BR9803712B1 - CONTROLLED RELEASE COMPOSITION TO PROVIDE AN AGRICULTURAL CHEMICAL PRODUCT FOR A PLANT, PROCESS TO PROVIDE A TRIZOLIC FUNGICIDE TO A PLANT AND PROCESS FOR PRODUCTION OF SUCH COMPOSITION. - Google Patents

Description

Report of the Invention Patent for "Controlled Release Composition to Provide a Product"

AGRICULTURAL CHEMISTRY TO A PLANT PROCESS TO PROVIDE

A Triazolic fungicide to a plant and process for the production of said composition ".

Background of the Invention This invention relates to compositions and processes for controlled release of agricultural chemicals. Most agricultural chemicals, such as biocides, chemical hybridizing agents or plant growth regulators, are applied to plants, seeds or soil at the beginning of the growing season and should remain effective throughout the growing season. plant, which should last for several months. However, chemicals can be degraded by chemical or biological processes and are removed by wind or water from the application site. As a result, it is necessary to apply high rates to maintain the desired effect over time or to apply chemicals repeatedly during the growing season.

However, high rates of some agricultural chemicals may be phytotoxic. Many fungicides, especially triazole fungicides, can also be very phytotoxic when applied in amounts that are necessary to provide adequate disease control.

Published patents and patent applications describing various controlled release formulations include US Patents 4,172,119, 4,915,947, 5,225,278, 5,277,979 and 5,725,869, European Patent Publications 0 004 758-A2, 0 018 119 A1, and 0 763 510-A1, and PCT application WO 88/08300.

There remains a need for controlled release formulations in which the agricultural chemical can be released to a plant throughout the growing season at rates that are agriculturally effective, reducing or eliminating phytotoxicity from the agricultural chemical to the plant or seeds. Preferably, these formulations may include an amount of an active compound that is close to the minimum amount required to achieve the desired effect in order to reduce environmental impacts and reduce costs.

Summary of the Invention Applicants have discovered controlled release formulations for agricultural chemicals comprising microparticles wherein one or more agricultural active compounds are dispersed or distributed in a polymer matrix. These controlled release formulations are safe when applied to seeds or plants even if they contain high levels of active compound that would be phytotoxic if applied to seeds or plants in standard rapid release formulations. Microparticles according to the present invention may release an active ingredient (s) at beneficial levels throughout the growth period of common crop plants (for example, for at least two to twelve months). weeks or more), and thus may reduce or eliminate the need for subsequent applications of the agricultural chemical. The release rate of agricultural chemicals, and the period in which effective amounts of these chemicals can be released, can be marked as desired. These controlled release compositions increase the period during which an agricultural chemical is effective, reduce the initial toxicity of the chemical to seeds or crop plants, increase the rate of compounds that can be used for agricultural applications, and decrease the environmental impact. of chemical treatment.

According to one aspect of the invention, controlled release compositions for releasing an agricultural chemical to a plant comprise microparticles having an average diameter of from about 0.2 microns to about 200 microns. The microparticles each comprise a polymer matrix and at least one agricultural chemical distributed throughout the matrix. The microparticles include about 1 to about 50 weight percent of the agricultural chemical and about 50% to about 99 weight percent of polymer matrix.

According to another aspect of the invention, these compositions include suspensions of microparticles in an aqueous medium, wettable powders, wettable granules, dry granules, and seed coatings, for example. According to at least some embodiments of the invention, the microparticles adhere to a surface of a seed or plant.

According to another aspect of the invention, these compositions include an amount of an agricultural chemical and release the agricultural chemical at a rate such that the composition releases an agriculturally active amount of agricultural chemical to the plant over a period of time. at least about two weeks to about twelve weeks, preferably throughout the plant growth period.

According to another aspect of the invention, these compositions reduce the phytotoxicity of agricultural chemical by at least twice (as compared to conventional quick release formulations of the chemical). For example, in the case of seed coating compositions according to the present invention, the composition may include an amount of agricultural chemical that would be substantially phytotoxic if applied to the seed surface as a rapid release formulation of the agricultural chemical. .

According to another aspect of the invention, the agricultural chemical is a biocide (e.g. a triazolic fungicide such as cyproconazole, epoxiconazole and tebuconazole), a plant growth regulator, a chemical hybridizing agent, a plant nutrient, or combinations thereof.

According to another aspect of the invention the polymer is selected from the group consisting of poly (methyl methacrylate), poly (lactic acid), poly (lactic acid-glycolic acid) copolymers, acetate butyrate cellulose, poly (styrene), hydroxybutyric acid-hydroxyvaleric acid copolymers, styrene maleic anhydride copolymers, poly (methylvinyl ether-maleic acid), poly (caprolactone), poly (n-amyl methacrylate), wood rosin, polyanhydrides, polyorthoesters, poly (cyanoacrylates), poly (dioxanone), ethyl cellulose, polymers of ethyl vinyl acetate, poly (ethylene glycol), poly (vinyl pyrrolidone), mono-, di- and acetylated triglycerides, poly (phosphazene) chlorinated natural rubber, vinyl polymers, polyvinyl chloride, hydroxyalkylcelluloses, polybutadiene, polyurethane, vinylidene chloride polymers, styrene butadiene copolymers, styrene acrylic copolymers, alkylvinyl ester polymers, phthalates d and cellulose acetate, ethyl vinyl phthalates, cellulose triacetate, polyanhydrides, polyglutamates, polyhydroxy butyrates, polyvinyl acetate, vinyl ethyl acetate copolymers, vinyl pyrrolidone vinyl acetate copolymers, acrylic polymers, acrylate polymers alkyl, aryl acrylate polymers, aryl methacrylate polymers, poly (caprolactams), epoxy resins, polyamine epoxy resins, polyamides, polyvinyl alcohol polymers, polyhalic resins, phenolic resins, abietic acid resins, silicones, polyesters, and copolymers and combinations of the same.

According to another aspect of the invention, as the compositions also include a dispersing agent, including methyl cellulose, polyvinyl alcohol, lecithin, and combinations thereof.

According to another aspect of the invention, seeds are provided which comprise these compositions, for example seed coatings.

According to another aspect of the invention, processes are provided for releasing an agricultural chemical to a plant comprising providing the plant with a composition as discussed above, for example by applying the composition to the soil, applying the composition to the foliage. and seed coating prior to seed germination to produce the plant. When applied to soil or foliage, for example, the composition may be applied, for example, in an amount such that about 1 g to about 10 kg of agricultural chemical is applied per hectare. When applied as a seed coat, the composition may be applied in an amount such that from about 1 gram to about 500 grams of agricultural chemical is applied to 100 kg of seed.

According to another aspect of the invention, the processes are provided to produce the compositions described above. These processes include the steps of: (a) dissolving at least one agricultural chemical and polymer in an organic solvent to form a hydrophobic solution, (b) mixing the hydrophobic solution and an aqueous medium at a shear rate. for a period of time sufficient to produce an emulsion having hydrophobic droplets dispersed in the aqueous medium; and (c) evaporating the organic solvent from the emulsion to produce a plurality of microparticles having an average diameter of from about 0.2 microns to about 200 microns and said at least one agricultural chemical distributed throughout. the polymer matrix. According to some embodiments of the invention, these processes include one or more other steps of: dissolving the dispersing agent in an aqueous solution to produce the hydrophilic solution, and suspending the microparticles in an aqueous medium.

Other aspects of the present invention will be apparent to those skilled in the art when studying this description and the appended claims.

Brief Description of the Drawings Figure 1 shows the effect of matrix microparticle formulations of Example 7 and Alto® 005LS when used as wheat seed treatments at various rates (g cyproconazole per 100 kg of seed) expressed as the height. of wheat germinating 11 days after planting (DBH) as a percentage of height of untreated controls. Figure 2 shows the effect of matrix microparticle formulations of Example 8 and Alto® 005LS when used as wheat seed treatments at various rates (g cyproconazole per 100 kg of seed) expressed as wheat germinating height. 10 DBH as a percentage of height of untreated controls. Figure 3 shows the effect of matrix microparticle formulations of Example 9 and Alto® 005LS when used as wheat seed treatments at various rates (g cyproconazole per 100 kg of seed) expressed as the height of wheat germinating at. 10 DBH as a percentage of height of untreated controls. Figure 4 shows the effect of Example 10 and Alto® 005LS matrix microparticle formulations when used as seed treatments on wheat at various rates (g cyproconazole per 100 kg of seed) expressed as the height of wheat germinating at 11 DAP. as a percentage of height of untreated controls.

Figures 5 and 6 show the effect of a matrix microparticle formulation of example 11, NBP5881012C, and Alto® 005LS when used as a multi-rate wheat seed treatment (g cyproconazole per 100 kg seed) expressed as wheat height germinating at 10 dbp (Figure 5) or 9 dbp (figure 6) as a percentage of untreated control height.

Figure 7 shows the effect of matrix microparticle formulations of example 12, NBP 5881012C, NBP 5890983A, and Alto® 005LS when used as wheat seed treatments at various rates (g cypro-conazole per 100 kg seed). expressed as the height of wheat germinating at 9 DAP.

Figure 8 shows the effect of matrix microparticle formulations of Example 12, NBP 5890983A, NBP 5890983B, and Alto® 005LS when used as wheat seed treatments at various rates (g cyproconazole per 100 kg seed). expressed as the height of wheat germinating as a percentage of the height of untreated controls at 10 DAP.

Figure 9 shows the effect of matrix microparticle formulations of Example 13, NBP 5890983C and NBP 5890983D, and Alto® 005LS when used as wheat seed treatments at various rates (g cyproconazole per 100 kg seed) expressed as the height. germinating as the percentage of untreated controls at 10 DAP.

Figure 10 shows the effect of matrix microparticle formulation of Example 13, NBP 5890977D, and Alto® 005LS when used as wheat seed treatments at various rates (g cyproconazole per 100 kg seed) expressed as the germinating wheat height. as a height percentage of untreated controls at 10 DAP.

Figure 11 shows the effect of matrix microparticle formulations of example 14 and Alto® 005LS when used as wheat seed treatments at various rates (g cyproconazole per 100 kg of seed) expressed as the height of wheat germinating as a percentage of height of untreated controls at 10 DAP.

Figure 12 shows the effect of matrix microparticle formulations of Example 15 and Alto® 005LS when used as wheat seed treatments at various rates (g cyproconazole per 100 kg seed) expressed as the height of wheat germinating as a percentage of height of untreated controls at 10 DAP.

Figure 13 shows the effect of matrix microparticle formulations of example 16 and Alto® 005LS when used as wheat seed treatments at various rates (g cyproconazole per 100 kg of seed) expressed as the height of wheat germinating as a percentage of height of untreated controls at 10 DAP.

Figure 14 shows the effect of matrix microparticle formulations of examples 17 and 18, MON 38410 and MON 38411, respectively, and Raxil ® when used as wheat seed treatments at various rates (g epoxiconazole per 100 kg seed), expressed as as tribe height germinating with a percentage of untreated controls height at 11 DAP.

Figure 15 shows the effect of matrix microparticle formulations of examples 19 and 20, MON 24530, and MON 24540, respectively and Opus® when used as seed treatments on wheat at various rates (g tebuconazole per 100 kg seed), expressed as as tribe height germinating with a percentage of untreated controls height at 11 DAP.

Figure 16 shows the effect of matrix microparticle formulations of Example 21 at an application rate of 16 g cyproconazole per 100 kg of seed and Alto® 005LS when used as wheat seed treatments, expressed as a percentage height of untreated controls. -treated at 8 DAP.

Figure 17 shows the effect of NBP 6273923C ["fenpropimorf (matrix)"] and Corbel ® (fenpropimorf) when used as seed treatments on wheat at various application rates, expressed as a percentage height of untreated controls in 10 days after planting.

Figure 18 shows the effect of NBP 6248096B ["MON 46100 (Matrix)"] and unformulated MON 46100 ["MON 46100 (Acetone / H20):"] when used as wheat seed treatments at varying rates. application, expressed as the percentage of height of untreated controls within 10 days after planting.

Figure 19 shows the effects of foliar applications of MON 38412, MON 24555, Raxil®, and Opus ® on soybean plant vigor five days after treatment (on a scale of 1-5, untreated control plants = 5). .

Figure 20 shows the effects of MON 24555, Opus ®, MON 38412, and Raxil ® when used as soybean seed treatments at various application rates, expressed as a percentage of untreated controls 9 days after planting.

Figure 21 shows efficacy against wheat powdery mildew of seed treatments employing MON 38414 (30, 45 and 60 g, tebuconazole / 100 kg seed) and Raxil ® (30 g tebuconazole / 100 kg seed (42 days after planting) ).

Figure 22 shows the efficacy against powdery wheat downy mildew of seed treatment employing MON 38414 and MON 38416 (45 and 60 g active compound / 100 kg seed), and Raxil ® (30 g tebuconazole / 100 kg seed) (44 days after planting).

Figure 23 shows control of brown wheat rust (second leaf) by seed coatings comprising matrix microparticle formulations 5932839A, MON 24682, MON 24647 (each at 32 g cyproconazole per 100 kg seed) and Alto® 005LS ( 1 g cyproconazole per 100 kg of seed). Plants were inoculated 20 DAP. Disease severity in untreated controls was 61.3%.

DETAILED DESCRIPTION OF THE INVENTION The matrix microparticle formulations of this invention are usable in agriculture for a variety of purposes, including, for example, controlling seed and soil source pathogens and pests, as well as pests affecting above ground portions of plants (stems, foliage, flowers, fruits) for nutrient release, chemical hybridizing agents and plant growth regulators, etc. It will also be noted that these formulations have various non-agricultural uses, such as the release of pharmaceuticals to humans or animals for therapeutic or prophylactic purposes, for the controlled release of chemicals in water treatment or conditioning, aquaculture, etc.

Controlled release formulations according to the present invention substantially reduce the phytotoxicity of an agricultural chemical to a seed or plant compared to a standard rapid release formulation of the chemical (i.e. one having a lipid rate of about which is substantially similar to that of the unformulated product). That is, these controlled release formulations increase the safety of (or make safe) the agricultural chemical. Thus, for a given level of phytotoxicity, more of the product may be applied to a seed or plant in the controlled release formulation form according to the present invention than in standard rapid release formulation. Preferably, a controlled release formulation according to the present invention makes a particular product safe at least twice more preferably at least five times, even more preferably at least ten times, and most preferably at least twice. twenty times or more. In fact, we have applied more than 100 times the amount of standard formulations of some phytotoxic chemicals with only minimal damage to plants. As shown in the examples below, the safety of various agricultural products with triazole fungicides allows their use as seed treatments at levels that otherwise prevent or retard germination or stop the growth of seed-germinating plants, increasing them. effectiveness of these fungicides against various pathogens and pests.

The matrix microparticles according to the invention may be used according to any conventional formulation, including but not limited to: suspending matrix microparticles in an aqueous medium (e.g., water), wettable powders, wettable granules (dry flowable) and dried granules. If formulated as a slurry or slurry, a formulation suitable for storage and dispatch, the concentration of active compound in the formulation is preferably about 0.5 to 50 weight percent (w / w), preferably about 5% by weight. about 40%. This concentration can be adjusted even based on the relative proportion of matrix microparticles and carrier medium (solid or liquid).

Matrix Microparticles - The term "matrix" is defined as a surrounding material in which other material is trapped, embedded, dissolved or dispersed.

The microparticles of the present invention include a matrix that includes one or more polymers and one or more active compounds, which are distributed throughout the matrix. The microparticles may also include one or more inactive ingredients or additives (such as dispersants for example). The microparticles of the present invention differ from "microcapsules" in which the polymeric envelope surrounds a liquid or solid core containing an active compound. In at least one embodiment of the microparticles of the present invention, the end product appears in solid fracture electron micrographs, generally solid appearing spherical particles, indicating that the active ingredient (s) is ( are) molecularly distributed or dispersed substantially and evenly through the matrix material. However, it is possible in at least some embodiments that an active compound may be macromolecularly distributed in the matrix, that is, that a plurality of particles of the active compound are dispersed in the matrix. The agriculturally active active compound comprises at least 1.0 to 50 weight percent preferably at least 15 weight percent of microparticles of the present invention. The matrix constitutes from about 50 to about 99 weight percent of microparticles, preferably about 50 to about 90%. It is more economical if the microparticle comprises a high proportion of active compound. If the ratio of entrapped matrix to active compound components is too large, the release rate of entrapped material is generally too slow to be effective and the amount of active compound in the formulation is reduced, increasing the cost of an effective amount of end product. . If the matrix component ratio of entrapped material component is too small, the release rate will generally be very high, leading to phytotoxicity and reducing the effectiveness of the active compound. As the concentration of active compound increases in the microparticle, release rates also generally increase. The average matrix component weight as a percentage of the total matrix microparticle weight (combined matrix weight, active compound and any inactive ingredient in the polymer matrix) can be estimated from the amount of ingredients in the composition. to prepare the product, assuming the ingredients are mixed thoroughly and evenly.

The microparticle preparations of the present invention preferably have average particle sizes in the range of from about 0.2 microns to about 200 microns in diameter, more preferably from about 1 microns to about 50 microns in diameter, even more preferably. about 3 microns to about 50 microns in diameter. Smaller average particle sizes generally have a higher release rate and active compound area coverage, along with greater activity and phytotoxicity of the active compound. Conversely, larger average microparticle sizes are associated with lower area coverage and reduced phytotoxicity, but also lower activity and reduced phytotoxicity. In addition, the small microparticle size of the present invention allows these microparticles to be taken by a plant along with soil water and to be transported through the plant, effecting systemic release of the active compounds. The size of the matrix microparticles is controlled during the entrapment process by employing mixing, stirring or stirring media (including homogenizers and sonicators) at an appropriate rate of velocity to form droplets of the entrapped ingredients. The particle size of the inventive matrix microparticles is measured by using a microscope with a calibrated reticulum and visually assessing the average particle size. Alternatively, size can be determined by electronic means using a Coulter LS Counter or by laser light scattering. The microscopy determination is usually within + 5 microns of the size measured by the Coulter Counter. From the microparticle size distribution, di6, dso and d84 values were determined and plotted on a log probability plot. The value d-16 represents the size (diameter in microns), where 16 weight percent of the capsules in the sample are equal to or larger than di6, d50 represents the size where 50 weight percent of the capsules are equal to or greater than d50, and d84 represents the size at which 84 percent by weight of the microparticles are equal to or larger than ds. 4 The matrix microparticles of the present invention preferably adhere to the surface of seeds and plants. Without being bound by theory, the matrix microparticles are believed to become entrapped in micro-hairs or hairs on the seed or plant surfaces. The adhesion of microparticles to seeds and plants can be improved by the use of conventional "gripping agents" or other compounds that have been used to apply various coatings to the seeds.

Microparticles may affect the mobility of an active compound in soil, because the binding of matrix material to soil particles may be substantially different than the binding of the active compound itself.

As a result, depending on the matrix materials selected, the compositions according to the present invention may increase the effectiveness of agricultural chemicals that would be rendered less effective due to their tight binding to soil particles.

Also encompassed by the present invention are microparticles according to the present invention which are encapsulated or coated using conventional processes and materials to provide other active compound release control, add additional active or inactive compounds or impart desirable properties. to the resulting product.

Polymers - The term "polymer" or "polymeric material" as used herein is taken to mean either a single polymer or copolymer or a combination of different polymers or copolymers.

A matrix material is selected such that the release rate of the active compound provides an "agriculturally effective amount" of the active compound to a seed or plant, that is, an amount of active compound that is effective to obtain adequate crop protection or other agricultural activities characteristically associated with the agricultural chemical. Thus, for an biocide an agriculturally effective amount is an amount that is sufficient to provide commercially acceptable control of a pathogen or pest, for a plant growth regulator, an amount that is sufficient to substantially alter plant growth or development in a plant. characteristic of the plant growth regulator, for a nutrient, an amount that is sufficient to provide at least the minimum amount of nutrient required for normal plant growth and development, etc. Preferably, the active compound is released at a rate that does not cause "substantial phytotoxicity" that is, does not reduce plant growth or vigor to commercially unacceptable levels or produce other types of unacceptable damage to the plant. Preferably, the active compound is released at beneficial levels throughout the germination, emergence, and / or later developmental stages of the crop or plant, and more preferably throughout the plant growth period. The active compound may be released by matrix diffusion or matrix degradation or dissolution in a soil, plant or leaf environment. In addition, the polymer and breakage products thereof, if present, should not interfere with the effectiveness of the active compound (or other components, such as the dispersing agent), or be substantially phytotoxic to the seed, seedling or plant. .

Examples of polymers suitable for the practice of this invention include, but are not limited to, the following non-exhaustive list of polymer (and copolymers and mixtures thereof): poly (methyl methacrylate) poly (lactic acid) [Cronopols 50, 95, and 100] and copolymers such as poly (lactic acid-glycolic acid) copolymers [Lactel BP-400] and combinations with polystyrene, for example poly (styrene) cellulose acetate butyrate hydroxyvaleric acid copolymers [Biopol D400G] anhydride copolymers maleic styrene [SMA 1440 A Resin, Sartomer Co.] poly (methylvinyl ether maleic acid) poly (caprolactone) poly (n-amyl methacrylate) wood rosin polyanhydrides, for example poly (sebacic anhydride), poly (valeric anhydride) ), poly (trimethylene carbonate), etc., and copolymers such as poly (carboxyphenoxypropane-sebacic acid), poly (fumaric acid-sebacic acid), etc. polyorthoesters poly (cyano acrylates) poly (dioxanone) ethyl cellulose ethyl vinyl acetate polymers and copolymers poly (ethylene glycol) poly (vinylpyrrolidone) mono-, di- and acetylated triglycerides poly (phosphaene) chlorinated natural rubber vinyl chloride polymers and copolymers polyvinyl hydroxy alkyl celluloses polybutadiene polyurethane vinylidene chloride polymers and copolymers styrene butadiene copolymers styrene acrylic copolymers vinyl acetate polymers and copolymers (for example, ethylene vinyl copolymers (Vinumuls) and vinyl acetate - vinylpyrrolidone polymers and copolymers alkyl vinyl ether cellulose acetate phthalates ethyl vinyl phthalates cellulose triacetate polyglutamates polyhydroxy butyrates acrylic polymers (Rhoplexes) alkyl acrylate polymers polymers and copolymers polyacrylate acrylate polymers and copolymers (caprolactams) (ie containing nitrogen counterparts for caprolactones) epoxy / polyamine epoxy / polyamides polyvinyl alcohol polymers and copolymers polyester silicones (for oil-based approaches including alkyds) phenolic (polymers and copolymers with drying oils) Preferred polymers include: poly (methyl methacrylate) poly (lactic acid) [Cronopols 50, 95, and 100] and combinations with polystyrene poly (lactic acid-glycolic acid) copolymers [Lactel BP-400] cellulose acetate butyrate poly (styrene ) Poly (methyl methacrylate) or poly (maleic styrene anhydride copolymer) is currently preferred for use with triazole fungicides such as tebuconazole, cyproconazole, and epoxiconazole, for example.

It will also be contemplated that some resins such as polyalkyl resins, phenolic resins, abietic acid and epoxy resins should also be suitable for the practice of this invention. Also encompassed by the present invention are systems loaded with polymers and copolymers, that is, using calcium carbonate, silica, clay, etc.

Active compounds. The microparticles of the present invention may include a single agriculturally active ingredient entrapped in polymeric matrix or multiple active compound having similar or different activities (eg different biocides such as fungicides and insecticides). The active compounds include, but are not limited to any of a number of conventional biocides, including fungicides (e.g., triazoles, imidazoles, methoxycrylates, morpholine series fungicides such as fenpropimorf, etc.), herbicides (e.g. glyphosate, phosphinothricin, Trialate, Alachlor, etc.), insecticides (eg organophosphorus compounds, imidacloprid, pyrethroids, etc.), nematicides (eg Tribute), ascaricides, molluscicides, nematicides, rodenticides, bactericides and termiticides, agents chemical hybridizers (eg Genesis), herbicidal safety agents, inducers or chemical elicitors (eg protein activators), plant growth regulators (eg auxins, cytokines, gibberellins, etc.) , elicitors, or nutrients such as fertilizers, minerals, etc.).

Suitable triazole fungicides for the practice of this invention are exemplified by cyproconazole, epoxiconazole, triticonazole, and tebuconazole with cyproconazole being preferred. A complete discussion of the properties for each fungicide can be found in U.S. Patent No. 4,664,696, EPA 196038, and U.S. Patent 4,723,984 respectively.

Representative fungicides, herbicides, insecticides, and growth regulators that are useful with the present invention are listed below: _________________________Fungicides_______________________ Benomila Fludioxonil Benzothiadiazoles Flutolanil Captan Fosetil-AI

Chlorothalonil kresoxim-Methyl Cyproconazole Cyprodinil Mancozeb Metalaxyl Epoxiconazole Tebuconazole Prochloraz Fenarimol Triticonazole fenpropimorph Vinclozolin herbicides 2,4-dichlorophenoxyacetic acid Isoxaflutole Alachlor Acetochlor Lactofen Mecoprop Atrazine metolachlor metribuzin Bensulfeto Bromacil Norflurazon Bromoxynil Butachlor oxadiazon propachlor propanil chlorsulfuron Clomazone Quinclorac Dicamba sethoxydim dinoseb Diuron Sulcotrione sulfentrazone Doclofop methyl Sulfossulfuron flumetsulam Thiobencarb flumiclorac pentyl Triallate Glyphosate triclopyr Halossulfuron Trifluralin Imazaquin Vernolate Insecticides / Nematicides Aldicarb Fenvalerate azinphos-methyl Imidacloprid Carbarila Lindanc Carbofuran Malathion Chlorpyrifos methyl Parathion Cyfluthrin Monocrotophos Diazinon Oftanol Dicofol Oxamila Disulfoton Parathion endosulfan propoxur Fenamiphos Pyrethrins Growth Regulators 6-benzyladenine Endotall alpha-Naftiláctico Etepon Ancimidol Gibberellic Acid Clorprofam Hydrazine Male Daminozide Paclobutrazol _____________Chemical Hybridizing Agents _______________ Clofenset (K + salt) In addition to the active compounds, microparticles may also include one or more inactive ingredients such as solvents, dispersants, adjuvants, or plasticizers, and may be formulated as suspensions, granules, coatings. seed, etc. together with other active or inactive compounds.

Release of active ingredient (s) from microparticles: The microparticles according to the present invention release an agriculturally active compound in a diffusion-controlled mode (for example in the case of poly (methyl methacrylate) or poly (maleic styrene anhydride) or by matrix disintegration or dissolution (eg in the case of polylactic acid polymers), depending on the matrix polymer employed. Release rates also vary with the size of microparticles (affecting surface area / volume ratio) The matrix material is selected to have properties that lead to the appropriate release and action of the agriculturally active compound in space and time.The formulations can also be prepared so that the active compound varies in concentration of the active compound. external surface of the matrix microparticle as its core, providing "programmed" rates and active release levels over the duration of germination. the seeds and subsequent growth periods. The release rate of an active compound from a microparticle according to the present invention depends on the polymer, particle size, the active compound charge, and the dispersing agent used, if present. The manner in which an active compound is released from a microparticle depends on whether the charged material is suspended or dissolved in the matrix. The steps involved when the active compound is dissolved in the matrix material are: diffusion of the active compound on the matrix surface; division of active compound between the matrix and the eluting medium or medium (eg soil water, seed coating, or leaf surface), and transport off the surface of the microparticle. In addition, if the active compound is dispersed (such as microparticulate macromolecular particles), the active compound must dissolve in the matrix material before surface diffusion.

Another mode of release of the active compound is by biodegradation or erosion of the matrix material, the rate of which is influenced by the hydrophobicity or hydrophilicity of the polymer and the microparticle morphology, for example.

In addition, the active compound may be released by swelling of the polymer matrix after soaking a liquid such as water. In controlled diffusion systems, the matrix is considered to be unaffected by growth, but in controlled swelling systems, the polymer matrix undergoes a transition from a glassy state to a gel state upon interaction with the penetrating solvent. . The release rate is determined by the glass-to-gel transition process.

Another factor that affects the release rate is osmotic pressure, which can be created within the microparticle if the active compound or polymer has affinity for water. The active compound is released when osmotic pressure exceeds the maximum force that the microparticle matrix can tolerate.

Mathematical models for these release mechanisms are described in U. Pothakamury and G. Barbosa-Canovas, Trends in Food Science & Technology 6: 397-406, 1995, and R. Langer and N. Peppas, JMS-Rev.

Macromol. Chem. Phys. C (23): 61-126, 1983.

Formulations including microparticles - Conventional inert or inactive ingredients may be incorporated into the matrix microparticles or in various media, such as in aqueous medium used to produce suspensions and other matrix microparticle formulations according to the present invention. These inactive ingredients include but are not limited to: adhesives, dispersing agents such as methylcellulose (Methocel® A15LV or Methocel® A15C, for example serve as combined dispersing / adhesion agents for use in seed treatments), polyvinyl alcohol (eg Elvanol ® 51-05), lecithin (eg Yelkinol ® P, and polymeric dispersants (eg PVP / VA S-630), thickeners (eg clay thickeners such as Van Gel ® B to improve viscosity and reduce particle suspension settling), emulsion stabilizers, surfactants, antifreeze compounds (eg urea), colorants, colorants, etc.

Any conventional inert or active material may be used for microparticle seed coating in accordance with the present invention as conventional film coating materials including but not limited to water based film coating materials such as Sepiret and Opaque The formulated product, when used as a suspension in an aqueous vehicle, preferably comprises a dispersing agent to allow the formation of a relatively uniform or homogeneous mixture. The dispersing agent preferably also provides a degree of "stickiness" or stickiness in the microparticle formulation so that the formulation attaches to the treated seeds or other leaf surfaces. Suitable dispersing agents include, but are not limited to, 0.25-1.0% aqueous polyvinyl alcohol such as Elvanol® 51-05 (DuPont) and Methocel® A15LV.

Processes for producing matrix microparticles. The matrix microparticles of the present invention may be produced by any process that results in a polymer matrix having active compounds substantially uniformly distributed therein, including but not limited to solvent evaporation, solvent division, hot melt microencapsulation, and spray drying.

A preferred process for entrapping the agriculturally active ingredient according to the present invention includes the following steps: (A) preparing a hydrophobic solution ("oil phase) including an active compound and a polymer in an organic solvent, (B) preparation of a hydrophilic solution ("aqueous phase") by dissolving a dispersing agent in water (or an aqueous or alcoholic solution) (C) forming an emulsion by combining the hydrophobic solution with the hydrophilic solution with stirring, homogenization (D) stirring the emulsion formed in (C) until all the organic solvent of (A) has evaporated, the organic solvent may also be removed under reduced pressure using a rotary evaporator, and (E ) optionally isolating the matrix microparticles by letting the evaporated emulsion formed in (D) settle, decanting the supernatant liquid from the matrix microparticles, then washing, filtering and drying. The microparticles may be resuspended in an aqueous carrier system comprising water and for example a dispersing, coloring or coloring agent, etc. or the microparticles may be used without isolation.

Specifically, the matrix microparticle entrapment process is performed by dissolving the agriculturally active compound and the polymer in a sufficient amount of organic solvent to form the hydrophobic solution. This dissolution is carried out at room temperature or at temperatures no higher than 50 ° C with mechanical stirring. For microencapsulation of the active compounds according to this general process, the active compound is preferably soluble in the hydrophobic phase rather than the hydrophilic phase, and is preferably substantially insoluble in the aqueous phase (by substantially insoluble means a solubility of less than 1 percent by weight). weight in water at 25 ° C). A dispersing agent is then dissolved in deionized water to form the hydrophilic solution. This dissolution is performed at room temperature with mechanical stirring. The hydrophobic solution is then poured into the hydrophilic solution while stirring, homogenizing, or sound-treating the hydrophilic solution vigorously to form an emulsion, or by any other process conventionally used in the emulsification technique. The emulsion consists of hydrophobic solution micro-droplets that are uniformly dispersed and suspended in the hydrophilic solution. The droplet size and final size of the matrix microparticle are controlled by shear rate and degree of agitation, temperature, volumetric ratio of dispersed hydrophobic phase to continuous aqueous phase, and the type of dispersing agent used, if present. Stirring of the emulsion is continued until all organic solvent has evaporated. Once the organic solvent has evaporated, the supernatant liquid is decanted and the matrix microparticles are washed, filtered and dried or used, preferably as such.

In the process given above, the organic solvent used to prepare the hydrophobic solution should be suitable for co-dissolving the required amounts of the active and polymer to form a hydrophobic (water immiscible) solution. The organic solvent should not otherwise interact with or alter the intended functions of the active or polymer in the prepared matrix microparticles. The organic solvent must also have adequate volatility at room temperature (boiling point sufficiently low at ambient pressures) in order to evaporate at a reasonable rate from the emulsion. Methylene chloride is an example of an organic solvent suitable for the practice of the invention. Other suitable organic solvents include, but are not limited to ethyl acetate, chloroform, and carbon tetrachloride. The amount of organic solvent used in forming the hydrophobic solution is in the range of about two to about eight times and preferably about three times the weight of the polymer (or the combined weight of the polymer and the active).

In general, system pH adjustment is not required during matrix microparticle processing to achieve satisfactory performance and trapped material production. The presently preferred process for producing matrix microparticles of the present invention uses solvent evaporation. In summary, the solvent evaporation technique involves mixing a hydrophobic liquid medium and a hydrophilic liquid medium to produce an emulsion. Emulsions may be made with a hydrophobic phase in a hydrophilic phase or a hydrophilic phase in a hydrophobic phase, the former is currently preferred. In addition, it is preferred to produce an emulsion in which the volume of the hydrophilic phase is in significant excess of the volume of the hydrophobic phase. An active compound is added which preferably dissolves in the hydrophobic phase, and preferably is substantially insoluble in the hydrophilic phase. The shear rate and the time period for mixing the hydrophobic and hydrophilic phases are selected to produce uniformly dispersed hydrophobic droplets having average diameters in the range of about 0.2 to 200 microns, preferably about 1 microns. about 50 microns. The solvent is then evaporated from the hydrophobic phase producing matrix microparticles of the present invention.

In the solvent division technique (R. Langer et al, Polymer, 31: 547-555, 1990, Kirk Othmer Encyclopedia of Chemical Technology, 4, ed, vol.16 (Curt Thies), an active compound is dissolved or dispersed. In a volatile organic solvent, the resulting solution is suspended as a fine dispersion in an organic oil in which the organic solvent is extracted to produce microparticles. This technique can be performed at room temperature and does not require water. The polymer is dissolved in methylene chloride, the required amount of active compound (eg fungicide) is added, and the mixture is suspended in silicone oil containing a nonionic emulsifier such as Span 85 and additional methylene chloride. Add the polymer solution to the silicone oil, petroleum ether is added and the mixture is stirred until the matrix microparticles have hardened.The microparticles may be removed by filtration or centrifugation. washed with petroleum ether and dried under vacuum.

In hot melt microencapsulation (E. Mathiowitz and R.

Langer, J. Contr. King. 5: 13-22 1987, Microcapsules and Nanoparticules in Medicine and Pharmacy, ed. M. Donbrow, CRC Press, 1992, p. 105-107), a polymer melt is mixed with the active compound which may be suspended or dissolved therein. The resulting mixture is suspended in a non-miscible solvent (eg silicone oil or olive oil), which is heated to about 5 ° C above the melting point of the polymer while stirring continuously. After an emulsion is formed and stabilized, it is cooled until the microparticles have solidified. After cooling, the microparticles are washed by decantation with petroleum ether to produce a free-flowing powder. In general, the resulting microparticles are smaller than about 50 microns in diameter.

Application of Matrix Microparticles to Soil, Seed or Plant: Controlled release formulations according to the present invention may be applied to soil where they are released and eventually affect a target pest either directly or indirectly, for example by first be taken by the plant, which part is ingested by the pest.

Microparticle formulations may be applied by any conventional method, including but not limited to: (1) injecting a formulation (for example an aqueous microparticle suspension) directly into the soil around the seeds or in the root zone under development (eg injection at a depth of 2 cm and within a radius of 3 cm from the crown of the plant), (2) application as a drain into the soil (eg at the point where the soil is at field capacity), (3) application as a foliar spray preferably in a volume sufficient to fully moisten the foliage, and (4) application directly to the seeds as a seed coat. Release of the active compound from the microparticles provides a desired biological effect in the application zone or upon absorption of the active compound by the plant.

The matrix microparticles and formulations thereof can be applied to the seed using any standard seed treatment methodology and coating material, for example by mechanical application (eg using a Hege 11 liquid seed coater), mixed with - in a container (eg a bottle or bag), etc.

The matrix microparticles of the present invention may be applied in combination with other active compounds which are provided for fast or slow release formulations. The slow release matrix microparticles of the present invention may also be applied together with a fast release formulation of the same or different active compounds (or with microparticles comprising the same active compounds) in order to obtain for example an application regimen. chemistry with a high initial release rate followed by a slower release rate over a longer period of time.

EXAMPLES

Example 1 3.72 g of cyproconazole (96.3% purity; Sandoz Agro, Ltd., Basel, Switzerland) and 14.3 g of polylactic acid (Chronopol® 95; Chronopol, Golden, CO) were dissolved in 156 g. of methylene chloride (Burdick &

Jackson, Miskegon, M1) in a shaking glass bottle to produce a hydrophobic solution. 7.5 g of polyvinyl alcohol (Elvanol® 51 - 05; Dupont, Wilmington, DE) was dissolved with stirring in deionized water to yield 1500 g of hydrophilic solution. The hydrophobic solution was added to a hydrophilic solution and the mixture was vigorously stirred to produce an emulsion. The stirring continued for an hour. Microscopic examination of the appearance and size of oil droplets in the emulsion showed that the average oil droplet size was in the range 30 - 50 micrometres (micron, μ). The emulsion was then transferred to a two liter round bottom flask (L) and fixed to a spinner to remove methylene chloride at reduced pressure. The residue from the final methylene chloride was removed by heating the flask in a hot water bath at 40 ° C while in the vaporizer. The resulting microparticle suspension was filtered on a Buechner funnel to produce a filter cake, which was washed with three portions of deionized water to remove the last traces of the aqueous filtrate. The filter cake was then air dried by spreading the product placed on a clean sheet of paper.

An aqueous carrier solution was prepared by dissolving urea (Fischer Scientific, Pittsburg, PA) and Methocel® A15LV (Dow Chemical Co., Midland, M1) in stirring water. Urea was added as an antifreeze and Methocel® A15LV as a combined dispersant and non-phytotoxic sticking agent for use in seed treatments. (A clay thickener such as Van Gel® B [R.T. Vanderbilt Co., Inc., Norwalk, CT) is optionally added to an aqueous carrier solution to improve viscosity and reduce settlement. The dried microcapsules were shaken into an aqueous carrier solution to produce a homogeneous suspension. The composition of the final formulation (NBP 5881024C) is shown below.

Example 2 1.56 g of cyproconazole (96.3% purity) and 13.44 g of cellulose acetate butyrate polymer (Sigma Chemical Co., St. Louis, MO) were dissolved in 82.22 g of methylene in a shaking glass bottle to produce a hydrophobic solution. 1.00 g Methocel® A15LV and 20 g urea were dissolved in 64 g deionized water to prepare 85 g hydrophilic solution. The hydrophobic solution was added to a stirring hydrophilic solution to produce an emulsion. The stirring emulsion was added for 5 minutes to equilibrate. To further reduce particle size, the emulsion was sound-treated for 5.5 minutes with a sonic breaker (Model 550, Fischer Scientific, Pittsburgh, PA) using a variable power range. To cool, an ice bath was provided to keep the temperature below 30 ° C. Microscope examination showed mainly particles in the 4-5 micron range. The emulsion was transferred to a spinner and the methylene chloride distributed as described in Example 1. The resulting product was passed through a No. 325 mesh sieve to remove foreign particles and tested for particle size, density. (at room temperature), and% active compound.

The following are the properties of matrix particles (NBP 5932858): NBP5932858 - Properties Example 3 Following the general procedure of Example 2, matrix microparticle suspensions having the compositions given below were produced. For NBP 5932866, methylene chloride was evaporated with stirring at atmospheric pressure. For NBP 5932869, NBP 5932889A, NBP 5932889B and NBP 5932893, methylene chloride was evaporated with a rotary vapors under reduced pressure. For NBP 5932893, Van Gel® B was added as part of the aqueous vehicle medium. Poly (methyl methacrylate) (PMM) and polystyrene (50,000 PM) were obtained from Polysciences Inc. (Warrington, PA) * 100% base i.a. Compensate for polymer purity.

Matrix microparticle suspensions had the following properties: Viscosity in centipoises (cps) was determined using a Brookfield viscometer (LVT model, Brookfield Engineering Laboratories, Stoughtories, MA) according to the manufacturer's instructions.

Following the general procedure of Example 2, matrix microparticle suspensions having the compositions given below were produced: * 100% base i.a. Compensation for polymer purity.

Matrix microparticle suspensions were analyzed for the following properties: * Revolution per minute.

Following the general procedure of Example 2, matrix microparticle suspensions having the compositions given below were produced. Hydrophilic and hydrophobic solutions were sound-treated to produce an NBP 593298 preparation emulsion and homogeneity with a Silverson L4R laboratory homogenizer (Silverson Machines, In., East Longmeadow, MA) to produce an NBP 6061406 and NBP preparation emulsion. 6061409. * 100% basic ia Compensate for polymer purity.

The matrix microparticle suspensions had the following properties: Gel structure Example 6 Following the general procedure of Example 2, matrix microparticle suspensions having the compositions in the table below were produced. Hydrophilic and hydrophobic solutions were homogenized in a cooling bath to prepare NBP 6061413 and NBP 6061415, but not in the preparation of NBP6061406 and NBP 6061411. * 100% base i.a. Compensate for polymer purity.

Matrix microparticle suspensions were analyzed for the following properties: Example 7 Following the general procedure of Example 1, matrix microparticle suspensions having the compositions given below were produced. In the table below, cycles designated (a) employed microparticle preparations which were not filtered, washed and dried after solvent evaporation, cycles designated (b) employed microparticles which were filtered, washed and dried. See Example 1. * 100% baseline Compensate for polymer purity. ** (1) Chronopol® 95; (2) cellulose acetate butyrate; (3) poly (methyl methacrylate).

Matrix microparticle suspensions were analyzed for the following properties: The formulations produced in this Example were applied as follows. The wheat seed was weighed within 50 g of batches for each treatment. Filler solutions were prepared by weighing the formulation and adding deionized water to prepare the high rate filler solutions for each formulation, then dilutions were prepared from the fillers to provide various application rates.

A Hege 11 laboratory scale rotostatic seed handler with a small capacity 200 gram seed treatment drum was used for seed treatments.

For each treatment, a sample batch was treated with the formulation or only the solvent to wet / soak the drum as recommended by the manufacturer. This seed sample was then taken into a syringe and slowly applied to a fresh batch of 50 g of seed in the seed keeper. Once the seed appeared dry (usually about 30-45 seconds) it was emptied within 1 L of a plastic bottle. The seed was then transferred to a 113 gram (4 oz) glass jar for storage. The jar lid remained raised for several hours to ensure that the seed was completely dry.

Treatments were applied in order of lowest rate to highest rate for each formulation. After the highest rate for each formulation, the seed keeper was completely extracted with absolute ethanol on a paper tissue to prevent contamination of the next formulation. The syringe, funnel and beaker were also rinsed with ethanol.

This procedure was repeated for each of the formulations that were tested.

At the end of all treatments and / or when the active compounds were changed in the course of the same study, the applicants also used an additional cleaning step with a soap-in-water solution and an additional ethanol mop. In order to assess the safety of the formulations, wheat seed that was previously treated with test formulations was sown. Sowing was done at a rate of 12-25 seeds per pot, with four replica pots at each treatment rate. The seeds were covered with approximately 2 cm of the same dirt and incubated under a 12 hour photoperiod, 50% relative humidity at 18 ° C. Eight to twelve days after planting (DBH), each replica pot of each treatment was taxed for the number of seedlings emerged and the average height of seedlings emerged was calculated. The main indicator of formulation performance was relative seedling height measurement for untreated control plants (untreated = 100%).

Figure 1 shows the safety of these treatments, expressed as the time to germinate wheat at 11 days after planting (DBH) as one percent of the height of untreated controls. For comparison, Alto® 005LS (Sandoz Agro, Ltd., Basel, Switzerland) was included as a standard, non-matrix rapid release formulation of cyproconazole liquid seed treatment.

Example 8 Following the general procedure of Example 2, matrix microparticle suspensions having the following compositions were produced. Cellulose acetate butyrate was obtained from Sigma Chemical Co. (St. Louis, MO). SMA® 1440A resin, a maleic ester / styrene anhydride copolymer was obtained from Sartomer Co. (West Chester, PA). Polymethyl vinyl ether / maleic acid was obtained from Sigma Chemical Co., (St. Louis, MO). Wood rosin was obtained from Westvaco (Charleston Heights, NC). * 100% base i.e. Compensate for polymer purity.

The suspensions produced in this Example were applied to wheat using the procedure specified in Example 7. FIGURE 2 shows the safety of these treatments 10 days after planting as compared to Alto® 005LS.

Following the general procedure of Example 1, matrix microparticle suspensions having the following compositions were produced. Lactel® BP-400 was obtained from Sigmal Chemical Co. (St. Louis, MO). * 100% base i.e. Compensate for polymer purity.

The suspensions produced in this Example were applied to wheat using the procedure specified in Example 7. FIGURE 3 shows the safety of these treatments 10 days after planting as compared to Alto® 005LS.

Following the general procedure of Example 1, matrix microparticle suspensions having the following compositions were produced. * 100% base i.e. Compensate for polymer purity.

The suspensions produced in this Example were then applied using the procedure specified in Example 7. FIGURE 4 shows the safety of these treatments at 11 days after planting as compared to Alto® 005LS.

Following the general procedure of Example 1, matrix microparticle suspensions having the following compositions were produced. * 100% base i.e. Compensate for polymer purity.

The suspensions produced in this Example were applied for use using the procedure specified in Example 7. FIGURES 5 and 6 show the safety of NBP 5881012C at 10 days after planting and 9 days after planting, respectively, as compared to Alto® 005LS.

Following the general procedure of Example 1, matrix microparticle suspensions having the following compositions were produced. * 100% base i.e. Compensate for polymer purity.

The suspensions produced in this Example were applied for use using the procedure specified in Example 7. FIGURE 7 shows the safety of NBP 5881012C and NBP 5890983A at 9 days after planting as compared to Alto® 005LS. FIGURE 8 shows the safety of NBP 5890983A and NBP 5890983B at 10 days after planting as compared to Alto® 005LS.

Following the general procedure of Example 1 and using the ingredients listed below, matrix microparticle suspensions having the following compositions were produced. Biopol® D400G was obtained from Monsanto Company (St. Louis, MO). Polyvinylpyrrolidone / vinyl acetate copolymer (PVP / VA S-630), which was used as a dispersant, was obtained from GAF Chemicals Corp. (Wayne, NJ). * 100% base i.a. Compensate for polymer and inherent purity.

The suspensions produced in this Example were applied for use using the procedure specified in Example 7. FIGURE 9 shows the safety of NBP 5890983C and NBP 5890983D at 10 days after planting as compared to Alto® 005LS. FIGURE 10 shows the safety of NBP 5890977D 10 days after planting as compared to Alto® 005LS.

Example 14 Following the general procedure of Example 1, matrix microparticle suspensions having the following compositions were produced.

The suspensions produced in this Example were applied to wheat using the procedure specified in Example 7. FIGURE 11 shows the safety of these suspensions 10 days after planting as compared to Alto® 005LS.

Following the general procedure of Example 1 and using the ingredients listed below, the matrix microparticle suspensions below having the following compositions were produced.

The suspensions produced in this Example were then applied using the procedure specified in Example 7. FIGURE 12 shows the safety of these suspensions 10 days after planting as compared to Alto® 005LS.

Following the general procedure of Example 2, matrix microparticle suspensions having the following compositions were produced. Lucite ® N229 was obtained from Polysciences Inc. (Warrington, PA). * 100% base i.e. Compensate for polymer purity.

The suspensions produced in this Example were applied in full using the procedure specified in Example 7. FIGURE 13 shows the safety of these compounds 10 days after planting as compared to Alto® 005LS.

Following the general procedure of Example 2, a matrix microparticle suspension having the following compositions and properties was produced. Tebuconazole was obtained from Bayer (Leverkusen, Germany). * 100% base i.e. Compensate for polymer purity.

Following the general procedure of Example 1, a matrix microparticle suspension having the following composition and properties was produced. * 100% base i.e. Compensate for polymer purity. MON 38410 and MON 38411 were applied to wheat using the procedure specified in Example 7. FIGURE 14 shows the safety of these compounds 10 days after planting as compared to Raxil® (Bayer, Leverkusen, Germany), a fast release formulation with - tebuconazole merchant.

Following the general procedure of Example 2, a matrix microparticle suspension having the following composition and properties was produced. * 100% base i.e. Compensate for polymer purity.

Following the general procedure of Example 2, a matrix microparticle suspension having the following composition and properties was produced. * 100% base i.e. Compensate for polymer purity.

The suspensions of MON 38410 and MON 38411 were applied to wheat using the procedure specified in Example 7. FIGURE 15 shows the effects of these suspensions compared with the effect of Opus® (BASF AG, Limburgerhof, Germany), a formulation. rapid-release epoxiconazole drug. The maximum insurance rate for applying Opus as a seed treatment is approximately 1 g / 100 kg of seed.

Example 21 Wheat seeds were coated with a suspension of the matrix microparticles of the present invention using the following procedure.

The following water-based film coating concentrates were used for seed film coating: Blue Opa-coat AG (Colorcon, West Point, PA), Sepiret 8127 Rouge (Seppic, Paris, France), and Sepiret 2020 The Rouge (Seppie, Paris, France). Sepiret and Opacoat formulas are ready to use colored film formed compositions designed for the application of thin films of biodegradable polymers, usually derived from naturally occurring cellulose.

A batch film coating system (Coating Machinery Systems [CMS] PSC-5, Ames, IA) was used to apply a precision coating to specify seed quantities. Water-based film coating concentrates were usually diluted to 15% w / w solids concentration with water prior to application. Microparticle formulations were usually diluted to a concentration of 0.12% w / w and seed-coated active compound as a comparative coating (using the procedure of Example 7) or in combination with water-based film coatings. . Drying temperatures were usually started / terminated at 37 ° C / 32.2 ° C (100 ° F / 90 ° F) with air flows at 4914 cm3 (300 cubic feet per minute) (CFM). Added coating weights were usually calculated at about 2% w / w, which provides for uniform coverage. After coating, the individual coated seed batches were analyzed for cyproconazole content ("found i.a."). Q.S. = sufficient amount to dilute to a required concentration. Figure 16 shows the safety of suspensions at an application rate of 16 g of active compound per 100 kg of seed as compared to Alto® 005LS. Differences in safety between matrix microparticle formulations at lower application rates were less pronounced.

Example 22 In this example, the polymers used were poly (methyl methacrylate) (350,000 MW, Polysciences, Inc., Warrington, PA) or poly (styrene / maleic anhydride) (75% styrene, Sigma Chemical Co., St. Louis, MO). The organic solvent was methylene chloride (American Chemical Society analytical reagent grade). Dispersing agents used were Methocel A15LV (methyl cellulose, Dow Chemical, Midland, M1); Elvanol 51-05 (polyvinyl alcohol, DuPont, Wilmington, DE); or Yelkinol P (lecithin, Archer Daniels Midland Company, Decatur IL). Active compounds used were epoxyconazole (technical grade @ 96.2%, BASF) or tebuconazole (technical grade @ 98.6%, Bayer).

All formulations were prepared by an oil-in-water (O / W) emulsion / solvent evaporation procedure. Briefly, the polymer and active compound were dissolved in methylene chloride at room temperature to form a hydrophobic solution (15% solids). The hydrophobic phase (oil, O) was added to a cooled 0.5 - 3.0% (<5 ° C) aqueous dispersing solution (water, W) and sheared with a Silverson Model L4R homogenizer large hole, 1.5 cm) for 5 minutes to fix N25 to form an emulsion. The organic solvent was then evaporated with stirring at room temperature in a smoke hood.

The resulting microparticle preparations were normally passed through a No. 60 mesh sieve to remove large particles. These microparticles are examined microscopically with a Leitz Dialux 20 EB microscope for crystals and microparticle morphology, and evaluated using a Coulter LS-130 particle size analyzer to determine the mean particle size and number of modes in the distribution. .

To test the release rate of active compound from microparticle formulations, an aliquot of a formulation was housed in a glass bottle at a concentration at which a released active compound was expected to have <1/2 the solubility level of. Water. A solvent was then added (water or 10% acetone). At various intervals, the bottle was shaken (200 times at 0 ° C, 20 times for other intervals). An aliquot was removed, centrifuged 15 minutes at 2700 rpm, and filtered through a 0.45 micron PTFE filter (then discarding the first 2 ml). Tests for epoxiconazole and tebuconazole were performed by HPLC.

Microparticle suspensions having the following compositions were produced.

Epoxyconazole-containing matrix microparticle formulations - Composition (%, w / w) Ingredients 6239153A 6239162 6151653C

Epoxiconazole 3.00 3.00 3.00 (100% basic ia) Polymer 27.00 (a) 12.00 (b) 12.00 (c) Methocel® A15LV - - 2.00 Elvanol® 51-05 4 Yelkinol® P - 1.50 Water 83.50 83.50 83.00 100.00 100.00 100.00 Evaluation Data Ia load (% w / w) 10% 20% 20% emulsion O / W rate 1/5 3/2 3/2 average particle size, 11.3 µm, trimodal 1.37μ, bimodal 30 µm, bimodal mode:% i. The. initial./% REA * 3.57 / 0.18 3.44 / 1.00 3.94 / 0.2 Polymers: (a) poly (methyl methacrylate), (b) poly (styrene / maleic anhydride) ) * REA = Promptly Pullable Asset Tebuconazole-containing matrix microparticle formulations - Composition (%, w / w) Ingredients 6248014A 6248014B 6248014C

Tebuconazole 3.00 4.50 6.00 (100% basic ia) Polymer * 12.00 (a) 10.50 (a) 9.00 (a) Methocel® A15LV 1.00 1.00 1.00 Water 84.00 84.00 84.00 100.00 100.00 100.00 Evaluation Data Ia loading,% 20 30 40 taxO / Ana 3/2 3/2 3/2 emulsion average particle size, 914 μ, βιτχχ & Ι 7.36μ.bimodal 13.48 | i, thymodal mode: initial% ia /% REA: 3.25 / 0.68 4.92 / 2.01 5.75 / 2.21 * (a) poly (methacrylate) (b) poly (styrene / maleic anhydride) In addition, the phytotoxicity of the wheat formulations and their release rates in water and in 10% acetone solutions have been determined. This formulation is summarized below.

Matrix microparticle formulations containing epoxyconazole - Phytotoxicity and release rates Formulation 6239153A 6239162 6151653C% release, 269 hours: -Water 0.9 6.56 1.63 - 10% acetone: 9.71 46.7 26 .6 Safety in wheat * - 25 g / 100 kg of seed 96.9% (25.4 g) 66.4% (12.4 g) 92.2% (28.6g) - 50 g / 100 kg of seed 91.8% (46.4 g) 20.0% (42.2g) 75.4% (53.3g) Opus®, 8g / 100kg) 22.5% (6.4g) Control (0 g / 100 kg) 100% (0 g) * The plant height as a% of the height of untreated control plants. The number in parentheses is the kilograms of active compound found by the test to have in 100 kg of treated seed.

Matrix microparticle formulations containing tebuconazole - Phytotoxicity and release rates Formulation 6248014A 6248014B 6248014C% release, 269 hours: -Water: 2.53 3.79 14.5 - 10% acetone: 24.9 46.2 60, 0 Safety in wheat * - 50 g / 100 kg of seed 89.7% (47g) 78.4% (45 g) 70.3% (49g) - 75 g / 100 kg of seed 83.8% (70g) 77.3% (72 g) 68.7% (78 g) -100 g / 100 kg of seed 78.4% (95 g) 74.1% (92 g) 60.8% (99 g) - Raxil ®, 25 g / 100 kg 40.3% (26 g) Control (0 g / 100 kg) 100% (0 g) *% of untreated control height. The numbers in parentheses are the kilograms of the active compound found by the test to have 100 kg of treated seed.

The microparticles having the same polymer and the active loading compound (6239162 versus 6151653C), but using a different dispersant that had very different release rates and corresponding differences in safety in wheat. The high release rate and the highest initial% REA of 6239162 gives a product having poor wheat security. However, the same loading on the same polymer processed with a different dispersant gives a formula with a lower release rate and readily extractable activity (REA) and higher safety in wheat.

In addition, the release rates of active compounds are higher (and safety in wheat correspondingly decreased) as the microparticle charge is increased.

This study indicates that release rates can be exchanged for processing and loading of active compound (concentration) in the matrix microparticle. As the concentration of active compound increases, release rates also increase. Lower release rates tend to result in higher safety in wheat. When different dispersing agents are used for the preparation of emulsions, the emulsion quality and release rate of the resulting microparticles are affected.

Poly (methyl methacrylate) and poly (styrene maleic anhydride) are polymers useful for producing microparticles that increase the safety of epoxiconazole and tebuconazole in wheat.

Example 23 For this Example, the polymer used was poly (styrene / maleic anhydride) (75% styrene, Sigma Chemical, Co., St. Louis, MO)). All organic solvents were from the American Chemical Society (A.C.S.) analytical reagent grade. The dispersing agent used was Methocel A15LV (methyl cellulose, Dow Chemical, Midland, M1). The active compounds used were as follows: triazole fungicide triticonazole (technical grade> 91.8%, Rhône-Poulenc Ag Co., Research Triangle Park, NC), trialate herbicide (technical grade> 94%; Monsanto Company, St. Louis, MO), strobilurin fungicide MON 46100 (technical grade> 95%; Monsanto Company, St.

Louis, MO), furilazole safety herbicide (MON 13900, technical grade> 95%; Monsanto Company, St. Louis, MO); chlorpyrifos insecticide (high purity> 99%; Dow Chemical Co., Midland, M1); a morpholine-like fungicide fenpropimorph (used "as is" in the form of the 750 g / L Corbel® formulation, BASF AG, Limburgerhof, Germany); an imidazole carbamoyl-like fungicide, prochloraz (high purity> 99%; Monsanto Company, St.

Louis, MO).

Matrix microparticle formulations were prepared by an oil-in-water emulsion / solvent evaporation procedure. Briefly, the polymer and active compound used were dissolved in methylene chloride at room temperature to form a 15% hydrophobic solids solution (oil, O). This oil phase was added to a 0.5-3% (<5 ° C) aqueous dispersing solution (water, A) cooled and sheared with a Silverson Model L4R homogenizer (1.5 cm large hole screen). ) for 5 minutes to fix N25 to form an emulsion. The organic solvent was then evaporated with stirring at room temperature in a smoke hood. The resulting formulations were usually passed through a No. 60 mesh sieve to remove large particles and then evaluated. The microparticles were subjected to microscope examination with a Leitz Dialux 20EB microscope to verify crystals and microparticle morphology and a particle size evaluation using a particle size analyzer to determine average particle size and model number. in distribution.

Test compositions were prepared and their physical properties evaluated. Both formulas are described below. Formula B was necessary for triticonazole because a lot of crystalline growth occurs when formula A is used. Formula A produces a 20% active compound loading for microparticles and formula B produces a 5% loading. Formulas (%, w / w) Ingredients Formula A Formula B

Active compound 3.00 0.75 Poly (styrene / maleic anhydride) 75:25 12.00 14.25 Methocel® A15LV 2.00 2.00 Water 83.00 83.00 100.00 100.00 Formula References Active Compound Reference Number Formula Average Size (ii) Triticonazole NBP6256301 B ~ 5 MON 46100 NBP 6248096B A 5.4 Fenpropimorf NBP6273923C A 2.7 Furilazole NBP 6237196-4 A ~ 5 Trialate NBP 6237196-3 A ~ 5 Chlorpyrifos NBP 6237196-2 A ~ 5 Proclor NBP 6237101 A 4.8 Particle size analyzes were performed on MON 46100 and fenpropimorf formulation; Estimates from photographs were used for other formulations. Figure 17 shows the safety of NBP 6273923C ["fenpropimorf (matrix)"] 10 days after planting when applied as a seed treatment for wheat at rates of 50-200 g ai / 100 kg seed, as compared to Corbel. ®, a commercial fast release formulation of fenpropimorf.

Figure 18 shows the safety of NBP 6248096B [“MON 46100 (matrix)”] 10 days after planting when applied as a seed treatment for wheat at various rates as compared to MON 46100 ["MON 46100 (Acetone / H20)] not formulated.

Example 24 Polymers used were poly (methyl methacrylate) (350,000 MW, Polysciences, Inc., Warrington, PA) and poly (styrene / maleic anhydride) (75% styrene, Sigma Chemical Co., St. Louis, MO). used. All organic solvents were of the American Chemical Society (A.C.S.) analytical reagent grade. Dispersing agents used were Methocel® A15LV (Dow Chemical, Midland, M1) and Elvanol 51-05 (polyvinyl alcohol, DuPont, Wilmington, DE).

The microparticles were prepared by an oil-in-water emulsion / solvent evaporation procedure. Briefly, the polymer and active compound used was dissolved in methylene chloride at room temperature to form a 15% hydrophobic solids solution (oil phase, O). This oil phase was added to a cooled and sheared 0.5-3% (<5 ° C) aqueous dispersing solution (aqueous solution, A) with a Silverson Model L4R homogenizer (large hole screen, 1 0.5 cm) for 5 minutes to set N2 3 to form an emulsion. The solvent was then evaporated with stirring at room temperature in a smoke hood.

Tests for active compound concentration were made and another water evaporation was performed to give the calculated final concentration. The resulting microparticles were passed through a No. 60 mesh sieve to remove the large particles and then evaluated. Several evaluations were made, including microscope examination with a Leitz Dialux 20EB microscope, pH, density, viscosity, and particle size distribution by a Coulter LS-130 particle size analyzer.

Seed treatment formulations, their physical properties and phytotoxicity data from greenhouse trials are described below. The dispersant used for all formulations was Methocel® A15LV except mon 24531. This formulation showed better process with Elvanol® 51-05 as a dispersant.

Seed Treatment Formulations% (W / W) Ingredients MON MON MON MON MON MON MON 24531 24532 24533 24534 38413 38414 38415 Epoxiconazole 3.00 * 3.00 * 3.00 * 3.00 * Tebuconazole - 10.00 * 10 .00 * 10.00 * Polymer 27.00 (1) 12.00 (2) 27.00 (2) 12.00 (1) 40.00 (2) 15.00 (2) 40.00 (1) Methyl Cellulose - 1.86 1.00 1.50 1.40 1.70 1.40 Polyvinyl 3.85 ...... Water alc. 66.15 83.14 69.00 83.50 48.60 73.30 48.60 100.00 100.00 100.00 100.00 100.00 100.00 100.00 * 100% basis i.a.

Polymers: (1) poly (methyl methacrylate); (2) poly (styrene maleic anhydride) 75:25 copolymer ratio The table below provides information regarding the physical properties of microparticle preparations.

Physical Properties CER-9802- 8638-F 8637-F 8640-F 8652-F 8651-F 8641-F 8644-F

Ownership MON MON MON MON MON MON MON MON 24531 24532 24533 24534 38413 38414 38415% ia 2.94 3.01 2.96 2.93 9.39 10.13 9.89% REA 0.27 0.19 0.03 0 .55 0.08 1.19 0.24 ts (C) when 23.7 23.7 24.2 23.0 23.3 23.2 22.9 of the measured Density, 1.07 1.03 1, 05 1.03 1.08 1.05 1.10 g / cm3 Viscosity, 3.61 2.04 3.34 1.97 19.0 4.46 25.9 60rpm, cps pH 7.07 4.02 3 , 36 6.82 3.31 3.77 6.25 Phytotoxicity of formulations containing tebuconazole [% control height] CER-9802 -F -F -F -F Ref Ref g / 100 kg se- MON MON MON MON MON

38413 38414 38415 38416 38412 RAXIL 16 ..... 76.3 25 .... 95.5 50 82.1 69.8 89.7 70.3 89.6 75 84.5 64.4 83.8 68.7 100 - - 78.4 60.8 LDS (0.05) = 19.14 Phytotoxicity of epoxiconazole containing formulations [% Control Height] CER-9802 8638-F 8637-F 8640-F 8652-F 978221 Ref.

g ai / 100 ka se- MON MON MON MON MON OPUS 24531 24532 24533 24534 24555 5 ..... 32.5 25 93.8 91.2 93.8 83.0 96.2 8.6 50 83, 4 73.3 98.0 43.3 90.5 75 77.9 61.4 86.8 24.3 87.9 Formulations containing epoxiconazole showed much less phytotoxicity than the commercial reference, Opus®. Also, formulations containing tebuconazole showed lower phytotoxicity than the commercial reference, Raxil®. MON 38412 and MON 24555 have also been tested as soybean leaf treatments. At rates of 50 and 250 ppm of active compost, MON 38412 and MON 24555 soybean plants treated as leaf treatments showed a substantially higher vigor than Foliculur® and Opus® treated plants, particularly the rate of treatment. highest application.

FIGURE 19 shows the effect of foliar applications of MON 38412, MON 24555, Raxil®, and Opus® on soybean plant vigor five days after treatment (on a scale of 1-5, untreated control plants. = 5).

FIGURE 20 shows the safety of MON 24555, Opus®, MON 38412, and Raxil® 9 days after planting when applied as soybean seed treatments at various application rates.

Applicants have conducted field trials to evaluate the effectiveness of seed treatments using microparticle formulations to control naturally occurring infections of wheat powdery mildew. Four replicates were performed for each treatment. FIGURE 21 shows the effectiveness of seed treatments using MON 38414 (30, 45 and 60 g of tebuconazole / 100 kg of seed) and Raxil® (30 g of tebuconazole / 100 kg of seed) controlling the severity of powdery mildew. 42 days in Artisan wheat cultivar. FIGURE 22 shows the effectiveness of seed treatments using MON 38414 and MON 38416 (45 and 60 g of active compound / 100 kg of seed) and Raxil® (30 g of tebuconazole / 100 kg of seed) controlling seed severity. powdery mildew 44 days on Minaret wheat cultivation. The table below shows the safety of MON 24555, Opus ®. MON 38412, and Raxil ® 16 days after planting when applied as pea (Pisum sativum) seed treatments at various rates. RAXIL 10 1 The table below shows the safety of NBP 6237101 and Spork®, a rapid commercial release form of prochloraz, when applied as wheat seed treatments (cv. Rhythm) at various rates. These results show that NBP 623 6237101 significantly improved porchloraz safety, resulting in an increase in the total number of germination for 11 days after planting and the average height of germination.

Application rate Treatment (iaq / ioo ka sementel N2 Plants Height (cm) 5 DBH 8 DBH 11 DBH 12 DBH 6237101 50 72.3 95.0 92.2 40.5 6237101 100 86.3 92.2 100.3 34 , 1 6237101 200 72.2 92.5 95.0 34.3 Sportak® 50 39.6 73.3 75.8 44.9 Sportak® 100 5.3 51.4 64.5 32.0 Sportak® 200 0 , 0 29.7 46.1 17.3 LSD (0.5) 16.6 9.6 Example 25 Applicants evaluated cyproconazole-containing microparticle formulations for efficacy and duration in controlling wheat leaf rust (caused by recondite guccinia in greenhouse experiments Wheat seed (cv. Fortuna) was treated with test treatments (5932839A, MON 24682, or MON 24647, all at 32 g cyproconazole per 100 kg seed and Alto ® 005LS (at 1 g of cyporconazole per 100 kg of seed) and sown in standard 10.16 cm (4M) square pots containing sterile Dupo peat soil, sown at a rate of 1 seed per pot with four pots. in replicate of each treatment fee.

The seeds were covered with approximately 2 cm of the same soil and incubated under a 12 hour photoperiod at 50% relative humidity. Growth room temperatures were maintained at 16 ° C during the 12 hour light period and at 12 ° C during the 12 hour dark period. Twenty days after planting, the treated seedlings were inoculated with P. recondita ureido spores. Inoculated plants were incubated for 24 hours in a humidity probe at 20 ° C to leave disease infection. Disease severity was assessed 8-10 days after inoculation. Figure 23 shows control of brown wheat rust by seed coatings comprising matrix microorganism formulations NBP 5932839A, MON 24682, MON 24647 (each at 32 g cyproconazole per 100 kg seed) and Alto® 005LS (1 g cyproconazole per 100 kg seed). The plants were inoculated 20 days after planting (second leaf stage). Disease severity in untreated control plants was 61.3%. Applicants observed an increase in disease control efficacy and duration in matrix microparticle formulations, which allowed the treatment of plants with a higher rate of active compound than would be tolerated if the plants were treated with a standard formulation. as Alto® 005LS.

Many changes and modifications of the invention described in this report will occur to those skilled in the art when studying the teachings of this report. All changes and modifications which are within the spirit of the present invention are intended to be included in the claims.

Claims (25)

Controlled release composition for supplying an agricultural chemical to a plant, characterized in that it comprises a dispersing agent selected from the group consisting of methyl cellulose and polyvinyl alcohol, and spherical microparticles having an average diameter of 0, 2 microns to 200 microns; each microparticle comprising a triazolic fungicide uniformly dispersed in a polymer matrix, wherein the triazolic fungicide is selected from the group consisting of cyproconazole, epoxiconazole, tebuconazole and triticonazole and wherein the polymer is selected from the group consisting of poly (methacrylate). poly (styrene), poly (styrene maleic anhydride copolymer), poly (lactic acid) and cellulose acetate butyrate. Composition according to Claim 1, characterized in that the microparticles comprise from 1% to 50% by weight of the triazolic fungicide. Composition according to Claim 2, characterized in that the microparticles comprise from 15% to 50% by weight of the triazolic fungicide. Composition according to Claim 1, characterized in that the microparticles comprise from 50% to 99% by weight of polymer matrix. Composition according to Claim 1, characterized in that the microparticles comprise from 50% to 85% by weight of polymer matrix. Composition according to Claim 1, characterized in that the microparticles have an average diameter of from one micron to fifty microns. Composition according to Claim 6, characterized in that the microparticles have an average diameter of three to fifty microns. Composition according to Claim 1, characterized in that it has the form which is selected from the group consisting of a suspension of microparticles in an aqueous medium, a wetting powder, wetting granules, dry granules and a seed coating. Composition according to Claim 8, characterized in that it comprises a suspension of microparticles in an aqueous medium. Composition according to Claim 9, characterized in that the composition comprises from 5% to 25% by weight of the triazolic fungicide. Composition according to Claim 1, characterized in that the microparticles comprise an amount of triazolic fungicide and releasing the triazolic fungicide at a rate so that the composition releases an active amount of triazolic fungicide to the plant during the plant. a period of at least two weeks to twelve weeks. Composition according to Claim 1, characterized in that it consists of a seed coating comprising the microparticles. Composition according to Claim 1, characterized in that the triazolic fungicide is selected from the group consisting of cyproconazole, epoxiconazole and tebuconazole. 14. Controlled release composition for supplying an agricultural chemical to a plant, the composition being characterized by the fact that it comprises spherical microparticles having an average diameter of 3 microns to 50 microns, a dispersing agent selected from the group consisting of methyl. cellulose and polyvinyl alcohol, and a triazole fungicide evenly distributed through a polymer matrix wherein the fungicide comprises from 15% to 50% microparticles by weight, and wherein the triazolic fungicide is selected from the group consisting of in cyproconazole, epoxiconazole, tebuconazole and triticonazole and wherein the polymer is selected from the group consisting of poly (methyl methacrylate), polystyrene), poly (styrene maleic anhydride copolymer), poly (lactic acid) and cellulose acetate butyrate. Composition according to Claim 14, characterized in that the microparticles comprise an amount of triazolic fungicide and release the triazolic fungicide at a rate such that the composition releases an effective composition of the triazolic fungicide to a plant during a period. period of at least two to twelve weeks. Process for providing a triazolic fungicide to a plant, characterized in that it comprises a) providing a plant; and b) administering to the plant a controlled release composition comprising spherical microparticles having an average diameter of 0.2 microns to 200 microns, a dispersing agent selected from the group consisting of methyl cellulose and polyvinyl alcohol, and a triazole fungicide distributed through of a polymer matrix and wherein the fungicide comprises from 15% to 50% of microparticles by weight and wherein the triazolic fungicide is selected from the group consisting of cyproconazole, epoxyconazole, tebuconazole and triticonazole and wherein the polymer It is selected from the group consisting of poly (methyl methacrylate), poly (styrene), poly (styrene maleic anhydride copolymer), poly (lactic acid) and cellulose acetate butyrate. Process according to claim 16, characterized in that it includes providing the composition to the plant by a process selected from the group consisting of applying the composition to the soil, applying the composition to the plant foliage, and coating the seed. before seed germination to produce the plant. Process according to Claim 16, characterized in that an amount of the composition is applied to the soil or plant foliage so that 1 g to 10 kg of triazolic fungicide is applied per hectare. Process according to claim 16, characterized in that it comprises coating a seed with an amount of composition such that 1 gram to 500 grams of triazolic fungicide is applied to 100 kg of seed. Process according to claim 16, characterized in that it comprises coating a plant seed with the composition, wherein upon germination of the seed to produce the plant, the composition provides an effective amount of the triazolic fungicide to the plant. plant for at least two to twelve weeks after germination. Process for producing a composition comprising microparticles for controlled release of a triazolic fungicide, characterized in that it comprises the following steps: (a) dissolving at least one triazolic fungicide selected from the group consisting of cyproconazole, epoxiconazole, triticonazole and tebuconazole, and a polymer in an organic solvent to form a hydrophobic solution, (b) dissolving a dispersing agent in an aqueous solution to produce an aqueous medium wherein the dispersing agent is selected from the group consisting of methyl cellulose and polyvinyl alcohol; (c) mixing the hydrophobic solution and aqueous medium at a shear rate and for a time sufficient to produce an emulsion having hydrophobic solution droplets dispersed in the aqueous medium; (d) evaporating the organic solvent from the emulsion to produce a plurality of spherical microparticles having an average diameter of 0.2 microns to 200 microns and said at least one triazole fungicide distributed throughout the polymer matrix, wherein the microparticles are: they comprise 15% to 50% by weight of triazolic fungicide and wherein the polymer is selected from the group consisting of poly (methyl methacrylate), poly (styrene), poly (styrene maleic anhydride copolymer), poly (acid lactic acid) and cellulose acetate butyrate. Process according to claim 21, characterized in that it includes the step of mixing the hydrophobic solution and the aqueous medium and evaporating the solvent to produce microparticles having an average diameter of one micron to fifty microns upon evaporation. of the organic solvent of the emulsion. Process according to claim 21, characterized in that it includes the step of mixing the hydrophobic solution and the aqueous medium and evaporating the solvent to produce microparticles having an average diameter of three microns to fifty microns upon evaporation. of the organic solvent of the emulsion. Process according to Claim 21, characterized in that it includes the step of suspending the microparticles in an aqueous medium. Process according to claim 21, characterized in that said at least one agricultural chemical is selected from the group consisting of a biocide, a plant growth regulator, a chemical hybridizing agent, a nutrient for plants, and combinations thereof.