamine, N,N'- dimethylethylenediamine, and hexamethylenediamine.

[0140] 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

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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 Goias, 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],

[0145] 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.

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

[0146] 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 GM, 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 monoprimary, 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.

[0147] 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

[0148] Embodiment 1. A method, comprising: 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 comprises an agrochemical active ingredient, and the second composition comprises a liquid curable, solidifiable or polymerizable resin; emulsifying the third composition such that the first composition is the dispersed phase and the second composition is the continuous phase of the third composition, optionally wherein the median diameter of the dispersed phase is less than 200 pm; adding a dispersant to the third composition after the emulsifying to form a fourth composition; effecting cure, solidification, or polymerization of the liquid curable, solidifiable or polymerizable resin in the fourth composition to form polymer matrix microparticles having the agrochemical active ingredient distributed therein.

[0149] Embodiment 2. The method of embodiment 1, wherein the dispersant is selected from a sulfonated dispersant, a substituted or unsubstituted polyvinyl pyrrolidone, and/or a non-ionic comb shaped polyacrylate polymer.

[0150] Embodiment 3. The method of embodiment 2, wherein the dispersant is the sulfonated dispersant selected from a lignosulfonate and/or a naphthalene sulfonate, optionally wherein the dispersant is present from 0.01 to 10% w/w, preferably 0.1 to 5 % w/w, or most preferably 0.1 to 2 % w/w. [0151] Embodiment 4. The method of embodiment 2, wherein the dispersant is the substituted or unsubstituted polyvinyl pyrrolidone, optionally wherein the dispersant is present from 0.01 to 10% w/w, preferably 0.1 to 5 % w/w, or most preferably 0.2 to 2 % w/w.

[0152] Embodiment 5. The method of embodiment 2, wherein the dispersant is polyvinyl pyrrolidone, optionally wherein the dispersant is present from 0.01 to 10 % w/w, preferably 0.1 to 5 % w/w, or most preferably 0.1 to 2% w/w.

[0153] Embodiment 6. The method of embodiment 5, wherein the polyvinyl pyrrolidone is alkylated.

[0154] Embodiment 7. The method of embodiment 5, wherein the dispersant is unsubstituted.

[0155] Embodiment 8. The method of embodiment 7, wherein the dispersant is a mixture of lignin sulfonated lignosulfonate, polyvinyl pyrrolidone, and non-ionic comb shaped polyacrylate polymers and optionally present in 0.1 to 20 % w/w, preferably 0.2 tol5% w/w, or most preferably 0.5 to 10 % w/w.

[0156] Embodiment 9. The method of any one of embodiments 1-8, wherein the second composition comprises a colloidal solid emulsion stabilizer, optionally wherein the colloidal solid emulsion stabilizer is present from 0.1 to 25 % w/w, preferably 0.5 to 15% w/w, or most preferably 1 to 12 % w/w.

[0157] Embodiment 10. The method of any one of embodiments 1-9, wherein at least one of the first composition or the second composition contains a plasticizer, optionally wherein the plasticizer is present from 0.1 to 20 % w/w, preferably 0.5 to 10% w/w, or most preferably 1 to 8 % w/w.

[0158] Embodiment 11. The method of any one of embodiments 1-10, wherein the first composition contains a chemical curing agent, optionally wherein the chemical curing agent is present from 0.1 to 20 % w/w, preferably 0.5 to 10 % w/w, or most preferably 1 to 5 % w/w. [0159] Embodiment 12. The method of any one of embodiments 1-11, wherein the liquid curable, solidifiable or polymerizable resin is selected from epoxy, polyisocyanate, polyamine, aminoplast, phenolic and polyester.

[0160] Embodiment 13. The method of embodiment 11, wherein the resin is a thermosetting epoxy resin.

[0161] Embodiment 14. The method of any one of embodiments 1-13, wherein the second composition is more than 50 wt% water or a mixture of water and a substantially water-miscible non-aqueous liquid, wherein the non-aqueous liquid that forms a single phase when present in water at a concentration up to at least 50 wt%.

[0162] Embodiment 15. The method of any one of embodiments 1-14, wherein the first composition further comprises a solvent to dissolve the agrochemical active ingredient, optionally wherein the solvent is present from 5 to 75 % w/w, preferably 10 to 50 % w/w, or most preferably 15 to 30% w/w.

[0163] Embodiment 16. The method of any one of embodiments 1-15, wherein the hardness of the polymer matrix microparticles is less than 6 MPa, for example, less than 5MPa, less than 1 MPa, less than 0.1 MPa, less than 0.001 MPa, alternatively, 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.

[0164] Embodiment 17. The method of any one of embodiments 1-16, wherein the polymer matrix microparticles have a median diameter less than 200pm, for example, 1- 200pm, l-100pm, l-50pm, l-20pm, or 8-18pm.

[0165] Embodiment 18. The method of any one of embodiments 1-17, wherein the viscosity of the fourth composition during the effecting cure, solidification, or polymerization of the liquid curable, solidifiable or polymerizable resin remains below 2000cP, for example, I OOCP-IOOOCP or 300-600cP.

[0166] Embodiment 19. The method of any one of embodiments 1-18, further comprising shear mixing the fourth composition during effecting cure, solidification, or polymerization of the first composition, optionally wherein the shear mixing is above 500rpm, for example lOOOrpm to 25,000rpm 1500rpm to lOOOOrpm, or 2000rpm to 5000rpm.

[0167] Embodiment 20. The method of any one of embodiments 1-19, wherein the third composition is greater than 90% w/w, for example 90% w/w to 99.9 % w/w, 95 to 99.9% w/w of the fourth composition.

[0168] Embodiment 21. A manufacturing system, comprising: a first vessel, comprising: a mixer configured to agitate and/or mix to liquids within the first vessel, a heater configured to heat the liquid composition within the first vessel; a second vessel in fluid communication with the first vessel, the second vessel comprising: a shearing system configured to apply shearing to liquids within the second vessel; a third vessel, comprising: a mixer configured to agitate and/or mix to liquids within the third vessel; a pump system configured to transfer liquids between the first vessel and the second vessel.

[0169] Embodiment 22. The system of embodiment 21, wherein: the first vessel has a volume of greater than 10 gallons, for example 10 to 1,000,000, or 100 to 500,000; the second vessel has a volume of greater than 10 gallons, for example for example 10 to 1,000,000, or 100 to 500,000; and/or the third vessel has a volume of greater than 1 gallon, for example 1 to 1,000 or 1 to 500.

[0170] Embodiment 23. The system of either embodiments 21 or 22, further comprising at least one bulk storage tote in fluid communication with the first vessel, optionally wherein the at least one bulk storage tote has a volume of greater than 100 gallons, for example 275 to 330 gallons.

[0171] Embodiment 24. The system of embodiment 23, further comprising a mesh filter between the at least one bulk storage tote and the first vessel, optionally wherein the mesh filter is a 100 mesh.

[0172] Embodiment 25. The system of either embodiments 23 or 24, further comprising a plurality of end-use product containers, optionally wherein the plurality of end-use product containers have a volume of less than 5 gallons, for example 2 gallons, 1 gallon, 1 liter, or 0.5 liters.

[0173] Embodiment 26. A method of preparing an agrochemical composition comprising the system of any one of embodiments 22-25, comprising: loading the first vessel with a first composition comprises an agrochemical active ingredient a liquid curable, solidifiable or polymerizable resin, optionally mixing or agitating the first composition; loading the second vessel with a second composition that is substantially immiscible in the first composition, optionally mixing or agitating the first composition; pumping the first composition from the first vessel into the second vessel containing the second composition to form a third composition; shearing the third composition with the shearing system to emulsify the third composition such that the first composition is a dispersed phase; preparing a dispersant composition in the third vessel: transferring the dispersant composition in the third vessel to first vessel; transferring the third composition after shearing to the first vessel; effecting cure, solidification, or polymerization of the liquid curable, solidifiable or polymerizable resin after the transferring of the dispersant composition and the transferring of the third composition to form polymer matrix microparticles having the agrochemical active ingredient distributed therein. [0174] Embodiment 27. An agrochemical composition prepared by the methods of any one of embodiments 1-21 and 26.

[0175] Embodiment 28. A liquid dispersion composition comprising:

(a) a continuous phase;

(c) a dispersant system, comprising:

(cl) a sulfonate dispersing agent and a polyacrylate copolymer, and/or

(c2) an alkylated vinyl pyrrolidone, non-ionic polyacrylate polymer.

[0176] Embodiment 29. The composition of embodiment 28, wherein the polyacrylate copolymer is present in 0.01 to 10% w/w, preferably 0.1 to 5 % w/w, or most preferably 0.2 to 2 % w/w.

[0177] Embodiment 30. The composition of either claim 28 or 29, wherein the sulfonate dispersing agent is present in 0.01 to 10% w/w, preferably 0.1 to 5 % w/w, or most preferably 0.1 to 2 % w/w.

[0178] Embodiment 31. The composition of any one of embodiments 28-30, the alkylated vinyl pyrrolidone, non-ionic polyacrylate polymer is present in 0.01 to 10 % w/w, preferably 0.1 to 5 % w/w, or most preferably 0.1 to 2% w/w.

[0179] Embodiment 32. The composition of any one of embodiments 28-31, wherein the sulfonate dispersing agent is a sodium salt.

[0180] Embodiment 33. The composition of any one of claims embodiments 28-32, wherein the sulfonate dispersing agent is a naphthalene sulfonate.

[0181] Embodiment 34. The composition of any one of embodiments 28-33, wherein the sulfonate dispersing agent is a lignosulfonate. [0182] Embodiment 35. The composition of any one of embodiments 29-34, wherein the agrochemical active ingredient is selected from azoxystrobin, benzovindiflupyr, fludioxonil, propiconazole, pydiflumetofen and tefluthrin.

[0183] Embodiment 36. The composition of embodiment 35, wherein the agrochemical active ingredient is tefluthrin.

[0184] Embodiment 37. The composition of embodiment 35, further comprising a second agrochemical active ingredient distributed in the polymer matrix microparticle, wherein the agrochemical active ingredient is benzovindiflupyr and the second agrochemical active ingredient is fludioxonil.

[0185] Embodiment 38. A liquid dispersion composition comprising:

(a) a continuous phase;

(c) at least one dispersant; wherein serum formation remains below 10% after 2 months of storage at 23 °C or 54°C and/or wherein the helipath max remains below 120 after 2 months of storage at 23°C or 54°C.

[0186] Embodiment 39. The composition of embodiment 38, wherein each dispersant can be 0.1 to 25 % w/w, preferably 0.5 to 10 % w/w, and most preferably 0.5 to 5 % w/w, and optionally wherein the total amount of dispersant is 0.1 to 25 % w/w, preferably 0.5 to 10 % w/w, and most preferably 0.5 to 5% w/w.

[0187] Embodiment 40. The composition of embodiments 38 or 39, wherein the composition comprises at least two dispersants.

[0188] Embodiment 41. The composition of embodiments 38 or 39, wherein the composition comprises at least three dispersants. [0189] Embodiment 42. The composition of embodiments 38 or 39, wherein the composition comprises at least four dispersants.

[0190] Embodiment 43. The composition of any one of embodiments 38-42, wherein the at least one dispersant is selected from polyvinylpyrrolidone homopolymer, sulfonate dispersing agent, polyvinylpyrrolidone-vinyl acetate random copolymer, alkylated polyvinylpyrrolidone, lignosulfonates, sulfonated urea-formaldehyde condensates, styrene acrylic copolymers, comb polymers with alkyl backbone and side chains of polyacrylic acid, and alkylated polyvinylpyrrolidone.

[0191] Embodiment 44. A method of controlling pests, comprising: applying a pesticidally effective amount of the composition of any one of embodiments 28-43 to a plant, a plant propagation material, or a locus of the pest.

[0192] Embodiment 45. The method of embodiment 44, further comprising identifying a plant, a plant propagation material, or a locus of the pest susceptible to attack from a pest.

[0193] Embodiment 46. The method of either embodiments 44 or 45, further comprising diluting the composition prior to the applying.

EXAMPLES

[0194] 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.

[0195] Products and tradenames used in the following example are described in the below table.

Manufacture

Example 1

[0196] A first composition was prepared by creating a mixture of water (about 80%w/w) and glycerine (about 20%w/w).

[0197] A second composition was prepared by mixing fludioxonil (about 19%w/w) and benzovindiflupy (about 2%w/w) in Hallcomid® M-8-10 (about 64%w/w) until the fludioxonil and benzovindiflupy were dissolved. Tri-iso-phosphate and resorcinol diglycidyl ether were then mixed into the second composition.

[0198] The first composition, second composition, and Jeffamine® D230 were combined to form a third composition and mixed at high shear for 15 minutes. To the third composition, a premix of water (about 40% w/w) and aluminium silicate (about 40% w/w) was added and sheared until the desired particle size was reached.

[0199] The composition was then heated at 70°C for 4 hours. The resulting formulation was a highly viscous rendering it difficult to further process.

[0200] The batch was further processed by adding Agrimer® AL 10 LC and then adding XIAMETER® ACP-1500, Acticide CT, Proxel GXL, and Water resulting in the below composition.

Example 2

[0201] Using the procedure of Example 1, the third composition was prepared but without the tri-iso-phosphate. After the third composition was sheared to the desired particle size, a premix of water (about 80%w/w) and Agrimer® AL 10LC (about 20%w/w) was added and mixed with gentle agitation for 15 minutes. [0202] The third composition was then heated at 70°C for 4 hours. The resulting formulation remained flowable.

[0203] The batch was further processed by adding Dispersogen® PSL100; lignosulfonic acid, sodium salt, sulfomethylated; XIAMETER® ACP-1500, a biocide system, water, and phosphoric acid 75%. Dispersant Testing

[0204] A formulation blank was designed as described in the below Table:

Values have been rounded to the nearest tenth

[0205] A formulation (Ex. 1) was prepared using where the varied dispersant VI was 0.56% w/v of Reax® 1 OOM. The formulation was test for storage stability over a variety of temperatures up to six months. Serum formation (FIG. 2A) and viscosity was measured via helipath (FIG. 2B) was recorded. [0206] Using the above-described formulation blank, the post-cure was varied with the following dispersing agents.

[0207] The differences between various Reax® products is summarized in the below table.

[0208] The effects of the dispersants on viscosity and pH are shown in FIG. 2C and FIG. 2D, respectively.

[0209] The above formulations were also reviewed for sedimentation and on a helipath at -18°C, 23°C, and 54°C after two-weeks of storage. The test for sedimentation was performed as a binary review where 0 indicated no sedimentation (less than 10%) and 1 indicated sedimentation (more than 10%). The results are shown in FIG. 2E and FIG. 2F, respectively.

[0210] The formulation blank was modified to include Attagel® 50 (0.5% w/w) and to review 2- way and 3 -way combinations of dispersants giving the following formulation blank.

[0211] The following combinations were tested.

[0212] These formulations were tested for sedimentation and helipath max as discussed above. Surprisingly, only Tersperse® 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. Other combinations did not show sedimentations after 2 weeks. The helipath results and summary of sedimentation are shown in FIG. 2G.

Experiments on the above formulations were extended to for two-months, the helipath and sedimentation results are shown in FIG. 2H.

Re- Suspendability in Hard Water

[0213] The following two formulations were prepared according to the methods described herein.

[0214] Both formulations were diluted in 1000 ppm hard water and allowed to sit for 24 hours. The compositions were then run through 50 and 100 mesh sieves. Results for Ex. 1 are provided in FIG. 2A. Results for Ex. 2 are provided FIG. 2B. As illustrated significant residue resulted in Ex. 1 whereas no residue was observed for Ex. 2. [0215] 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

1. A method, comprising: 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 comprises an agrochemical active ingredient, and the first composition comprises a liquid curable, solidifiable, or polymerizable resin; emulsifying the third composition such that the first composition is the dispersed phase and the second composition is the continuous phase of the third composition, optionally wherein the median diameter of the dispersed phase is less than 200 pm; adding a dispersant to the third composition after the emulsifying to form a fourth composition; and effecting cure, solidification, or polymerization of the liquid curable, solidifiable or polymerizable resin in the fourth composition to form polymer matrix microparticles having the agrochemical active ingredient distributed therein.

2. The method of claim 1, wherein the dispersant is selected from a sulfonated dispersant, a substituted or unsubstituted polyvinyl pyrrolidone, and/or a non-ionic comb shaped polyacrylate polymer.

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

4. The method of claim 2, wherein the dispersant is the substituted or unsubstituted polyvinyl pyrrolidone, optionally wherein the dispersant is present from 0.01 to 10% w/w, preferably 0.1 to 5% w/w, or most preferably 0.1 to 2% w/w.

5. The method of any one of claims 1-4, wherein the second composition comprises a colloidal solid emulsion stabilizer, optionally wherein the colloidal solid emulsion stabilizer is present from 0.1 to 25% w/w, preferably 0.5 to 15% w/w, or most preferably 1 to 12% w/w.

RECTIFIED SHEET (RULE 91)

6. The method of any one of claims 1-5, wherein the viscosity of the fourth composition during the effecting cure, solidification, or polymerization of the liquid curable, solidifiable or polymerizable resin remains below 2000cP, for example, IOOCP-IOOOCP or 300-600cP.

7. The method of any one of claims 1-6, further comprising shear mixing the fourth composition during effecting cure, solidification, or polymerization of the first composition, optionally wherein the shear mixing is above 500rpm, for example lOOOrpm to 25,000rpm 1500rpm to lOOOOrpm, 2000rpm to 5000rpm.

8. The method of any one of claims 1-7, wherein the third composition is greater than 90% w/w, for example 90% w/w to 99.9 % w/w, 95 to 99.9% w/w of the fourth composition.

9. A manufacturing system suitable for carrying out the method of any one of claims 1 to 8, comprising: a first vessel, comprising: a mixer configured to agitate and/or mix to liquids within the first vessel, a heater configured to heat the liquid composition within the first vessel; a second vessel in fluid communication with the first vessel, the second vessel comprising: a shearing system configured to apply shearing to liquids within the second vessel; a third vessel, comprising: a mixer configured to agitate and/or mix to liquids within the third vessel; a pump system configured to transfer liquids between the first vessel and the second vessel.

10. A method of preparing an agrochemical composition comprising the system of claim 9, comprising: loading the first vessel with a first composition comprising an agrochemical active ingredient and a liquid curable, solidifiable or polymerizable resin, optionally mixing or agitating the first composition; loading the second vessel with a second composition that is substantially immiscible in the first composition, optionally mixing or agitating the second composition;

RECTIFIED SHEET (RULE 91) pumping the first composition from the first vessel into the second vessel containing the second composition to form a third composition; shearing the third composition with the shearing system to emulsify the third composition such that the first composition is a dispersed phase; preparing a dispersant composition in the third vessel: transferring the dispersant composition in the third vessel to first vessel; transferring the third composition after shearing to the first vessel; effecting cure, solidification, or polymerization of the liquid curable, solidifiable or polymerizable resin after the transferring of the dispersant composition and the transferring of the third composition to form polymer matrix microparticles having the agrochemical active ingredient distributed therein.

11. An agrochemical composition prepared by the methods of any one of claims 1-8 and 10.

12. A liquid dispersion composition comprising:

(a) a continuous phase;

(c) a dispersant system, comprising:

(cl) a sulfonate dispersing agent and a polyacrylate copolymer, and/or (c2) an alkylated vinyl pyrrolidone, non-ionic polyacrylate polymer.

13. The composition of claim 12, wherein the polyacrylate copolymer is present in 0.01 to 10% w/w, preferably 0.1 to 5% w/w, or most preferably 0.2 to 2% w/w; and/or wherein the sulfonate dispersing agent is selected from a naphthalene sulfonate and/or a lignosulfonate, optionally is present in 0.01 to 10% w/w, preferably 0.1 to 5% w/w, or most preferably 0.1 to 2% i/ r, and/or the alkylated vinyl pyrrolidone, non-ionic polyacrylate polymer is present in 0.01 to 10% w/w, preferably 0.1 to 5% w/w, or most preferably 0.1 to 2% w/w.

RECTIFIED SHEET (RULE 91)

14. A method of controlling pests, comprising: applying a pesticidally effective amount of the composition of any one of claims 12-13 to a plant, a plant propagation material, or a locus of the pest.

RECTIFIED SHEET (RULE 91)