OA16271A - Stabilized chemical composition. - Google Patents

Abstract

Stabilized liquid agrochemical compositions are provided that comprise flowable, aqueous dispersion concentrates comprising : a) a continuous aqueous liquid phase; b) at least one dispersed, solid phase comprising a dispersion of polymer particles having a mean particle size of at least one micron, wherein the outside surfaces of the particles comprise a colloidal solid material and wherein the particles have at least one agrochemically active ingredient distributed therein, optionally a non-porous particulate mineral that acts as a diffusion barrier to slow the release of the active ingredient, and optionally at least one non-cross-linkable mobile chemical such that the extraction of this chemical from the disperse phase renders it porous in a manner that allows the active ingredient to diffuse out. The colloidal solid is used to stabilize the polymenzable resin in an emulsion state during preparation.

Description

STABILIZED CHEMICAL COMPOSITION [0001] The présent invention relates to stabilized, liquid, chemical compositions, the préparation of such compositions and a method of using such compositions, for example, to combat pests or as plant growth rcgulators.

BACKGROUND OF THE INVENTION [0002] Agriculturally active ingrédients (agrochcmîcals) are often provided in the form of concentrâtes suitable for dilution with water. Many forms of agricultural concentrâtes arc known and these consist ofthe active ingrédient and a carrier, which can include various components. Water-based concentrâtes are obtained by dissolving, emulsifying and/or suspending agriculturally active materials in water. Duc to the relatively complex supply chain for crop protection agents, such conccntrate formulations can be stored for long periods and may be subjected during storage and shipping to extreme température variations, high-shear and répétitive vibration patterns. Such supply chain conditions can increase the likelihood of formulation failurc such as, for example, flocculation, thickening and sédimentation.

[0003] In some cases it may be désirable to combine different agrochcmîcals in a single formulation takîng advantage of the additivc properties of each separate agrochcmical and optionally an adjuvant or combination of adjuvants that provide optimum biological performance. For example, transportation and storage costs can be minimized by using a formulation in which the concentration of lhe active agrochemical(s) îs as high as is practicablc and in which any desired adjuvants arc built-in to the formulation as opposcd to being scparatcly tank-mixed. The higher the concentration of the active agrochemical(s) however, the greater is the probability that the stability of the formulation may be compromised, or that one or more components may phase separate. in addition formulation failurc can be more challenging to avoid when multiple active ingrédients are présent because of physical or chemical incompatibilities between thèse chcmicals such as, for example, when one active ingrédient is an acid, a base, an oily liquid, a hydrophobie crystalline solid or a hydrophiiic crystalline solid and the other active ingrcdicnt(s) has or hâve different properties.

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[0004] It also may be désirable to improve the effectiveness of the agrochemicals by controlling the release rate of agrochemîcal into the application site from the formulation. In particular it may be désirable to combine agrochemicals in a single formulation and control their release rates independently, for instance in cases where the modes of action 10 of the agrochemicals renders them antagonistic if both are delivered at the same rate.

[0005] In addition, spray tank mixes can contain a varicty of chcmicals and adjuvants that may înteract and change the effectiveness of one or more of the agrochemicals încludcd therein. incompatibility, poor water quality and insufficient tank agitation can 15 lcad to reduced effectiveness of sprays, phytotoxicîty and can affect cquîpment performance.

[0006] Pcstîcide-comprising aqueous polymer dispersions with a mean particle size of the dispersed particles of <1000 nm which are obtained from mîniemulsion polymerization of ethylenically unsaturated monomers are known, forcxample, from US 2008/0171658. A limitation of polymer dispersions of this type is that the mtnicmulsions are stabilized by conventional surfactants and thcrcforc hâve small particle size and high spécifie surface area, which can resuit in a rapid release of the agrochemîcal(s) contained therein.

[0007] Considertng the varicty of conditions and spécial situations under which agrochemîcal liquid concentrate formulation arc stored, shipped and used around the world, there remains a nced for aqueous polymer dispersions comprising agrochemicals, including watcr-soluble, watcr-dispcrsible or water-sensitive agrochemicals, having a 30 mcan particle size of the dispersed particles of > 1000 nm and which provide additional stability benefits under at least some of those conditions and situations. Thcrc is a further nced for such formulations having high loading that are stable when diluted with water under a wide range of field conditions. There is yet a further nced for such formulations that havc controlled release rates of agrochemicals into the application site from the formulation and that work in complex aqueous Systems and under a varicty of conditions.

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-3[0008] Similar properties arc rcquired in formulations in non-agricultural fîelds, for instance for controlled delîvery of pharmaceutically active ingrédients, for controlled delîvery of flavors from foods, for controlled dclivcry of dyes or pigments, for controlled release of fragrances from cosmctic or household products, or for controlled delîvery of enzymes and détergents in clcaning products. In these industries and others therc is a need for the ability to préparé stable formulations of components that can bc released to the target site upon application.

SUMMARY OF THE INVENTION [0009] Stabilized liquid agrochemical compositions are provided which comprise flowable, aqueous dispersion concentrâtes comprising: a) a continuous aqueous liquid phase; b) at least one dispersed solid phase comprising polymer particles having a mean particle size of at least one ( l ) micron, wherein the oulsidc surfaces of the particles comprise a colloïdal solid material and wherein the particles hâve at least one chemical agent distributed therein. The polymer particles are prepared from either a curable or polymcrizablc resin or a solidifiable thermoplastic polymer. In one embodiment, the colloïdal solid material is présent in the dispersed solid phase in an amount effective to stabilize the polymer resin in an cmulsion state during the process which is used to préparé the dispersed phase. In another embodiment, surfactants are used in combination with the colloïdal material in order to more flexibly control the size of the polymer particles. In another embodiment, the chemical agent is a solid and is distributed within the dispersed solid phase, or is a liquid and is distributed within the dispersed solid phase. In a further embodiment the continuous liquid phase is water or is a mixture of water and either a watcr-miscible liquid or a water-soluble solid. in another embodiment the polymer particles also contain a non-cross-linkable mobile chemical such that the extraction of this chemical from the dispersed solid phase renders it porous in a manner that allows the chemical agent to diffuse out from the dispersed phase. In another embodiment, the polymers forming the polymer particles contain hydropbilic groups that hydrate on exposure to water, thereby increasing the pcrmcability of the polymer matrix and allowing the chemical agent to diffuse out from the dispersed phase. In another «L r

-45 embodiment, the dispersed solid phase comprises polymer particles prepared by solidifying a thermoplastic polymcric rcsin, curing a thermoset resin or polymerizing a thermoplastic resin. When the at least one chemical agent is an agrochemically active ingrédient, the compositions of the invention can be used dircctly or with dilution to combat pests or as plant growth rcgulators

I0 [0010] In accordance with one embodiment of the invention, it has been found that aqueous dispersion concentrâtes of agrochemically active ingrédients in an aqueous liquid can be prepared by using polymerizcd. cured or solidified polymeric resin to entrap the agrochemically active ingrédients in a polymer matrix when a colloïdal solid is used 15 to stabîlîze the polymer rcsin in an émulsion statc during the curing réaction or solidification process. At least one agrochemically active ingrédient can be distributed within the polymer matrix which is dispersed as particles within the continuous aqueous liquid phase. Other active ingrédients may optionally be dispersed, dissolved, cmulsified, microemulsified or suspended within the continuous phase.

[001l] The release rate of agrochemically active ingrédients from the dispersed solid phase can be controlled by the optional incorporation within the dispersed phase of mobile non-cross-linkablc molécules, where these molécules are chosen to bc insoluble or partially soluble in the aqueous continuous phase, miscible or immisciblc with the 25 polymer rcsin that will form the particulate polymer matrix, soluble in water or some other medium to which the formulation will bc exposed upon use, and of molecular dimensions such that the voids they croate in tlie disperse phase upon extraction, allow the desired release of the agrochemically active ingrédients. The mobile non-crosslinkablc molécules may bc présent in the dispersed solid phase either as a molecular 30 dispersion (if miscible with the polymer resin), or as discrète inclusions (if immiscible with the polymer rcsin).

[0012] The release rate of agrochemically active ingrédients from the dispersed solid phase can bc further controlled by the optional incorporation within the dispersed phase 35 of non-porous particulate minerais as a diffusion banicr. For purposes of the présent

-55 invention, non-porous means that the minerai lacks porcs largcr than individual molécules of the agrochcmîcally active ingrédients, such that the diffusion coefficient of the agrochemica! through particles of the minerai is less than 10 ^iS m³/s.

[0013] The aqueous dispersion concentrâtes ofthe invention hâve a uscfully long period !0 of protection for watcr-solublc, water-dispcrsiblc, water-sensîtive and other agrochemicals such that the chemical and physical stability of the formulation is improved and which provides a practîcal utility in terms of storage, shipment and use. The dispersion concentrâtes of the invention also convcniently allow the combination of multiple active ingrédients in a single formulation, irrespective of whether they are liquida or solids, by incorporâting them separatcly or together în polymer matrix particles that are mutually physically compatible. The dispersion concentrâtes of the invention also providc the abîlity to control tlie release rate of the agrochemical into the target site from the concentratc or an end-usc dilute formulation and to enhance biological performance against target pests..

[0014] The aqueous dispersion concentrâtes ofthe invention hâve utility also outside the agriculturai field where there is need to prépare stable formulations and deliver chemical agents to a target site. For these purposcs the agrochemicals may bc rcplaccd with other chemical agents as required. In the context of the présent invention, chemical agents 25 thcreforc include any catalyst, adjuvant, vaccine, genetic vcctor, drug, fragrance, flavor, enzyme, spore or other colony forming unît (CFU), détergent, dye, pigment, adhcsîve or other component where release of the chemical agent from the formulation is required. In addition the aqueous dispersion concentrâtes may be dried to préparé a powder or granular product as desired.

[0015] The polymcrizablc rcsins suitable for use in prcparîng the dispersed phase curcd polymer matrix can bc selected from monomers, oligomers or prepolymers which arc polymcrizablc to either thermoset or thermo plastic polymer particles. In accordance with the invention, the disperse phase polymer matrix also can bc formed by dissolving 35 polymers in a volatile, watcr-immiscible solvent that also contants at least one

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-65 agrochcmical, stabilizing this solution in water as a Pickcring émulsion using colloïdal stabilizcrs, and then bcating this émulsion to cvaporatc the volatile solvent and fonn a disperse solid phase of a thermoplastic polymer matrix. In addition, the disperse phase polymer matrix can be formed by dissolving or suspending at least one agrochcmically active ingrédient in a non-aqueous liquid mixture comprising a melt of at least one

I0 suitable thermoplastic polymer, emulsifying said dispersion concentrate into a heated aqueous liquid to a mcan droplct size of l - 200 microns, which liquid also contains a colloïdal solid as (Pickcring) cmulsion stabilizer; and cooling the émulsion to producc thermoplastic polymcric particles.

[0016] The présent invention further relates to polymer particles comprising an entrapped agrochcmical that is either homogencously or non-liomogcneously distributed within such particles or prescrit in the form of domains within such particles and wherein the outsidc surface régions of the particles comprise a colioidal solid material.

[0017] The présent invention also includes a method for combatîngor controlling pests or regulating the growth of plants at a locus such as soil or foliage which comprises treating said locus with a dispersion concentrate according to the invention or dispersing a concentrate according to the présent invention in water or liquid fertilizer and treating said locus with the obtained diluted aqueous end-use formulation.

DETAILED DESCRIPTION OFTHE INVENTION [0018] Accordingly, in one embodiment, lhe aqueous liquid dispersion concentrate compositions of the présent invention comprise:

a) a continuons, aqueous liquid phase, optionally comprising at least one chemical agent; and

b) at least one disperscd, solid phase comprising polymer particles having a mcan particle size of at least onc micron, wherein the outside surfaces of the particles comprise a colloïdal solid material présent in an amount effective to stabilize the polymer particles in an cmulsion statc during the process which is used to prépare the disperscd phase and wherein the polymer particles bave at least onc chemical agent distributed thcrcin.

'ÇA [00 i 9} In one embodiment, the chemical agents are agrochcmically active ingrédients.

[0020] In one embodiment, the colloïdal solid material is a Pickering eolloid émulsion stabilizçr, [0021] In one embodiment, the polymer particles comprise an entrapped agrochcmical that is either homogcncously on non-homogcncously distributed within such particles or présent in the form of domains within such particles.

[0022] In the context of the présent invention, mean particle or droplet size indicatcs the volume-weighted mean, commonly designated D(v,0.5).

[0023] In one embodiment, the agrochcmically active ingrédient is a solid and is distributed within the dispersed solid phase or is a liquid and is distributed within the dispersed solid phase.

[0024] In one embodiment, the agrochemically active ingrédient (a.i.) in the dispersed phase is water-soluble, watcr-dispcrsiblc or watcr-scnsitivc.

[0025] In another embodiment, the dispersion concentrâtes for use în the liquid agrochcmical compositions of the présent invention arc those that are formed using curing agents, monomers, oligomcrs, prepolymers or blcnds thereof that exhibit a slow curîng or polymcrization réaction when combined with the curing agents at ambient conditions. Particularly suitable arc those curing agents, monomers, oligomers, prepolymers or blcnds thereof lhat exhibit no significant increase in viscosity under ambient conditions fora period ofat least I5 minutes, more particularly 30 minutes, most particularly l hour, after mixing with the curing agent.

[0026] In accordance with one embodiment of the invention, polymcrizablc thermoset resins arc understood to include ail molécules that may be irrcvcrsibly polymerized or

-8curcd to form a polymeric matrix that docs not mclt or deform at elevated températures below the point of thermal décomposition. The polymerization réaction may be initiated thcrmally, by addition of chemical curing agents or by suitable irradiation to croate radicals or ions such as by visible, UV, microwave or other clcctromagnctic irradiation, or électron bcam irradiation. Examples include the phenotics, ureas, melamines, cpoxics, polyesters, silicones, rubbers, pol y isocyanates, polyamines and polyuréthanes. In addition, bioplastic or biodégradable thermoset rcsins may be used including epoxy or polyester rcsins derived from natural materials such as vegetable oil, soy or wood and the like.

[0027] In accordance with another embodiment of the invention, polymcrizable thermoplastic resins are understood to include ail molécules that may be polymerized or cured to form a polymeric matrix that can mclt or deform at elevated températures below the point of thermal décomposition. The polymerization reaction may be initiated thcrmally, by addition of chemical curing agents or by suitable irradiation to croate radicals or ions such as by visible, UV or other electromagnctic irradiation, or électron bcam irradiation. Examples of suitable cthylenîcally unsaturated monomers include styrene, vînyl acetate, α-mctliylstyrene, methyl méthacrylate, those described in US 2008/017l 658 and the like. Examplcs of thermoplastic polymers for polymer particles that can be prepared from in-situ mini-cmulsîon polymerization include polymcthylmcthacrylatc, polystyrène, polystyrcnc-co-butadicnç, polystyrenc-coacrylonitrile, polyacrylatc, polyalkyI acrylalc, polyalkyl acetate, polyacrylonitrile or their copolymers.

[0028] In accordance with yet another embodiment of the invention, solidifiable thcrmoplastic rcsins are understood to include ail molécules that may be dissolved in a volatile solvent such that the solvent may be evaporated by heating to croate a polymeric matrix that can melt or deform at elevated températures below the point of thermal décomposition. The volatile solvent is chosen to be immîsciblc with the continuous aqueous phase and sufficicntly volatile that it can be convcnicntly removed from the composition by heating to a température below that where any significant décomposition *

-9occurs. Examples include polymers of the ethylcnically unsaturated monomers described above, as well as polymers such as cellulose acetate, polyacrylatcs, polycaprolactonc and polylactic acid. There may also bc mentïoncd polymethylmcthacrylate, polystyrène, polyethylvinyl acetate, cellulose acetate, polyacrylate, polyacrylonitrilc, polyamide, polyalkylencterephthalatc, polycarbonate, polyester, polyphenylcne oxide, polysulfone, polyimide, polycthcrimide, polyuréthane, polyvinylidene chloride, polyvinyl chloride, polypropylene and waxes, etc. In addition, bioplastic or biodégradable polymers such as thcrmoplastic starch, polylactic acid, polyhydroxy alkanoatc, polycaprolactonc, polyesteramide arc 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 halogcnated solvents such as dicholoromethane and trichloromethane. Other examples of suitable polymers and solvents are described in WO201J/O4O956A1.

[0029] In accordance with the invention, the polymer particles of the dispersed phase hâve a mean particle size of from l to 200 microns, more particularly from l to 100 microns and most particularly, from 2 to 80 microns.

[0030] ln one embodiment, suitable polymcrizablc rcsins and polymer solutions are those which are substantially immiscible with the aqueous liquid used in the continuous phase.

[0031] In the context ofthe présent invention, a colloïdal solid material is one whose properties of interest are determined by its surface interactions with other materials. Colloïdal solids are therefore necessarily those with high spécifie surface area, typically above 10 mVg. For example, colloïdal solids are able to stabilîze émulsions of immiscible Iiquids, as described for instance in WO 2008/030749. When serving for this purposc, such colloïdal solids may bc callcd Pîckcring colloids, colloïdal émulsion stabilizers, or other équivalent terms. Functional tests arc known for whether a colloïdal solid can stabîlizc an cmulsion as used herein, One such test is described infra in paragraph 110 below. Not ail colloïdal solids arc able to stabilize an cmulsion of any given pair of ^ÎC

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-10immiscible liquids, and such a functional test may used by those skilled in the art to identify a suitable colloid.

[0032] As noted above, the release rate of agrochemically active ingrédients from the disperscd solid phase can bc further controlled by the optional incorporation within the disperscd phase of non-porotis particulate minerais as a diffusion barricr. In some circumstances the samc non-porous particulate minerai used as a diffusion barricr within the disperscd phase may also serve as the colloïdal émulsion stabilizcr, In this situation the particulate minerai may be added in two separatc points within the préparation process as described below - firstly to the disperscd phase concentrate in order to become incorporatcd within the particles of the dispersed phase, and sccondly to the aqueous continuons phase in order to stabilize the émulsion.

[0033] In another embodiment, the affinity of the aqueous liquids suitable for use in the continuous phase a) for the agrochcmically active ingrédient distributed în the disperscd solid phase b) is such that substantially ail of the agrochemically active ingrédient romains in the disperscd solid phase and substantially nonc migrâtes to the continuous phase. Those skilled in the art will readily be able to déterminé whether a particular aqueous liquid mccts this critcrion for a spécifie agrochcmically active ingrédient in question by following any standard test procedure for determîning the partition coefficient of a compound (în this case, the agrochemically active ingrédient of the dispersed phase) between the continuous phase and the disperscd solid phase. Accordingly, the disperscd solid phase b) is immiscible with the continuous phase a).

[0034] In a further embodiment, the aqueous liquîds suitable for use in the continuous phase a) are solutions of water-soluble solutés in water.

[0035] Water-soluble solutés suitable for use in the continuous phase include salts such as hali des, nitrates, sulfates, carbonates, phosphates, nitrites, sulfites, ni tri des and sulfidcs of ammonium and of mctals such as those of groups 1 to 12 of the periodic table. Other <1 G»

-11suitablc solutés include sugars and osmolytcs such as polysaccharides, proteins, bctaincs and amino acids.

[0036] In one embodiment, the aqueous liquids suitable for use in the contînuous phase

a) are mixtures of water and a substantially water-miscîble non-aqucous liquid. In the contcxt of the invention, the term substantielIy watcr-miscible” means a non-aqucous liquid that forms a single phase when présent in water at a concentration up to at least 50 wt%.

[0037] Substantially watcr-miscible non-aqueous liquids suitable for use in the cotninuous phase a) include, for example, propylcnc carbonate; a water-miscible glycol selected from ethylenc glycol, dicthylcnc glycol, triethyienc glycol, propylene glycol, dipropylenc glycol, tripropylene glycol, butylène glycol, hexylene glycol and polyethylene glycols having a molecular weight of up to about 800; an acetylatcd glycol such as difpropylcnc glycol) methyl ether acetate or propylene glycol diacctate; tricthyl phosphate; ethyl lactatc; gamma-butyrolactonc; a watcr-miscible alcohol such as propanol or tetrahydrofurfuryl alcohol; N-methyl pyrrolidone; dimcthyl lactamidc; and mixtures thereof. In one embodiment, the non-aqucous, substantially watcr-miscible liquid used in the continuous phase a) is a solvent for at least one optional agrochcmically active ingrédient, [0038] In another embodiment, the aqueous, substantially water-mîscible liquid used in the continuous phase a) is fuily miscible with water in ail proportions. Altcmativcly, the aqueous, substantially water-mîscible 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 maintaincd in the liquid state by forming the composition at an elevated température.

[0039] Those skilled in the art will appreciatc that the quantifies of water and the nature and quantity of the non-aqucous, watcr-miscible liquid or watcr-soluble soluté can be varîcd to provide mixed aqueous liquids suitable for use tn the continuous phase a) and these quantitics can be determined without unduc expérimentation. In one embodiment, $ U

-125 the aqueous continuous phase comprises 5 to 95 wt%, more preferably 30 to 90 wt%, cthylenc glycol with the balance being water. In another embodiment, the aqueous continuous phase comprises 5 to 95 wt%, more preferably 30 to 90 wt%, glyccrol with the balance being water.

[0040J In one embodiment, when the concentratc is diluted in water, some of the agrochemical slowly diffuses out of the polymer matrix particles. The agrochcmical release rate from the cmulsificd polymer particles in the spray tank can bc adjusted, for cxamplc, by varying the size of the dispersed polymer particles in the concentratc, the concentration of active ingrédient în the polymer, the pH of the spray tank dispersion, the optîonal inclusion of non-porous particulate minerais (as diffusion barriers) in the polymer matrix, and the amount and nature of the thermoplastic polymers or polymcrizablc resin including monomers, oligomers, prepolymers and/or hardeners used to form the polymer particles.

[0041 ] In this regard, the dispersed phase can also include one or more non-crosslinkable mobile chemicals such that the extraction of this chemical from the dispersed phase rendors it porous in a manner that allows the chemical agent to diffuse out from the disperse phase. The mobile chemical may bc chosen to diffuse out rapidly within the formulation concentratc, such that the polymer matrix is rendered so porous that the agrochcmical is rapidly released upon dilution în water. Alternat)vely the mobile chemical may be chosen to be of limitcd solubility în the aqueous continuous phase, such that the mobile chemical diffuses out of the polymer matrix slowly after the formulation lias been diluted in water or applied to its target location, so that the agrochcmical is only substantially released at the target location. Examples include surfactants, solvents, oligomers, polymers, copolymers, acids, bases, natural or synthetic oils, natural or synthetic alcohols, subslantially watcr-soluble compounds or substantially waterinsoluble compounds. In a spécifie embodiment, the mobile chemical is selected such that it has limitcd solubility în a particular aqueous continuous phase, for instance an organic acid may bc chosen that îs substantially insoluble in an acidic aqueous continuous phase, yet upon dilution in water or application to the target site, the pH is higher than within the $ C

-135 dispersion conccntrate such that the organic acid (mobile chemical) is dissolved out of the polymer matrix rendering it porous and allowing the active ingrédient to bc relcased. ln another spécifie embodiment the mobile chemical is selected such that it lias limited solubility in aqueous cnvîronmcnls but high solubility in waxy materials such as a plant ciiticlc, so that the mobile chemical is only substantially extracted from the matrix on contact with a plant leaf, and the active ingrédient is then maînly relcased only on the leaf surface.

[0042] In another embodiment, a pH-sensitivc release of the agrochemical active is achieved by crcating a polymer matrix with excess amine groups. On dilution the amine 15 groups hydrate, but the rate and extent of hydration incrcascs at lower pli. The pH on dilution in the spray tank can bc controlled by including within the dispersed phase base components, but after application the pH eventually bccomes neutral and the release rate incrcascs. Alternat ivcly, a polymer matrix is created with excess acidic groups or other bases than amines. The nature of the pH sensitivity can be further adjusted by choosing 20 acid or base groups of varying respective pKa or pKb values.

[0043] In another embodiment, the active ingrédient release profile from the dispersed phase may bc modified by incorporating cross-linkablc monomers that contain hydrophilic groups such that on dilution into water the polymer matrix particles hydrate 25 and expand so that the matrix becomes more perméable. In a particular embodiment, the cross-linkabîe monomers are glyccrol diglycidyl ether epoxy resin. ln another particular embodiment, the cross-linkable monomers are polypropyleneoxide diglycidyl ether epoxy resin.

[0044] The non-cross-linkablc mobile chemical in the disperse phase may optionally bc selected to also perform as a surfactant or dispersant within the liquid dispersion conccntrate that îs used to prépare the liquid agrochemical compositions ofthe présent invention. If selected in this manner, the mobile chemical will adsorb to the surfaces of particles présent in the dispersion conccntrate and thereby stabîlîzc the dispersion of those particles. This behaviour will be observable in at least onc of the following ways:

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-145 the particles will be distributed individually rather than as agglomérâtes within the dispersion concentrate when observed microscopically, the viscosity of the dispersion concentrate will be reduced when the mobile chemical îs added, or the particles will hâve a greater tcndcncy to romain within the disperse phase instead of being lost to the continuons phase when the Itquid agrochemical compositions are prepared. Examplcs of 10 suitable mobile chcmicals useful for this purpose include copolymcrs of an a-olcfin and an N-vinyipyrrolidonc such as, for cxamplc, alkylated vinylpyrrolidone copolymcrs such as the Agrimers (e.g., Agrimer’ AL-22, based on l-cthcnylhcxadccyl-2-pyrrolidinonc) (International Spccialty Products (ISP) Corporation), or copolymers of an ti-olcfïn and cthylene glycol such as, for cxamplc Atlox 4914 of Croda Corp, or organosilicon surfactants such as Silwet L-77 (Momentive Performance Chcmicals).

[0045] In one embodiment, the aqueous liquid dispersion concentrate compositions of the prescrit invention comprise a mixture of polymer particles each containing one or more than one chemical agents (such as an agrochemically active ingrédient). Each one of the 20 chemical agcnt(s) is contained within the same or different disperscd phase polymer particles, and each respective disperscd phase particle optionally includes a different mobile chemical and/or polymer matrix as described above, such that each chemical agent or agent mixture has a different release profile. Optionally each respective solid disperscd phase may hâve different particle sizes.

[0046] In one embodiment, the aqueous liquid dispersion concentrate compositions of the présent invention comprise a solid phase in the form of fmcly divided, suspended polymer particles comprising u colloïdal solid material at their outside surface and containing at least one agrochemically active ingrédient, where the mcan particle diameter of such polymer particles is generally below 200 microns, frcqucntly below 100 microns, for cxamplc in the range from l - 200, particularly in the range from 1- 100 and especially in the range from 2-80 microns.

[0047] The term “agrochemically active ingrédient'’ refers to chcmicals and biological compositions, such as thosc described herein, which arc effective in killing. preventing,

C «

-15or controlling the growth of undesirable pcsts, such as, plants, insccts, mîcc, microorgantsm, a[gac, fungi, bacteria, and the like (such as pcsticidaliy active ingrédients). The tcrm may also apply to compounds that act as adjuvants to promote the uptakc and delivery of other active compounds. The tcrm may also apply to compounds that control the growth of plants in a desired fashion (e.g., plant growth rcgulators), to a compound which mimics the natural systemic actîvated résistance response found in plant species (e.g., plant actîvator) or to a compound that reduces the phytotoxic response to a herbicide (e.g., safener). If more than onc is présent, the agrochcmically active ingrédients arc independently présent in an amount that is biologically effective when the composition is diluted, ifnecessary, 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, [0048] Examples ofagrochemical active ingrédients suitable for use within the continuons phase a) or disperse phase b) in accordance with the présent invention include, but are not limited to: fungicides such as azoxystrobin, chlorothalonil, cyprodinil, difcnoconazolc, fludioxonîl, mandipropamid, picoxystrobin, propiconazole, pyraclostrobin, tebuconazole, thiabendazole and trifloxystrobîn; herbicides such as acetochlor, alachlor, ametryn, anilofos, atrazine, azafenidin, benfluralin, benfuresate, bcnsulidc, bcnzfcndizonc, bcnzofcnap, bicyclopyronc, bromobutidc, bromofenoxim, bromoxynil, butachlor, butafenacil, butamifos. butralin, butylatc, cafcnstrolc, carbctamide, chloridazon, chlorpropham, chlorthai-dimcthyl, chiorthiamid, cînidon-cthyl, cinmcthylin, clomazonc, clomeprop, cloransulam-methyl, cyanazine, cycloate, desmedipham, desmetryn, dichlobenil, diflufcnican, dîmepiperatc, dimcthachlor, dimethametryn, dimethenamid, dimcthenamid-P, dtnitraminc, dinoterb, diphenamid, dithiopyr, EPTC, csprocarb, cthalfluralin, cthofumcsatc, ctobenzanid, fcnoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazaniide, flamprop-mcthyl, flamprop-M-isopropyl, fluazolate, fluchloraliti, flufcnacct, Humiclorac-pentyl, ilumioxazin, fluorochloridone, flupoxam, flurcnol, fluridone, flurtamonc, fluthiacct-methyl, indanofan, isoxaben, isoxaflutole, lenacil, linuron, mcfenacct, mesotrione, metamitron, mctazachlor, mcthabenzthiazuron, mcthyldymron, metobenzuron, mctolachlor, mctosulam, metoxuron, metribuzin, molinatc, naproaniltdc, napropamide, neburon, norflurazon, orbencarb, oryzalin,

-16oxadiargyl, oxadiazon, oxyfluorfen, pebulatc, pendimcthalin, pentanochlor, pethoxamid, pcntoxazonc, phcnmcdipham, pinoxadcn, pipcrophos, pretilachlor, prodiaminc, profluazol, promcton, prometryn, propaclilor, propanil, propazine, propham, propisochlor, propyzamide, prosulfocarb, pyraflufen-ethyl, pyrazogyl, pyrazolynate, pyrazoxyfcn, pyributicarb, pyridate, pyriminobac-methyl, quinclorac, siduron, simazine, simetryn, S-metolach!or, sulcotrione, sulfentrazonc, tcbutam, tcbuthiuron, tcrbacil, terbumeton, tcrbuthylazine, tcrbutryn, thcnylchlor, thiazopyr, thidiazimin, thiobencarb, tiocarbazil, triallatc, trictazinc, trifluralîn, and vcrnolatc; herbicide safeners such as benoxacor, dichlormid, fcnchlorazolc-ethyl, fenclorim, flurazole, fluxofenim, furilazolc, isoxadifcn-ethyl, mcfenpyr; alkali métal, alkaline carth métal, sulfonium or ammonium cation of mcfenpyr; mcfenpyr-dicthyl and oxabetrinii; insecticides such as abamectin, clothianîdin, emamectin benzoatc, gamma cyhalothrin, Îmidacloprid, cyhalothrin and its enantiomers such as lambda cyhalothrin, tefluthrin, permethrin, resmethrin and thiamethoxam; nematicides such as fosthiazate, fenamiphos and aldicarb.

[0049] AdditionalIy, volatile agrochemicalIy active ingrédients such as those with a vapour pressure of at least 1 Pa at ambient température are also suitably entrapped in the dispersed phase b), Examplcs of such active ingrédients include volatile nematicides such as methyl bromidc, methyl iodidc, chloropicrin and 1,3-dichloropropcnc.

[0050] In one embodiment, the active ingrédients in the continuous phase may be in the state of a solution, an émulsion, a microemulsion, a microcapsulc or a particle or fine particle. In the contcxt of the présent invention, a fine particle is one substantially smaller than the dimensions of the solid polymeric particles of the dispersed phase, such that a plurality (at least 10) of active ingrédient particles are within each particle of the dispersed phase, whcrcas a non-fine particle is one only slightly smaller than the dimensions of the solid polymeric particles of the dispersed phase, such that each polymeric particle contains only a few active ingrédient particles.

[0051] Further aspects of the invention include a method ofprcvcntingor combating infestation of plant spccics by pests, and rcgulating plant growth by diluting an amount of

-175 concentrate composition with a suitable liquid carrier, such as water or liquid fcrtilizcr, and applying to the plant, troc, animal or locus as desired. The formulations of the présent 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.

I0 [0052] The aqueous liquid dispersion conccntrate compositions can be stored convcniently in a container from which they are poured, or pumped, or into which a liquid carrier is added prior to application.

[0053] The advantages of the aqueous liquid dispersion concentrais compositions of the présent invention include: storage-stability for extendcd periods, for example 6 months or longer at room température; multiple agrochemicals of different physical states may be convenîetitly combined in dispersions of mutually compatible solid particies; the release profiles of agrochemicals may be flcxibly and independently controlled; simple handling is made possible for users because dilution is made with water, or other liquid carrier, for préparation of application mixtures; reduced settling of the suspension during storage or on dilution; the compositions can casily be resuspended or redispersed with only a minor amount of agitation and are not susceptible to coalescence when dilution is made with fcrtilizcr solutions for préparation of application mixtures.

[0054] The rate of application of the composition of the invention will dépend on a number of factors including, for example, the active ingrédients chosen for use, the identity of the pest to be controlled or the plants whosc growth is to be inhibited and the formulations selected for use and whether the compound is to be applied to foliage, soil, for or root uptake or by chcmigation. As a general guide, however, an application rate of from l to 2000 g active ingrédient per hectare is suitable, in particular from 2 to 500 g active ingrédient per hectare.

[0055] In one embodiment, suitable raies for the agrochcmically active ingrédients used in the inventive compositions arc comparable to the existing rates given on the currcnt product labels for prodnets containing such actives. For example, Quadris* brand

-18azoxystrobin can be applicd at a rate of from i 12g to 224g a.i,/hectare and Quilt™ brand premix of azoxystrobin (75g/L)/propiconazolc( I25g/L) can be applied at a rate of from 0.75 -I.5 L/ha.

[0056] In one embodiment ofthc présent invention, a further comportent may be présent to control the pH of the water used to dilute the composition prior to use.

[0057] If a solid agrochcmically active material is présent, the solid active ingrédient may bc millcd to the desired particle size prior to dispersion within the polymcrizable resin (monomers, oligomers, and/or prepolymers, etc.) that will form the polymer matrix particles. The solid may bc milled in a dry statc using an air-mill or other suîtable equîpment as ncccssary, to achicvc the desired particle size. The particle size may be a mean 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.

[0058] As used herein, the term “agrochemically effective amount means the amount of an agrochemical active compound which advcrsely controls or modifies target pests or régulâtes the growth of plants (PGR). For cxample, in the case of herbicides, a herbicidally effective amount” is that amount of herbicide sufficient for controlling or modifying plant growth. Controlling or modifying cffccts include ail déviation from naturel development, for examplc, killing, retardation, leaf bum, albinism, dwarfing and the like. The term plants refers to ail physical parts of a plant, including sceds, 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, prolifération, division, reproduction, or spread of fungi. As used herein, the term “fungicidally effective amount or “amount effective to control or rcducc fungi” in relation to the fungicidal compound is that amount that will kill or matcrially inhibit the growth, prolifération, division, reproduction, or spread of a signîficant number of fungi. As used herein, the terms insecticide’’, “nematicîde” or ‘‘acaricidc shall mean a material that kills or matertally inhibits the growth, prolifération, reproduction, or spread of insects, nématodes or acarids, respectively. An effective amount of the insecticide,

-195 nematicide or acaricîdc is that amount that will kill or materially inhibit the growth, prolifération, reproduction or spread of a significant number of insects, nématodes or acarids.

[0059] In one aspect, as used herein, “regulating (plant) growth”, plant growth rcgulator, PGR, “regulating” or régulation includes the following plant responses; inhibition of cell élongation, for example réduction in stem height and internodal distance, strcngthcnïng of the stem wall, thus incrcasing the résistance to lodgîng; compact growth in omamentals for the économie production of improved quality plants; promotion of better fruîting; increasing the number of ovarîes with a view to stepping up yield; promotion of scnescencc of the formation of tissue enabling fruit to absciss; défoliation of nursery and ornamcntal bushes and trocs for mail-order business in the fall; défoliation of trees to interrupt parasitic cliains 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, [0060] In another aspect, “regulating (plant) growth, plant growth regulator, “PGR”, “regulating or régulation also includes the use of a composition as defined according to the présent invention for increasing the yield and/or împroving the vigor of an agricultural plant, According to one embodiment of the présent invention, the inventive compositions arc used for improved tolérance 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 sait stress of an agricultural plant.

[0061] The sélection 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 dépend on factors such as level ofpcst pressure, plant conditions, wcathcr and growing conditions as well as the activity of the agrachemically active ingrédients and any applicable label rate restrictions.

[0062] The invention relates also to liquid agrochcmical compositions comprising *

a) a continuons, aqueous liquid phase, optionally comprising at least one agrochcmically active ingrédient (for example, in the state selected from a solution or a dispersion such as émulsion, a microemulsion, and/or a suspension of microcapsules or fine particles); and

b) at least one dispersed, solid phase comprising polymer particles prepared from either a curable or polymerizablc rcsin or a solidafiable thermoplastic polymer, wherein the outside surfaces of the particles comprise a colloïdal solid material and whcrcin the particles hâve at least one agrochcmically active ingrédient distributed thereîn, [0063] A further aspect of the invention relates to a dilate aqueous spray composition for combating pests or regulating the growth of plants at a locus comprising

a) a contînuous aqueous phase comprising a suitable liquid carrier, such as water or a liquid fcrtilïzer, in an amount sufficicnt to obtain the desired final concentration of each of the active ingrédients in the spray composition;

b) at least one dispersed, solid phase comprising polymer particles prepared from either a cureable or a polymcrizable resin or a solidifiable thermoplastic polymer, wherein the outside surfaces of the particles comprise a colloïdal solid material and whcrcin the particles hâve at least one agrochcmically active ingrédient distributed therein; and

c) optionally, at least one agrochemically active ingrédient dispersed, dissolved, suspended, microcmulsified and/or emulsified in the liquid carrier.

[0064] In another embodiment, the invention relates to a dilutc pesticidal and/or PGR composition for ultra low volume (ULV) application comprising:

a) a contînuous phase comprising a carrier solvent having a flash point above 55°C in an amount sufficicnt to obtain the desired final concentration ofcach of the active ingrédients in the ULV composition;

b) at least one dispersed, solid phase comprising polymer particles prepared from either a cureable or a polymcrizable rcsin or a solîdifiable thermoplastic, whcrcin the outside surfaces of the particles comprise a colloïdal solid material

K

-21and wherein the particles hâve at least one agrochemically active ingrédient distributed therein.

[0065] The invention relates also to a method for combating or preventing pests în crops ol useful plants or rcgulating the growth of such crops, said method comprising:

I ) 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 agrochcmically active ingrédient, and also optionally comprising at least one acidic or basic component;

b) at least one dispersed, solid phase comprising polymer particles prepared from either a curcable or a polymerizablc resin or a solidifiabte thermoplastic, wherein the outside surfaces of the particles comprise a colloïdal solid material and wherein the particles hâve at least one agrochemically active ingrédient distributed therein, or

2) diluting the concentrate composition, if necessary, in a suitable carrier, such as water, liquid fcrtilizer or a carrier solvent having a flash point above 55°C, în an amount sufficient to obtain the desired final concentration of each of the agrochemically active ingrédients; and thon treating the desired area, such as plants, the plant parts or the locus thereof with the dîlute spray or ULV composition, [0066] The term plants refers to ail physical parts of a plant, including sccds. sccdlings, saplings, roots, tu bers, stems, flowers, stalks, fo liage and fruits. The term locus refers to where the plant is growing or is expeeled to grow.

[0067] The composition according to lhe invention is suitable for ail methods of application conventionally used in agriculture, e.g. pre-émergence application, postcmcrgencc application, post-harvest and seed dressing, The compositions according to the invention arc suitable for pre- or post-cmcrgcncc applications to crop areas.

Λ L16271

-22[0068] The compositions according to the invention arc suitable cspcciaily for combating and/or preventing pests in crops of uscful plants or for rcgulating the growth of such plants. Preferred crops of useful plants include canota, cereals such as barlcy, oats, ryc and wheat, cotton, maize, soya, sugarbects, fruits, bernes, nuts, vegctablcs, flowcrs, 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 dépend upon the particular type of pests to bc controlled, the dcgrcc of control required, and the timing and method of application.

[0069] Crops are to bc understood as also including those crops which hâve been rendered tolérant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase and HPPD-inhibitors) by convcntional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolérant to imidazolinoncs, e.g. imazamox, by conventional methods of breeding is Clcarfield® summer râpe (canola). Examplcs of crops that hâve been rendered tolérant to herbicides by genelic engineering methods include e.g, glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.

[0070] Crops are also to be understood as being those which hâve been rendered résistant to harmful insects by genetic engineering methods, for examplc Bt maize (résistant to European corn borcr), Bt cotton (résistant to cotton boll weevil) and also Bt potatoes (résistant to Colorado beetle). Examples of Bt maize arc the Bt 176 maize hybrids of NK® (Syngenta Secds), The Bt toxin is a protein that is formed naturel! y by BaciHus fhitringiensix soil bacteria. Examplcs of toxins, or transgcnic plants able to syntliesise such toxins, arc 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 transgcnic plants comprising one or more genes that code for an insecticidal résistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTlN33B® (cotton), Boilgard® (cotton), NcwLcaf® (potatoes), NaturcGard® and Protexcta®. Plant crops or seed material thereof can be both résistant to herbicides and, at the same time, résistant to

U

-23inscct fccding (stackcd transgenic evcnts). For cxample, sccd can hâve the ability to express an însccticidal Cry3 protein while at the same time being tolérant to glyphosate.

[007] ] 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).

[0072] Other uscfùl plants include turf grass for cxample in golf-courses, lawns, parks and roadsides, or grown commercially for sod, and ornamental plants such as flowers or bushes.

[0073] Crop areas arc areas of land on which the cultivated plants arc alrcady growing or in which the seeds of those cultivated plants hâve been sown, and also areas of land on which It is intended to grow those cultivated plants.

[0074] Other active ingrédients such as herbicide, plant growth regulator, algaccide, fungicide, bactéricide, viricide, insecticide, acaricide, nematicide or molluscicide may be présent in the formulations of the présent invention or may be added as a tank-mix partner with the formulations.

[0075] The compositions of the invention may further comprise other inert additives, Such additives include thickeners, flow cnhancers, dispersants, cmulsifiers, wetting agents, antifoaming agents, bi oc ides, lubricants, fillers, drift control agents, déposition cnhancers, adjuvants, évaporation retardants, freeze protecting agents, insect attracting odor agents, UV protecting agents, fragrances, and the like. The thickencr may bc a compound that is soluble or able to swcll in water, such as, for cxample, polysaccharides of xanthans (e.g., anionic hctcropolysaccharidcs such as RHODOPOLCâ) 23 (Xanthan Gum)(Rhodia, Cranbury, NJ)), algînates, guars or celluloses; synthetic macromoleculcs, such as modified cellulosc-bascd polymcrs, polycarboxyiates, bentonites, montmorillonîtes, hcctonitcs, or attapulgites. The freeze protecting agent may bc. for cxample, cthylcnc glycol, propylene glycol, glycerol, dicthylene glycol, saccharose.

-24water-solublc salis such as sodium chloride, sorbîtol, triethylene glycol, tetracthylenc glycol, urca, or mixtures thereof. Représentative anti-foam agents arc silicone oiIs, polydialkylsiloxanes, in particular polydimethylsiloxancs, fluoroaliphatic esters or pcrfluoroalkylphosphonic/perfluoroalkylphosphonic acids or the salts thereof and mixtures thereof. Suitable antifoams are polydimethylsiloxanes, such as Dow ComingCR) Antifoam A, Antifoam B or Antifoam MSA. Représentative biocidcs include l,2benzisothiazolin-3-onc, available as PR.OXEL® GXL (Arch Chcmîcals).

[0076] The compositions of the invention may be mixed with fertîlizers and still maintain their stability.

[0077] The compositions of the invention may bc used in conventional agricultural methods. For cxample, the compositions of the invention may be mixed with water and/or fertilizers and may be applied precmergcucc and/or postemergencc to a desired locus by any means, such as airplane spray tanks, irrigation equipment, direct injection spray equipment, knapsack spray tanks, cattlc dipping vais, 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.

[0078] Within the scopc of the présent invention arc four different methods of producing dispersed phase polymeric particles containing chemical agents, which are described in a manner wherein the chemical agents are agriculturally active ingrédients. Each method results in a dispersed phase that comprises a solid polymer matrix with at least one agriculturally active ingrédient dîstributed therein, a colloïdal solid material at the surface, optionally a non-cross-linkable mobile chemical such that the extraction of this chemical from the dispersed phase renders it porous in a manner that allows the agrochemîcally active ingredient(s) to diffuseout from the dispersed phase, optionally a polymer matrix with hydraphîlic groups that hydrate on exposure to water and render the matrix perméable in a manner that allows the agrochemically active îngrcdîent(s) to diffuse out from the dispersed phase, and optionally a non-porous minerai that renders the dispersed phase more imperméable to the agrochemically active ingrcdicnt(s).

-25[0079] The first method comprises the following stcps:

1. preparing a dispersion concentrate by dissolvtng or suspending at least one agrochcmically active ingrédient 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 or initiator, and one or more optional componcnts selected from non-porous particulate minerais as diffusion barricr and/or non-crosslinkable mobile chemicals,

2. cmulsifytng said dispersion concentrate in to an aqueous liquid to a mean droplet size of l - 200 microns, which liquid also contains a colloïdal solid as (Pickering) émulsion stabilizcr, and, optionally, certain suitable hardener, catalyst or initiator capable ofdiffusing into the disperscd uneured resîn droplets; and

3. cffecting crosslinking or cure of the cross-linkablc resin mixture to produce cured thermoset polymeric particles.

[0080] The second method is substantially identical to the fîrst, except that the dispersion concentrate comprises as non-aqueous liquid a polymcrizable resin instead of a crosslinkablc resin. Instead of a curing réaction in step 3, the disperscd phase particles arc formed by a polymerization réaction, so that the resultîng disperscd phase comprises thcrmoplastic polymeric particles rather than lhermoset polymeric particles.

[0081] The third method comprises the following steps:

1. dissolving or suspending at least one agrochcmically active ingrédient in a nonaqueous liquid mixture comprising at least one suitable solidifîable polymer dissolved in a volatile solvent, and one or more optional componcnts selected from non-porous particulate minerais as diffusion barricr and/or non-crosslinkable mobile chemicals;

2. emulsifying said solution in to an aqueous liquid to a mean droplet size of l - 200 microns, which liquid also contains a colloïdal solid as (Pickering) émulsion stabilizcr; and «

*

3. effccting évaporation of the volatile solvent by heating the émulsion to a température of about 3O-I2O°C for about 0, l- 10 hr to produce solid thermoplastic polymer particles.

[0082] The fourth method of préparation comprises the following steps:

1. preparing a dispersion conccntrate by dissolving or suspending at least one agrochcmically active ingrédient in a non-aqueous curable liquid mixture comprising a mclt of at least one suitable solidifïablc thermoplastic polymer, and one or more optional components selected from non-porous particulate minerais as diffusion barrier and/or non-crosslinkable mobile chemicals,

2. emulsifying said dispersion conccntrate in to a heated aqueous liquid to a mean droplet size of I - 200 microns, which liquid also contains a colloïdal solid as (Pickcring) émulsion stabilizer, and

3. coolîng the émulsion to produce thermoplastic polymcric particles.

[0083] In one embodiment, the dispersion conccntrate is prepared by:

a. dissolving or suspending at least one agrochemically active ingrédient 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, catalyst or înîtiator, and one or more optional components selected from non-porous particulate minerais (as diffusion barrier) and/or non-crosslinkable mobile chemicals;

b. emulsifying said solution or suspension in to an aqueous liquid to a mean droplet size of l - 200 microns, which liquid also contains a colloïdal solid as (Pickering) émulsion stabilizer, and, optionally, certain suitable hardener, catalyst or initiators capable of dîffusing into the disperscd uneured or unpolymerizcd resin droplcts; and

c. effccting crosslinking, cure or polymcrization of the resin mixture to prodiicc curcd thermoset or polymerized thermoplastic resin polymer particles having at least onc agriculturally active ingrédient distributed thcrcin and at least one

4C

-275 colloïdal solid material at their surfaces and that after curing are dîspcrscd in the aqueous liquid, [0084] In one embodiment, the dispersion concentrate is prepared by adding the hardencr through the continuons phase, after the Pickcring émulsion is formed, so that the disperscd phase premix is incapable of curing, Altcrnatively a first very slow-reacting hardener can be used in the dispersion concentrate, and then a second fast-curing hardencr, an accclcrator or catalyst can be added through the continuous phase. These second agents arc added to the continuous phase after the dispersed phase is cmulsificd, so they must be chosen to be miscible in the continuous phase, Suitable fast cure water15 miscible hardeners include diethylcne triaminc, tricthylene tétramine, xylene diamine, polyethylene glycol diamine, and polyoxypropylene diamine. Mixtures of hardeners may also be employed for extra flexibil îty.

[0085] ln one embodiment, the dispersion concentrate is prepared by adding a premix of 20 the dispersed phase to a premix of the continuous phase, wherein:

l ) the premix of the dispersed phase is prepared by blending with a high shear mixer; at least one agriculturally active ingrédient, at least one suitable curable or polymcrizablc resin monomer, oligomer, prepolymer or blend thereof, a suitable hardener, catalyst or initiator, an optional non-crosslinkable mobile chemical, and an optional particulate non-porous minerai as diffusion barrier;

2) the premix of the continuous phase is prepared by blending with low shear mixer: an aqueous liquid with a colloïdal solid as an émulsion stabiîizer.

[0086] Tlic 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 Pickcring émulsion and then heated or exposed to light or other clectromagnetic radiation conditions (UV, micro wave), as needed, in order to polymerize the dispersed phase. The shear rate and duration of the émulsification may be readily determined by one skilled in the art, guidcd by the following observations: if the shear rate is too low, the émulsion and resulting polymer matrix particies are relutivcly coarsc and may bc larger than

ÜL f

-28dcsircd; if the shear rate is instcad too high or of too long a duration, the émulsion stabilizing colloid cvcntually bccomes so dcplctcd from the continuous phase that any new interfacial surface between the dispersed and continuous phases is effectively unprotcctcd, at which point rapid coalescence or heteroflocculation of the dispersed phase occurs and the Pickcring émulsion is cffcctively lost.

[0087] In one embodiment, the mixture of the dispersed phase premix and the continuous phase premix is stirred under high shear conditions for 5-J 0min and heated to a température of about 30-l20°C for about O.l- 10 hr in order to effect the curing réaction, [0088] In one embodiment. the dispersion concentrate is prepared by:

a. dissolving or suspending at least one agrochemically active ingrédient in a nonaqueous liquid mixture comprising at least one suitable polymer dissolved in a volatile solvent, and one or more optional components selected from non-porous particulate minerais (as diffusion barrter) and/or non-crosslinkable mobile chemicals;

b. cmulsifying said solution in to an aqueous liquid to a mcan droplct size of l 200 microns, which liquid also contains a colloïdal solid as (Pickering) émulsion stabilizer; and

c. effecting évaporation of the volatile solvent by heating the cmulsion to a température of about 30-l20°C for about 0.I- 10 hr to produce solid thcrmoplastic polymer particles having at least one agriculturally active ingrédient distributed therein and colloïdal solids at their surfaces and that arc dispersed în the aqueous liquid. If ncccssary more liquid may be added to the continuous phase to replace any liquid lost during the évaporation process.

[0089] Suitable polymcrizablc rcsins for use in preparing the solid polymer particles of the dispersed solid phase include thermosets such as epoxy rcsins, phcnolic rcsins, aminoplast restas and polyester rcsins.

-29[0090] Other suitable polymcrizablc rcsins for use in preparing the solid polymer particles of the dispersed solid phase include thcrmoplastics rcsins such as styrenés, methyl méthacrylates, and acrylics.

[0091] Suitable thermoplastic polymers include polymers of the thermoplastic rcsins described above, as wcll as polymers such as cellulose acetate, polyacrylatcs, polycaprolactone and polylactic acid.

[0092] With respect to the epoxies, ail customary di-and polyepoxide monomers, prepolymers or blends thereof arc suitable epoxy resîns for the practice of this invention. In one embodiment, suitable epoxy resins arc those that arc liquid at ambient température. The di- and polyepoxides may be aliphatic, cycloaliphatic or aromatic compounds. Typical examples of such compounds are the diglycîdyl éthers of bisphenol A glycerol or resorcinol, the glycidyl cthers and β-methylglycidyl ethers of aliphatic or cycloaliphatic diols or polyols, including those of hydrogenated bisphenol A, ethylcnc glycol, 1,2-propanediol, 1,3-propancdiol, 1,4-butancdîol, diethylcne glycol, polyethylene glycol, polypropylcnc glycol, glycerol, trimethylolpropane or 1,4-dimethylolcyclohexanc orof2,2-bis(4-hydroxycyclohcxyl)propane, the glycidyl ethers ofdi- and polyphcnols, typically resorcinol, 4,4'-dihydroxydiphcnylmethanc, 4,4'-dihydroxydiphenyl-2,2propane, novolaks and l,l,2,2-tetrakis(4-hydroxyphcnyl)ethane, Further examplcs are Nglycidyl compounds, including diglycidyl compounds of cthylene urea, 1,3-propylene urca or 5-dimcthylhydantoin or of 4₍4'-melhylene-5,5'-tetramethyldihydantoin, or those such as triglycidyl isocyanurate, or biodcgradable/bio-derivcd epoxies (vcgetable oilbascd).

[0093] Further glycidyl compounds of technical importance arc the glycidyl esters of carboxylic acids, especially di-and polycarboxylîc acids. Typical examplcs arc the glycidyl esters ofsuccinic acid, adipic acid, azclaic acid, scbacic acid, phthalic acid, terephtbalic acid, tetraand hexahydrophthalîc acid, isophthalic acid or trimellitic acid or of partially polymcrizcd, e.g. dimerised, fatty acids.

-305 [0094] Exemplary of polyepoxides that diffcr from glycidyl compounds arc the dicpoxides ofvinylcyclohexene and dicyclopcntadiene, 3-(3',4’-epoxycyclohexyl)-8_t9cpoxy-2,4-dioxaspiro[5.5]undccane, the 3',4'-cpoxycyclohexyimcthyl ester of 3,4cpoxycyclohexanecarboxylic acid, butadiene dicpoxidc or isoprene diepoxidc, cpoxidizcd linoleic dérivatives or cpoxidizcd polybutadicne.

[0095] Other suitable cpoxy rcstns arc diglycidyl ethers or advanced diglycidyl ethers of dihydric phénols or dihydric aliphatic alcohols of 2 to 4 carbon atoms, preferably the diglycidyl ethers or advanced diglycidyl ethers of 2,2-bis(4-hydroxyphcnyl)propane and bis(4-hydroxyphcnyl)methane or a mixture of these cpoxy rcsins.

[0096] Suitable epoxy resin hardeners for the practice of this invention may be any suitable cpoxy resin hardener, typically selected from primary and secondary amines and their adducts, cyanamide, dicyandiamidc, polycarboxylic acids, anhydrides of polycarboxylic acids, polyamides, polyamino-amides, polyadducts of amines and polyepoxides and polyols.

[0097] A variety of amine compounds (mono, di or poiyamincs) can be used as a hardener such as aliphatic amines (dicthyIcnc triamînc, polyoxypropylcnc triaminc etc), cycloaliphatic amines (isophorone diaminc, amînocthyl piperazinc or diaminocyclohexanc etc), or aromatic amines (diamino diphenyl methane, xylcnc diaminc, phenylcne diamine etc). Primary and secondary amines broadly can serve as hardening agents while tertiary amines gcnerally act as catalysts, [0098] Although epoxy hardeners are typically amines, other options exist and thesc will give extra flexibîlity to accommodate chemical agents that might be unstablc or soluble in the présence of amine, or allow a broader range of cure rates to be achieved.

[0099] For cxample, other suitable hardeners are anhydrides of polycarboxylic acids, typically phthalic anhydride, nadîc anhydride, mcthylnadîc anhydride.

-31methyItctrahydrophthalîc anhydride, metliylhcxahydroplithalic anhydride and, in addition, tctrahydrophthalic anhydride and liexahydrophthalic anhydride, [00100] In accordance with the invention, Pickering colloïdal cmulsion stabilizers of any type may be used to stabilîze émulsions prior to the step of solidifying the dispersed phase into a solid polymer matrix, rcgardless of polymer matrix type, where the dispersed phase contains a chemical agent such as an agrochemicai active ingrédient, and optionally where the dispersed phase contains a means to control lhe matrix permeability and thereby the agrochemicai active ingrédient release rate upon application.

[00101] More specifically, solids, such as silîcas and clays, hâve been taught in the litcrature for use as viscosity modifiers in agrochemicai formulations to inhibit gravitydrîvcn sédimentation or cream séparation by forming a network or gel throughout the continuous phase, thereby increasing the low-shcar viscosity, and slowing the movement of small particles, surfactant micclles or émulsion droplets. The colloïdal solids of the présent invention instcad serve as a processing aid to stabilîze the droplets containing the resin monomers during cure by adsorbing to the transient liquid-liquid interface, thereby forming a barricr around the curing droplets so that contacting or ncighbouring curing droplets arc not able to coalcscc, irrcspcctîvc of whether or not the curing droplets have collected in a sédiment or a cream layer. It is possible to distinguish the two different fonctions - rheologîcal modification or émulsion stabilization, by a functional test such as described below. The effectiveness of the colloïdal solid in stabilizing the émulsions of curing polymer droplets dépends on particle size, particle shape, particle concentration, particle wcttability and the interactions between particles. The colloïdal solids must be small cnough so that they can coat the surfaces of the dispersed curing liquid polymer droplets, and (he curing liquid droplets must bc sufficiently small for acceptable dispersion stability against sédimentation of the resulting solid polymer particles if the dispersion conccntratc containing such particles is diluted for use. The final polymer particles (and hence, the colloïdal solids) will also need to bc small enough to providc an acccptably even product distribution at the target site. The colloïdal solid also must have suffîcicnt affinity for both the Iiquids forming the dispersed and continuous phases so that

-32they arc able to adsorb to the transient liquid-liquid interface and thereby stabilize the émulsion during cure. This wetting characteristîc, particle shape and suitabilîty for Pickering-type émulsion stabilization may be rcadily assessed by preparing a control formulation lacking the colloïdal solid as émulsion stabilizer. In such a case the curing liquid polymer droplcts coalcsce and form a consolidatcd mass înstead of a dispersion of fine solid polymer particles.

[00102] In one embodiment, the colloïdal solids hâve a number-weighted médian particle size dîametcras measured by scanning électron microscopy ofO.O l - 2.0 microns, particularly 0.5 microns or less, more particularly 0.1 microns or less.

[00103] A wide varicty of solid materials may be used as colloïdal stabilizers for preparing the dispersions ofthe présent invention including carbon black, mctal oxides, métal hydroxides, mctal carbonates, métal sulfates, polymers, silica and clays. Suitable colloïdal stabilizers arc insoluble in any of the liquid phases présent in préparation of the concentratc formulation. If an agrochcmical active ingrédient has suitabi y low solubîlity in any liquid used to dilure the final composition, and in both the continuous and (transient) disperscd liquid phases, that is below about 100 ppm at room température, 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 ingrédient can serve as the colloïdal stabilizer. Examples of particulate inorganic materials arc oxy compounds of at least one of calcium, magnésium, aluminium and silicon (or dérivatives of such materials), such as silica, silicate, marblc, clays and talc. Particulate inorganic materials may be cithcr naturally occurring or synthesized in rcactors. The particulate inorganic material may be a minerai chosen from, but not limitcd to, kaolin, bentonitc, alumîna, lirnestonc, bauxite, gypsum, magnésium carbonate, calcium carbonate (either ground or prccipitated), perlitc, dolomite, diatomite, huntite, magnesite, bochmitc, sepiolite, palygorskite, mica, vermiculite, illite, hydrotalcite, hcctorite, halloysitc and gibbsite. Further suitable clays (for example aluminosilîcates) include those comprising the kaolinitc, montmorillonitc or îllitc groups of clay minerai. Other spécifie cxamplcs are attapulgitc, laponîte and sepiolite. Polymers that fiocculate

-33thc colloids (such as xanthan in the case of colloïdal kaolin) can also improve the stability of Pickcring émulsions.

[00104] In one embodiment, non-porous particulatc inorganic materials are distributed wîthîn the polymer particles along with the agrochemically active ingrédient to serve as an optional diffusion barricr. The diffusion barricr is prepared by dissolving or suspending such materials along with the (e.g., water-sensitive) agriculturally active ingrédient in the non-aqucous curable liquid mixture that is used to prépare the thermoset or thcrmoplastic rcsin polymer particles which serve as disperscd phase b). Suitable nonporous particulatc diffusion barricr materials include carbon black, métal oxides, métal hydroxides, métal carbonates, métal sulfates, polymers, silica, mica and clays.

[00105] In one aspect of the invention, the particulate inorganic material is kaolin clay. Kaolin clay is also referred to as china clay or hydrous kaolin, and contains predominantly minerai kaolinitc (AljShOjfOH^), a hydrous aluminium silicate (or aluminosilicatc).

[00106] In one aspect of the invention, the particulate inorganic material may be surface modified. Surfacc-modificd means that the inorganic particle surface has been niodifîed so as to hâve reactive groups. The surface of the particles may be modified using a wide variety of chemicals, with the general structure X—Y—Z, in which X is a chemical moiety with a high afflnity for the particle surface; Z is a (réactivé) chemical moîety with a desired functionality; and Y is a chemical moiety that links X and Z together.

[00l 07] X may be, for example, an alkoxy-silane group such as tri-cthoxysîlane or tri-methoxysilane or trichlorosilane, which rs particularly uscful when the particles hâve silanol (SiOH) groups on their surface. X may also be, for example, an acid group (such as a carboxylic or an acrylic acid group) which is particularly uscful when the particles hâve basic groups on their surface. X may also be, for example, a basic group (such as an

-34amîne group), an epoxy group, or an unsaturatcd group (such as an acrylic or vinyl group), [OOiOK] Y can bc any chemical group that links X and Z together, for example a polyamide, a polyisocyanate, a polyester or an alkylene chain; more suitably it is an alkylene chain; and even more suitably it is a C₂.₆ alkylene chain, such as ethylene or propylene.

[00109] Reactive groups Z can be selected from any groups, and may be different from Y, which can bc used to react with a cross-linkcr.

[00110] The type and amount of colloïdal solid is selected so as to provide acceptable physical stability of the composition during cure, polymerization, solvent évaporation or other polymer solidification proccsscs. This can readily be determined by onc of skill in the art by routine évaluation of a range of compositions having different amounts of this component. For example, the ability of the colloïdal sofids to stabilize the composition can be verificd by preparing a test sample with the colloïdal solid and it can be confirmed that the émulsion of droplcts is stable and does not exhibit coalescence. Coalescence is apparent by the formation of large droplcts visible to the cyc, and ultimately by the formation of a layer of liquid monomers, polymer mclt or polymer solution within the formulation. Physical stability of the composition during cure, polymerization, solvent évaporation or other polymer solidification is acceptable if no significant coalescence is évident and the solid polymer particles are présent as a fine dispersion.

[00111] For example, in onc embodiment the colloïdal solidsare employcd in an amount of from l to fi0%, particularly from 4 to 50% by weight of the dispersed phase. Mixtures of colloïdal solids may be employed.

[00112] In onc embodiment, onc or more surfactants may optionally bc used in addition to Pickcring émulsion colloïdal stabilizers, in order to convcnicntly control the

Su

-35sizc of the émulsion droplets in conjunction with the shçar rate applied during the émulsification process. If présent, the one or more surfactants arc employed în an amount of from 0.1% to 90%, particularly from l% to 60% by weight of the Pickering émulsion colloïdal stabilizers. In a particular embodiment, the surfactants are chosen to hâve a low HLB such as 6 or below. In another particular embodiment, the surfactant is alkylaminc

2-molc ethoxylatc, whether the alkyl group contaîns from about 8 to about 18 carbon atoms.

[00113] The following examplcs illustrate further some of the aspects of the invention but are not intended to limit its scope. Where not otherwise specified throughout this spécification and claims, perccntages are by weight.

Examples l - 4 - Hlustrating the use of different continuons phase liciuids [00114] A resin mixture A of I9.l g 635 Thin Epoxy Resin (US Composites of Wcst Palm Bcach, FL) and 9.5 g 556 2: l Epoxy Hardener (also of US Composites) was prepared. The following liquid continuous phase samples of 10 g liquid were then prepared cach by vortex mixing with 0.2 g Acrosil 200 fiimed silica as colloïdal stabilizer: 9:l ethylene glycohwater, 9;l PEG200:water, 9:l glycerine.water, and water. A 0.2 g of resin mixture A was then introduccd into cach continuous phase sample and disperscd by vortex mixing. The samples were placed on a platform shaker overnight at room température and then examîncd by light microscopy. In every case the présence of a dispersion of epoxy resin particles of diameter approximately 100 microns was confimied. These examplcs show that small particles of solid epoxy resin may be formed in a variety of different liquid continuous aqueous phases.

Examplcs 5-7. Hlustrating the use of different colloids to stabilize the resin before curing.

[00115] A resin mixture B was prepared by mixing together 9 g 635 Thin Epoxy Resin, 1.5 gof finely mi lied difcnoconazole and 4.5 g 556 2;l Epoxy Hardener. The following liquid continuous phases were then prepared cach by vortex mixing; 0.2 g Acrosil 200 fumed silica in 9.8 g water. and 0.2 g fumed aluminum oxide in 9.8 g water.

-360.2 g of resin mixture B was then introduced into each continuous phase sample and dispersed by vortex mixing. The samples were placed on a platform shaker overnight at room température and then examined by light microscopy. In every case the presence of a dispersion of fine epoxy resin particles of diameter approxîmately I00 microns was confirmed. In addition, a sample was prepared where the liquid continuous phase did not contain any colloïdal soltds, and the result was a iarge deposit of solid epoxy material adhered to the container wall. This example shows that a variety of different colloïdal solids may bc used to stabilîzc dispersions of epoxy resin but that if no colloïdal solid is used the resin sîmply coalesccs and ultîmately solidifies into a solid mass.

Exiimplcs 8 - 16. Incornorating different AI’s into the polymer matrix [00116] N inc different individual resin mixtures were prepared by mixing together 8 g 635 Thin Epoxy Resin, 4 g 556 2: l Epoxy Hardener and between l .0 and l ,5g of the following fînely mi lied active ingrédients: atrazinc, azoxystrobin, bicylopyrone, cyproconazole, difenoconazole, mesotrione, prodiamine, thiabendazole, thiamethoxam. By inspection it was clear that at these concentrations bicylopyrone and mesotrione were fully dissolved in the liquid resin, most of the cyproconazole was dissolved, and the other AI’s had not apprcciably dissolved. I g of each of these resin mixtures was separatcly dispersed by vortex mixing into 10 g continuous phase liquid samples each containing 0.2 g Aerosil 200 fumed silica dispersed în 9.8 g water. The samples were placcd on a platform shaker overnight at room température and then examined by light microscopy. In every case the presence of a dispersion of epoxy resin particles of diameter approxîmately I00 microns was confirmed. Crystals of the active ingrédient were visible insidc the epoxy particles under polarîzed light, exccpt that in the cases of bicyclopyrone and mesotrione individual crystals were not visible as these active ingrédients had dissolved in the epoxy resin - in these cases the entire epoxy resin particle was slightly biréfringent indîcating the présence of crystal domains within the matrix. These cxarnplcs show that a wide variety of different active ingrédients may bc efficicntly capturcd in the epoxy resin particles, rcgardless of whether they arc insoluble, partly-solublc or fullysolublc in the resin, and with no signîficant modification needed in the process nor the présence of other componcnts.

-37Examples 17 - 18 lllustrating the entraomcnt of an active ingrédient in polystyrène and nolyacrylate matrices.

A. Formulation préparation [001 17] The dispersed phase is premixed with a shear mixer as described in table l below. The continuons phase is premixed with low shear mixer. The premixed dispersed phase is added into the continuous phase, and then blend with high shear mixer for 5lOmin. In order to polymcrizc, the emulsified formulation is treated with high température (70°C) for 8hr. Average diameter of particles was determined by Malvem® master sizer.

Table 1:

	Example 17	Example 18
Dispersed phase	Atrazine 6% Styrene monomer 14.7% Methyl ethyl ketone peroxide 0.3%	Atrazine 6% Methylméthacrylate monomer 14.7% Methyl ethyl ketone peroxide 0.3%
Continuous phase	Aerosil A300 3% Phosphoric acid (8%) 0-05% water 7595%	Aerosil A300 3% Phosphoric acid (8%) 0.05% water 75.95%
Mean particle diameter (gm)	13	14

Examplcs 19 20 IIIustrating control of release rate by incorporation of a mobile noncross-linkable molécule into the polymer matrix and examples 21-22 illustrating the entrapment of liquid active ingrédients

A. Formulation préparation [00118] The dispersed phase is premixed with a low shear mixer as described în table 2 below. The continuous phase is premixed with a low shear mixer. The premixed dispersed phase is added into the continuous phase, and then mix with a high shear mixer for 5-10min. For accclcrating the epoxy curing reaction, the mixed formulation was treated with high température (70°C) for 3hr. Average diameter of particles was determined by Malvcrn® master sizer.

U

B. Release rate [00119] The curcd compositions 19 and 20 were diluted in water with appropriate cmulsi fiers (Toxi mu I TA-6, Stepfac 8180 and Toximul 8320 etc) in a glass bot tic and then stirred. The concentration of active ingrédient was monîtored by HPLC analysis.

Table 2

	Example 19	Example 20	Example 21	Example 22
Dispersed phase	Thiamethoxam 5% Epoxy 635 10% Hardener 556 5%	Thiamethoxam 5% Epoxy 635 9% Hardener 556 4.5% Polyethyleneglycol (Mw=200) 1.5%	Mefenoxam 5% Epoxy635 10% Hardener 556 5%	s-metolachlor 5% Epoxy 635 10% Hardener 556 5%
Continuous phase	Aerosil A200 2% water 78%	Aerosil A200 2% water 78%	Aerosil A200 2% water 78%	Aerosil A200 2% water 78%
Average particle diameter (P™)	55	45	25	27
%ai release Ohr 24hrs 48hrs	0.9 1.2 1.4	1.8 2.3 2.5	42 51 56

Exemples 21 - 24 Illustrating Pickcring émulsions using clay and flocculating polymers A. Formulation préparation [00120] The dispersed phase is premixed with a shear mixer as described in table 3 below. The continuous phase is premixed with low shear mixer. The premixed dispersed phase is added into the continuous phase, and then blend with a high shear mixer for 510min. In order to polymerize, the cmulsified formulation is treated with high température (70°C) for 8hr. Average diameter of particles was determined by Malvern® master sizer.

tvl

-395 Table 3

		21	22	23	24
Dispersed phase	Mefenoxam	7.5
s-metolachlor		7.5
Tefïtrthrin			7.5
Propiconazole				75
Resorcînol diglycidyi ether	5	5	5	5
Poiyoxypropyiene diamine (Mn=230 Da)	2.5	2.5	2.5	2.5
Continuous phase	Clay (kaolin)	1.2	1.2	1.2	1.2
Xanthan Pregel (2%)	2	2	2	2
Phosphoric acid (8.5%)				Û.1
water	18.8	18.8	1B.8	18.7
	Average Particle size (um)	30	25	17	30

[00121 ] Although only a fcw exemplary embodiments of this invention hâve been described in detail above, those skilled in the art will rcadily apprecîate that many I0 modifications are possible in the exemplary embodiments without materially departing from the novel tcachings and advantages of this invention. Accordingly, ail such modifications are întcnded to bc încluded within the scopc of this invention as defined in the following claims.

0 NOV. 2012

Claims (44)

1. We claim:

   1. An aqueous liquid dispersion concentrate composition comprising (a) a continuous aqueous liquid phase; and (b) at least one dispersed, solid phase comprising polymer particies having a mean particle size of at least one micron and prepared from either a curable or polymerizablc resin or a soiidifiable thermoplastîc polymer, wherein the outside surfaces of the polymer particies comprise a colloïdal solid material and wherein the polymer particies have at îcast onc chemical agent dîstributed thcrcin.
2. 2. The composition of claim I, wherein the chemical agent is an agrochemicaily active ingrédient.
3. 3. The composition of claim I, wherein the colloïdal solid material is présent in an amount effective to stabilize the polymer particies in an émulsion state during the process which is used to préparé the dispersed phase.
4. 4. The composition of claim 2, wherein the agricuiturally active ingrédient comprises a solid and is dîstributed within a dispersed solid phase or is a liquid and is dîstributed within a dispersed solid phase.
5. 5. The composition of claim I, wherein the dispersed phase comprises at least one non-cross-linkablc mobile chemical such that the extraction of this chemical from the dispersed phase renders it porous in a manner that allows the active ingrédient to diffuse out.
6. 6. The composition of claim I, wherein the polymer molécules that comprise the polymer particies contain hydrophi lie groups that hydrate on exposure to water in a manner that renders the polymer particies more perméable such that they allow the active ingrédient to diffuse ont.

   tK

   -415
7. 7. The composition of claim 1, wherein each dispersed phase optionally comprises at least onc non-porous particulate minerai that acts as a diffusion barrier to slow the release of the active ingrédient.
8. 8. The composition of claim 1, wherein the polymer particles are thermoset.
9. 9. The composition of claim 1, wherein the polymer particles arc thermoplastic.
10. 10. The composition of claim 1, wherein the continuous phase (a) comprises water and a substantîally water-miscible, non-aqueous liquid.
11. 11. The composition of claim 10, wherein the substantîally water-miscible, nonaqueous liquid is selected from propylene carbonate, ethylene glycol, dicthylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylène glycol, hcxylcne glycol, polyethylene glycols having a molecular weight of up to about

    20 800, di(propylenc glycol) methyl ether acetate, propylene glycol diacetate, triethyI phosphate; ethyl lactate, gamma-butyrolactonc, propanol, tetrahydrofurfuryl alcohol, Nmethyl pyrrolidone, dimcthyl lactamide, and mixtures thereof.
12. 12. The composition of claim 1, wherein the continuous phase (a) comprises water

    25 and a watcr-solublc soluté.
13. 13. The composition of claim 12, wherein the water-solublc soluté is selected from an acid, a base, a sait, a sugar, a polysaccharide, a protein, an amîno acid, betaine and mixtures thereof.
14. 14. The composition of claim 2, wherein the continuous phase (a) further comprises at least onc agrochcmically active ingrédient and that active ingrédient is in the statc selected from a solution, an émulsion, a microemulsion, or a suspension ofmicrocapsulcs or fine particles.

    L
15. 15. The composition of claim I, wherein the continuous phase (a) further comprises one or more surfactants or dispersants.
16. 16. The composition of claim I, wherein the colloïdal solid comprises a particulate inorganic material distributed at the surface of the polymer particles.
17. 17. The composition of claim 2, wherein the colloïdal solid comprises an agrochcmically active ingrédient in fine particulate form and functional as a Pickcring stabilizer that is distributed at the surface of the polymer particles.

    !8. The composition of claim l, wherein each dispersed phase (b) optionally further comprises at least one non-cross-linkabîe mobile chemical selected from a surfactant, a polymer, a copolymer, an acid, a base, a natural or synthetic oil or alcohol, a substantially water-soluble compound and a substantially water-insoluble compound.
18. 19. The composition of claim l, wherein each dispersed solid phase (b) comprises a cured epoxy resin polymer.
19. 20. The composition of claim l, wherein each dispersed solid phase (b) comprises a cured phenolic resin polymer.
20. 21. The composition of claîm l, wherein each dispersed solid phase (b) comprises a cured polyuréthane polymer.
21. 22. The composition of claim I, wherein cach dispersed solid phase (b) comprises a cured polyurca resin polymer.
22. 23. The composition of claim I, wherein each dispersed solid phase (b) comprises a cured amînoplast resin polymer.
23. 24. The composition of claim I, wherein each dispersed solid phase (b) comprises a polyester or vinyl ester resin polymer.
24. 25. The composition of claim I, wherein each dispersed solid phase (b) comprises a thcrmoplastic polystyrène or polyacrylate polymer or biodégradable thcrmoplastic polymer.
25. 26. The composition of claim 19, wherein (b) comprises a curcd epoxy resin polymer matrix prepared by curing an epoxy resin selected from di-and polyepoxide monomers, prepolymers, biodégradable epoxy resins or blends thereof with a hardencr selected from primary and secondary amines and their adducts, cyanamide, dicyandiamide, polycarboxylic acids, anhydrides of polycarboxylîc acids, polyamines, polyaminoamides, polyadducts of amines and polyepoxides, polyols and mixtures thereof
26. 27. The composition of claim l, wherein each dispersed solid phase comprises polymer particles with mcan diameter between I and 200 microns.
27. 28. The composition of claim l, wherein the colloïdal solid comprises no more than about 80 wt% of the dispersed solid phase.
28. 29. A method of preventing or combating infestation of plant species by pests, or regulating plant growth by diluting an effective amount of concentratc composition according to claim 2 with an aqueous liquid carrier selected from water and liquid fertilizer, and applying the dilute composition to the plant species or locus thereof.
29. 30. A process for making an aqueous liquid dispersion conccntrate incorporating at least one agrochcmically active ingrédient comprising the steps of:

    a. dissolving or suspending at least one agrochcmically active ingrédient in a liquid curable, soïidifiablc or polymcrizablc resin optionally containing at least one non-cross16271

    -44Iinkablc mobile chemical, optionally containing a non-porous particulate minerai, and optionally containing a chemical curing agent;

    b. combining said solution or suspension with an aqueous liquid containing a colloïdal solid émulsion stabilizer and optionally a chemical curing agent and applying mcchanical agitation sufficicnt to form an émulsion of said solution or suspension; and

    c. effecting cure, solidification or polymcrization of the rcsin to producc an aqueous liquid dispersion of polymer particles which contain at least one agrochemically active ingrédient and a colloïdal solid distributed at the surface of the polymer particles .
30. 31. The process according to claim 30, wherein the polymerizable resin is selected from epoxy, polyisocyanatc, polyamine, aminoplast, phénol ic and polyester.
31. 32. The process according to claim 31, wherein the polymerizable rcsin îs a thermosetting epoxy resin.
32. 33. The process according to claim 32, wherein the epoxy resin comprises a diglycidyl ether of bisphcnol A, glyccrol, polypropylcncoxidc or rcsorcinol, or a mixture of two or more of these ethers.
33. 34. The process according to claim 32, wherein curing of the epoxy rcsin is accomplishcd using an amine hardener,
34. 35. The process according to claim 34, wherein curing i,s accomplishcd by using an amine hardener comprising a poly(oxypropylcnc)dianrtine.
35. 36. The process according to claim 30, where the colloïdal solid émulsion stabilizer is selected from carbon black, métal oxides, métal hydroxi des, métal carbonates, métal sulfates, polymers, silica and clays.
36. 37. The process according to claim 36, where the colloïdal solid émulsion stabîlizer is an agrochemically active ingrédient in finely dividcd form.
37. 38. A process for making an aqueous liquid dispersion concentratc incorporating at least one agrochemically active ingrédient comprising the steps of:

    a. dissolving or suspending at least one agrochemically active ingrédient in a solution of a thcrmoplastic polymer in a volatile solvent optionally containing a non-porous partîculatc minerai and optionally containing a non-cross-linkable mobile chemical;

    b. combining said solution or suspension with an aqueous iiquîd containing a colloïdal solid émulsion stabilizer and applying mcchanical agitation sufficient to form an émulsion of said solution or suspension; and

    c. applying heat to evaporate the volatile solvent to produce an aqueous liquid dispersion of polymer particles which contain at least one agrochemically active ingrédient and a colloïdal solid distributed at the surface ofthe polymer particles .
38. 39. A process for making an aqueous liquid dispersion concentratc incorporating at least one agrochemically active ingrédient comprising the steps of:

    a. dissolving or suspending at least one agrochemically active ingrédient in a melt of a thcrmoplastic polymer optionally containing a non-porous particulate minerai and optionally containing a non-cross-linkable mobile chemical;

    b. combining said solution or suspension with an aqueous liquid containing a colloïdal solid émulsion stabilizer and applying mcchanical agitation sufficient to form an cmulsion of said solution or suspension; and

    I

    c. cooling the émulsion to solidify the disperse phase and thereby producc an aqueous liquid dispersion of polymer partîcles that contain at least one agrochemically active ingrédient and a colloïdal solid distributed at the surface of the polymer partîcles ,
39. 40. The process according to claims 38 or 39, where the colloidal solid émulsion stabilizcr is selected from carbon black, meta! oxides, métal hydroxides, métal carbonates, metai sulfates, polymers, silica and clays.

    4L The process according to claim 38 or 39, where the colloidal solid émulsion stabilizcr is an agrochemically active ingrédient in fïncly divided form,
40. 42. The process according to claims 30, 38 or 39, where the colloidal solid émulsion stabilizcr may be surface modîfied isotropically or otherwise, in a way that allows it to react chcmically with a cross-linking agent that may comprise the polymerizable resin or another agent added through the continuous phase.
41. 43. The process according to claim 30, 38 or 39, wherein the continuous phase is water and the colloidal solid is a hydrophilic fumed silica.
42. 44. The process according to claim 30, 38 or 39, wherein the continuous phase comprises water and a substantially water-misciblc, non-aqucous liquid, and the colloidal solid is a hydrophilic fumed silica.
43. 45. The process according to claim 30, 38 or 39, wherein the continuous phase is a solution of xanthan polysaccharide in water and the colloidal solid is kaolin clay.
44. 46. A polymer particle comprising at least one entrapped agrochemically active ingrédient that is either homogencously on non-homogcneously distributed within such particle or is présent in the form of domains within such particle, and wherein the outsidc surface région of such particle comprises a colloidal solid material, and optionally comprising at least orte mobile non-cross-linkable chcmical.