MX2008004076A - Granular controlled release agrochemical compositions and process for the preparation thereof - Google Patents

Abstract

A granular agrochemical composition is disclosed including a granular core material having a water soluble portion with a first coating layer applied on the surface of the core material and a second coating layer applied on the surface of the first coating layer. The first coating layer includes a wax composition having a biologically active ingredient incorporated therein and the second coating layer includes a polymeric composition. The granular agrochemical composition exhibits a controlled rate of release of the biologically active ingredient therefrom over a period greater than about 30 days from the date of initial exposure of the granular composition to moisture whereby essentially all of the biologically active ingredient incorporated in the wax material of the first coating layer is released from the granular composition before the water soluble portion of the granular core material is released from the granular composition.

Description

GRANULAR AGROCHEMICAL COMPOSITIONS OF CONTROLLED RELEASE, AND PROCESS FOR PREPARATION FIELD OF THE INVENTION The present invention relates to granular agrochemical compositions and processes for the production of such compositions. More particularly, it relates to controlled release agrochemical compositions having a first coating layer comprising a wax composition with a biologically active ingredient incorporated therein, applied on the surface of a core material and having a second layer of coating comprising a polymer composition applied on the surface of the first coating layer and processes for preparing such compositions. BACKGROUND OF THE INVENTION The agrochemicals referred to herein include biologically active ingredients / products for the protection of plants such as insecticides, herbicides, fertilizers, growth regulators, pheromones, biostimulants, acaricides, miticides, fungicides and the like. Such agrochemicals are well known and are commonly used for the control of pests and diseases and to promote the growth of plants in agriculture. In practice, it is important to make a sufficient quantity of such an agrochemical or active ingredient available for the Ref. 191319 biological system to control pests or disease or to promote growth. However, too much of the active ingredient is inefficient and undesirable because of economic and environmental issues. In addition, the higher amounts of the active ingredient lead to increased leaching risks to groundwater or surface water. Higher amounts can also lead to phytotoxicity for the crop. Insufficient levels of active ingredients lead to a lack of control of pests and an increased risk of resistance. Thus, it is already generally known that it is important to supply the correct amount of the active ingredient to the crop for the control of the pest or disease and to promote growth during a given period of time. However, multiple applications of the active ingredients become intense in terms of work and cost. With conventional applications of the liquid or powder formulations, relatively large amounts of active ingredients are applied several times to ensure control of the pests for a longer period of time, typically 3-6 times for control per season, and users are exposed to the active ingredients during each application, which is undesirable.

When the active ingredients are applied in the granular form instead of by spraying or applying a powder, the risk of exposure to the active ingredient is more limited. After the application of a granular pesticide, the active ingredient is released to the soil under the influence of water. The rate of release varies depending on the formulation of the granule. The granules can be divided into two categories. The first category releases the active ingredient quickly and has to be applied several times during the season. The second category releases the active ingredient over a period of time and provides control of the pests for a prolonged period until the entire season. To control the pests for a longer period of time, the concentration of the active ingredient must be above the minimum effective level for the entire period. To maintain this effective concentration, the loss of the active ingredient by means of leaching, degradation and absorption by the plant must be compensated. The rate of degradation and leaching depends on the active ingredient and the amount that is lost is directly related to the concentration of the active ingredient in the soil. A) Yes, high concentrations lead to relatively greater degradation and leaching. In general, known granular controlled release active ingredients suffer from serious limitations. They generally do not supply the active ingredient to the biological system for periods greater than about 30 days from the date of initial exposure to moisture and / or do not completely release the active ingredient. The practical limitations of the systems that release the active ingredient in less than about 30 days, are that they must be reapplied periodically during the growing season leading to an additional cost. The limitations of systems that do not completely release the active ingredient in the desired period of time are related to efficiency. The most active ingredient must be used to compensate for the portion that will not be released effectively. This causes an additional cost for the user. In addition, the active ingredient not released, residual, poses an environmental risk and can lead to biological resistance in pests. The active ingredient that is not released can not be used for the control of a pest or disease and will provide undesirable residues of the active ingredient. In a prolonged run this can lead to accumulation of chemicals in the soil and this is even less desirable. With no residues after the release period, the soil can be recycled without any risk to the subsequent crop. The use of lower amounts of active ingredients and high efficiency are especially desirable from an economic and environmental point of view. A number of methods have hitherto been used in the production of controlled release granular agrochemical compositions. For example, EP 079668 describes an encapsulated pesticidal product wherein a granular core is coated with a pesticide and then a plurality of layers of a membrane-like coating are applied over a pesticide coating to enable the controlled release of such a pesticide during a period of time during contact with water. However, the products described in EP 079668 are structurally different from the products of the present invention and, consequently, disadvantageously fail to exhibit a controlled release rate of the pesticide for a period longer than about 30 days from the date of Initial exposure of the product to moisture in a manner such that essentially all of the pesticide coated on the core is released from the granular composition before the water-soluble portion of the core material is released from the product, as is achieved with the compositions of the present invention. US 6,682,751 discloses a granular pesticide comprising a core material coated with an internal polymeric membrane formed in situ on the core material with a pesticide applied to the inner polymeric membrane and an external controlled, polymeric release membrane formed in situ on the pesticide to allow controlled release. The pesticide can be incorporated into several layers of "sandwich". Again, the products of US Patent No. 6,682,751 are structurally different from the products of the present invention and fail to exhibit a rate of controlled release of the pesticide for a period greater than about 30 days from the date of initial exposure of the product to the moisture such that essentially all of the pesticide coated on the core is released from the granular composition before the water-soluble portion of the core material is released from the product. US Patent No. 6,080,221 describes the coating of the porous surfaces of the fertilizer particles with tough resin-pesticide solids to form combined pesticide-fertilizer particles., resistant to crushing. In this description, the pesticide is dispersed in a resinoid matrix, which is subsequently bonded onto and within the surface of the fertilizer. US Patent No. 4,971,796 describes another granular slow release product in which the pesticide is converted into a matrix in the coating. The granule comprises a layer of proteinaceous material or more layers of the proteinaceous material with intermediate spacer layers. The active ingredient is in the proteinaceous layer and is released when this layer is degraded. The rate of release is changed by varying the crosslinking or thickness of the layer. The products of US Patent No. 6,080,221 and US Patent No. 4,971,796 fail to exhibit a controlled release rate of the pesticide for a period greater than about 30 days from the date of initial exposure of the product to moisture in such a manner that essentially all of the pesticide coated on the core is released from the granular composition before the core material is released from the product. US Patent No. 6,187,074 and US Patent No. 6,309,439 describe a fertilizer coated with a carboxyl-bearing ethylene copolymer, the carboxyl-bearing ethylene copolymer is composed of 75% -90% by weight of ethylene and from 10% - 25% by weight of an alpha-olefinically unsaturated C3-C8 carboxylic acid. The specifically coated fertilizer particles do not contain any chemical substance that protects the crop. Thus, the products described in these patents fail to exhibit a controlled release rate for a period greater than about 30 days from the date of initial exposure of the product to moisture such that essentially all of the pesticide coated on the core is released. of the granular composition before the core material is released from the product. The U.S. Patent No. 6,693,063 describes products that are structurally different from the present compositions that teach wax microcapsules and a wax dispersion of pesticides in the absence of a water soluble core material. Other encapsulated pesticides that do not include water-soluble core materials are described in Japanese Examined Patent Publication JP-B 5002/1989, JP-A 9304/1994 and JP-A 72805/1994. Other pesticides that exhibit matrix release systems are described in U.S. Pat. No. 4,435,383 wherein the solid controlled pesticide release products are formed comprising an active ingredient incorporated in a homogeneous combination with a polymer, melting the polymer and mixing it with the active ingredient. During this process an additional crosslinking agent is added. Another pesticide based on a matrix is described in US Patent No. 5,516,520 wherein a pesticidally active ingredient is encapsulated in a matrix of starch-borax-urea. The slow release of this matrix is limited to oil soluble pesticides. The rate of release is changed by varying the amount of urea. / EP 0755370 describes other matrix release products which are mixtures of a nitromethylene or substances related to fertilizers and glue. Patent EP 1063215 discloses briquettes that slowly release the active ingredients. The slow release is obtained by means of the absorption or adsorption of the active ingredient on the solids with a high surface area. The matrix systems all demonstrate release mechanisms wherein the release of the active ingredients of the matrix systems is by desorption from an absorbed state or by diffusion and not by an osmotic (pump) delivery mechanism as used herein . The rate of release of such matrix systems depends on the concentration of the active ingredient in the system. Thus, the release rate of such granules is reduced over time leading to an initial rapid release of the active ingredients that provides high amounts of active ingredients in the soil at the beginning, and a slow release at the end. Other types of agrochemicals that can release an active ingredient over a period of time are biodegradable systems such as those described in US Patent No. 4,062,855 wherein the active ingredients are incorporated into a polymer, which are released by means of biodegradation. US Patent No. 4,267,280 describes a product having a biodegradable polymer system containing the pesticide. It releases the pesticide depending on the environmental conditions by means of hydrolysis or depolymerization. A disadvantage of these biodegradable products is that the release of the active ingredient depends on the rate of degradation of the polymer and this degradation depends on the activity of the environmental microorganisms. The activity of microorganisms can vary widely depending on the type of soil and local environmental conditions, types of microbes, pH, temperature, humidity and the like. Thus, the release rate of the active ingredients varies and it is difficult to equalize the velocity precisely with the required, minimum active ingredient concentrations. Other coated granular pesticidal compositions are described in International Patent Publication WO 02/05641 where a pesticidal composition is described, which can slowly release an active ingredient. This publication describes the preparation of various granular materials with different numbers of coating layers or properties of the coating layers.

Each of the granular materials has its own release profile. By mixing the different granules, the desired release configuration of the product can be obtained. The variation of the release is based solely on the coating properties and not on the solubility of the components in the formulation. Patent EP 0966882 describes a granular controlled release product wherein only the single granules exhibit a delay of release after which the pesticide is released. Accordingly, after a period of time, a particular granule opens by rupture and supplies a portion of the active ingredient to the environment. The release over a period of time is established by the combination of multiple "delayed release" granules, which all have different delay times. The granules by themselves do not exhibit controlled release properties, only a delayed release. Patent EP 1148107 describes a coating process for granules with a lower content of volatile substances. This coating procedure ensures that the release function of the granules does not change in two weeks time. Another example of formulations of this general type is described in International Patent Publication WO 99/07654 which comprises fertilizers encapsulated with a polymeric shell containing a hormone (for example an auxin or cytokinin). The hormone is mixed with a monomer that forms a polymeric envelope. Again, the products described in this reference do not exhibit a rate of controlled release of the pesticide for a period greater than about 30 days from the date of initial exposure of the product to moisture in a manner such that essentially all of the pesticide coated on the core it is released from the granular composition before the core material is released from the product. In view of the benefits that can be derived from the agrochemical compositions that provide the controlled release of the active ingredients including the efficiency and economy of the use of the active ingredients, the reduced environmental impact achieved, the ability to employ a single application of the composition for the prolonged control of pests and diseases, the reduction of exposure to the user to the compositions, it is clear that new more technically advanced agrochemicals could be highly desirable. In particular, a desired goal is to provide agrochemical compositions that provide a prolonged shelf life with an essentially complete release of an active ingredient that is occurring for periods greater than about 30 days from the date of initial exposure to moisture. Thus, the agrochemical compositions of the prior art have failed to provide the desired functionality and the present invention is proposed to overcome such a problem by providing compositions that functionally demonstrate a controlled release rate of the active ingredient for a period of time greater than about 30 days from the initial date of exposure of the compositions to moisture such that essentially all of the active ingredient coated on the core is released from the granular composition before the core material is released from the product. BRIEF DESCRIPTION OF THE INVENTION The present invention relates to granular agrochemical compositions that exhibit functionality wherein the essentially complete release of the active ingredients occurs for a period of time greater than about 30 days. These granular compositions comprise a granular core material which is preferably at least partially soluble in water, coated with a first coating layer comprising a wax material having a protection product of the biologically active plant or an active ingredient. incorporated therein and having a second coating layer comprising a polymer composition applied on the surface of the first coating layer. The present invention involves the development of a new system for the release of the active ingredients, such as herbicides, growth regulators, pheromones, bactericides, insecticides, acaricides and fungicides and the like, for a defined period of time with high efficiency. In a preferred embodiment, the granular agrochemical composition of the present invention exhibits a controlled release rate of the biologically active ingredient therefrom for a period greater than about 30 days from the date of initial exposure of the granular composition to the moisture thereby essentially all of the active ingredient biologically incorporated in the wax material of the first coating layer is released from the granular composition while at least a residual amount of the core material remains in the granular composition. In this regard, it has been found that the rate of release of the compositions can be influenced by the change in the properties of the coating, the solubility of the core material and by the adjustment of several other constituents of the product.

BRIEF DESCRIPTION OF THE FIGURES Figure 1 illustrates the release rate of a granular agrochemical composition of the present invention. Figure 2 illustrates the rate of release of another embodiment of the granular agrochemical compositions of the present invention. Figure 3 illustrates the rate of release of another embodiment of the granular agrochemical compositions of the present invention. Figure 4 illustrates the rate of release of another embodiment of the granular agrochemical compositions of the present invention. Figure 5 illustrates the rate of release of another embodiment of the granular agrochemical compositions of the present invention. DETAILED DESCRIPTION OF THE INVENTION The products of the present invention comprise granular agrochemical compositions which include a granular core material having a first coating layer applied to the surface of the core material and a second coating layer applied to the surface of the first layer. coating layer. The first coating layer comprises a wax material having a plant protection product incorporated therein and the second coating layer comprising a polymer composition. The granular composition of this invention exhibits a controlled release rate of a plant protection product therefrom for a period greater than about 30 days from the date of initial exposure of the granular composition to moisture, preferably up to about 104 weeks. after the initial exposure to moisture, whereby essentially all of the plant protection product incorporated in the wax material of the first layer, is released from the granular composition while at least a residual amount of the core material is released. Water soluble remains in the granular composition and the invention also relates to the manufacture of such a granular agrochemical composition. Thus, the present inventions make possible lower application rates for the same control period because the protection products for the plants are essentially completely released at a controlled rate for a period greater than 30 days, preferably up to about 104 days. weeks, from the date of initial exposure to water. The products of this invention have a high efficiency. This means that essentially all of the active ingredient, preferably greater than 90% of the initial weight of the active ingredient in the coating layer of the wax is released to the environment before the water-soluble content of the core material is completely depleted. The present process for preparing the granular compositions of the present invention which exhibit an essentially complete release of the active ingredient for a period greater than about 30 days, preferably comprises coating a core material with a first coating layer comprising a wax material which has a biologically active ingredient incorporated therein and apply a second coating layer comprising a polymer composition applied on the surface of the first coating layer. Even more preferably, the core material is at least partially soluble in water ensuring the transport of the water to the granule through the first and second coating layers by means of osmosis. The "osmotic" transport of the ingredients occurs as a result of pumping the water inwardly and a solution out of the granule and continues until all of the core material has been released. Accordingly, once dissolved, the core material that can be dissolved in water as well as the biologically active ingredient in the first coating layer are transported out of the granule. They are examples of the core materials suitable for use here, fertilizers such as ammonium sulfate, potassium nitrate, potassium sulfate, urea, ammonium nitrate, monopotassium sulfate, ammonium phosphate, super-phosphate, calcium phosphates, potassium phosphate, potassium chloride, magnesium oxide , magnesium sulfate, dolomite and similar or any fertilizers obtained from the composition of a mixture of these fertilizers. Also, non-active materials such as sugar and other granular materials can be used as the core material here, if desired. In a preferred embodiment of this invention, the core materials comprise at least one nutrient and / or a secondary micronutrient. Suitable secondary nutrients include calcium, magnesium, sulfur and mixtures thereof. Suitable micronutrients, in the chelated or non-chelated form, include iron, copper, zinc, manganese, boron, cobalt, chlorine, sodium, molybdenum and mixtures thereof. With respect to the wax composition to be used to form the first coating layer, in an even more preferred embodiment of this invention, the wax must be soluble in water to facilitate an even better dissolution of the active ingredient in the coating layer. covering. The granular agrochemical composition of the present invention exhibits a controlled release rate of a plant protection product (the active ingredient) therefrom for a period greater than about 30 days from the date of initial exposure of the granular composition to the moisture, whereby essentially the entire protection product for the plant incorporated in the wax material of the first layer is released from the granular composition while at least a residual amount of the water-soluble core material remains in the granular composition . Exemplary of the biologically active ingredients suitable for use herein are pesticides, insecticides, herbicides, fungicides, fertilizers, growth regulators, pheromones, biostimulants, acaricides, miticides, nematocides and mixtures thereof. For example, one or more herbicides suitable for use herein include dichlorophenoxyacetic acid, dichloropicolinic acid, dichloro-o-anisic acid, diquation, phosphonomethyl) glycine, isopropyl-4-methyl-5-oxo-2-imidazolin-2-YL acid. ) -nicotinic, 2- ((((((4-methoxy-6-methyl-l, 3,5-triazin-2-YL) amino) carbonyl) amino) sulfonyl) methyl benzoate, butyl-4- (2, 4-Dichloro-5-isopropoxyphenyl-delta2- 1, 3, 4-oxadiazolin-5-one (Note: delta2 = delta subscript 2), ethylpropyl) -3,4-dimethyl-2,6-dinitrobericenamine, 2-chloro- Ethyl 5-4-chloro- (5-difluoromethoxy) -l-methyl-lH-pyrazole-3-YLY-4-fluorophenoxyacetate (CAS name), dichloro-8-quinolinecarboxylic acid, trichloro-2-pyridinyloxyacetic acid, glyphosate, glufosinate-ammonium, phenoxyacetic acid derivatives, phenoxypropionic acid, phenoxybutyric acid, 4-amino-3,5,6-trichloro-picolinic acid, phenoxyethyl sulfuric acid, halogenated benzoic acid, halogenated acetic acid, halogenated propionic acid , phenylurea, or bipyridylium, and certain mineral salts of sodium chlorate, 2,4-dichlorophenoxyacetate sodium or potassium, 4-chloro-2-methylphenoxyacetate sodium or potassium, 2,4,5-trichlorophenoxyacetate sodium or potassium, 2 Sodium or potassium (4-chloro-2-methylphenoxy) -propionate, sodium or potassium 2- (2,4-dichlorophenoxy) -propionate, sodium or potassium 4- (2,4-dichlorophenoxy) butyrate, 4 - Sodium or potassium (4-chloro-2-methylphenoxy) butyrate, sodium or potassium 4- (2,4,5-trichlorophenoxy) butyrate, 4-amino-3, 5,6-trichloropicolinate sodium or potassium , Sodium 2- (2,4-dichlorophenoxy) -ethylsulft, 2,3-trichlorobenzoic acid, 3,6-dichloro-2-methoxybenzoic acid, sodium chloroacetate, trichloroacetic acid, 2,2-sodium dichloropropionate , Sodium 2,2,3-trichloropropionate, N, -dimethyl-1-phenyl urea and its trichloroacetic salt, N, N-dimethyl-N 1 - (4-chlorophenyl) urea trichloroacetate, copper sulfate, iron sulfate, 1,1-dimethyl-4,41-bipyridylium dichloride, 1,1'-bis (3,5-dimethyl-4-morpholinyl) -carbonylmethyl-4,4'-dichloride bipyridylium, 9, 10-dihydro-8a, 10a-diazafenanthrene, 3-amino-1, 2,4-triazole, symmetrical triazines and the like. Suitable insecticides include one or more of the following: dimethyl acetylphosphoramidothioate; Etanimidamide, N-. { (6-chloro-3-pyridinyl) methyl} -N1-cyano-N-methyl-, (E) - (9CI) (CA Index name); hydrazincarboxylic acid, 2- (4-methoxy {1, 1 '-biphenyl} -3 -YL) -, 1-methylethyl (9CI) ester (CA Index Name); 3- (2-Chloro-3,3,3-trifluoro-l-propenyl) -2,2-dimethylcyclopropanecarboxylate methyl. { 1, 1'-biphenyl} -3-YL) methyl,. { 1. alpha, 3. alpha. (Z) } - (+ -.) -; naphthyl-n-methylcarbamate; pyrrole-3-carbonitrile, 4-bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl); chloro-alpha- (1-methylethyl) benzeneacetic acid, amino-1- (2,6-dichloro-4- (trifluoromethyl) phenyl) -4- (1, R, S) - (trifluoromethyl) sulfinyl) -lH-pyrazole -3-cyano (3-phenoxyphenyl) methyl ester carbonitrile; benzoic acid, 4-chloro-, 2-benzoyl-2- (1,1-dimethylethyl) hydrazide (9CI) (CA Index Name); pyrethrins; deoxy-2, 3, 4 -tri-o-methyl-alpha-L-mannopyranosyl) oxy) -13-. { . { 5- (dimethylamino) tetrahydro-?? methyl-2H-pyran-2-YL} oxy } -9-ethyl-2, 3, 3A, 5A, 5B, 6,9,10,11,12,13,14,16A, 16B-tetradecahydro-14-methyl-ß-as-indacene. { 3, 2 -D} oxacyclododecin- 7, 15 -dione, (cal. of cont.; oxadiazin-4-imine, 3- (2-chloro-5-thiazolyl) methyltetrahydro-5-methyl-N-nitro- (9CI) and the like. Suitable fungicides for use in the present invention include tetrachloroisophthalonitrile ethoxy-3- (trichlororaethyl) -1,2,4-thiadiazole; dichlorophenyl) -4-propyl-l, 3-dioxolan-2 -YL) methyl) -1H- 1, 2,4-triazole; carbamic acid, 2-1- (4-chlorophenyl) -lH-pyrazol-3-yl-oxymethyl-phenylmethoxy-methyl ester (CAS name); Dimethyl ((1,2-phenylene) bis (iminocarbonothioyl)) bis (carbamate) and the like. Plant growth regulators, suitable for use in the present invention include RS, 3RS) -1- (4-chlorophenyl) -4,4-dimethyl-2- (1H-1,2,4-triazole-1) -YL) pentan-3 -OL; cyclohexanecarboxylic acid, 4- (cyclopropylhydroxymethylene) -3,5-dioxo-, ethyl ester. Other examples of biologically active ingredients that can be employed in the preparation of granular compositions of this invention include (z) -11-tetradecenyl acetate; 1,2-benzisothiazolin-3 -one; 1,2-dibromoethane; 1,3-dichloro-5,5-dimethylhydantoin; 1,3-dichloro-5-ethyl-5-methylhydantoin; 1-bromo-3-chloro-5,5-dimethylhydantoin; l-chloro-2,3-epoxyethane; 1-methylcyclopropene; 1-naphthylacetamide; 1-naphthylacetic acid; 2 - (thiocyanomethylthio) benzothiazole; 2,2-dibromo-3-nitrilopropionamide; 2, 2'-bipidyryl; 2, 2 -dithiobisbenzamide; 2,4,5-T, 2,4-D, 2,4-DB; 2,4-dichloroanisole; 2,4-dichlorobenzoic acid; 2,4-dichlorophenol; 2,6-dichlorophenol; 2-aminopyridine; 2-bromo-2-nitro-1,3-propanediol; 2-bromo-4-hydroxyacetophenone; 2-phenylphenol; 2-methyl-4-isothiazolin-3-one; 2-methylthio-4-tert-butylamino-cyclopropylamino-s-triazine, 3-indoleacetic acid; 4, 4'-bipyridyl acid; 4,6-Dichloro-2-methylphenoxyacetic acid; 4,6-dichloro-o-cresol; 4, 6-dichloro-o-tolyloxyacetic acid; 4-chloro-2-benzylphenol; 4-chloro-3-methyl-sodium phenolate; 4-chloro-m-cresol; 4-chloro-o-cresol; 5-chloro-2-methyl-4-isothiazolin-3-one; 5-oxo-3,4-dichloro-1,2-dithiol; 6-chloro-2-methylphenoxyacetic acid; 6-chloro-o-tolyloxyacetic acid; 6-chloro-p-cresol; abamectin; Accept; acetamiprid; aclonifen; Alachlor; Aldicarb; Aldrin; alkylaryl polyglycol ether; alkyldimethylbenzylammonium chloride; alkyldimethylethylbenzylammonium chloride; alkyltrimethylammonium chloride; Alpha-Cypermethrin; Alpha-Cypermethrin; aluminum phosphide; aluminum sulfate; Ametryn; amphotensides; Amidate; amidosulfuron; Aminocarb; Amitraz; Amitrol; ammonium bichromate; ammonium bifluoride; ancimidol; Anilazine; arsenopentaxide; Asulam; Atrazine; auxin; azaconazole; azadirachtin-a; azamethiphos, Azinphos-methyl; azocyclotin; azoxyestrobin; barium metaborate dialdehyde of amber acid; beauveria bassiana; benazolin-ethyl; Bendiocarb; Benfluralin; Benfuracarb; Benomyl; Bensulfuron-methyl; Bensultap; Bentazone; benthiavalicarb-isopropyl; Benzoylprop-ethyl; benzyladenine; Benzyl benzoate; beta-Cyfluthrin; BHTO; bifenazate; Bifenox; Bifenthrin; Binapacryl; Bioallethrin; Bis (ethylenediamine) copper; Bitertanol; bitumen; borate; Borax, boric acid; boscalid; Brodifacoum; Bromacilo; Bromadiolone; Bromocresol green; Bromophenol blue; BromopHos; Bromothymol blue; Bromoxinyl; bromuconazole; mixtures of bromo-chloro-5,5-dimethylhydantoin; bromophenoxy; bromonitrostyrene; bromopropylate; buminafos; bupirimate; buprofezin; Butachlor; butocarboxim; butoxicarboxim; Butylate; butylmagnesium chloride; calcium cyanide; calcium hypochlorite; Captan; carbaryl; carbeetamide; Carbendazim; carbendosulf; Carbetamide; Carbofuran; carbon disulfide; Carbosulfan; carboxy; carfentrazone-ethyl; Cartap; Cetylpyridinium bromide; Chinomethionat; chlofentezin; Chloramben; Chlordimeform; chlordioxide; chlorphacinon; chlorophenoxyacetic acid; Chlorfenvinphos; Chloridazon; Chlormequat; Chlorobenzilate; chlorobromuron; chlorodedecone; Chloropropylate; Chlorothalonil; Chlorotoluron; Cloroxuron; Chlorphoxim; Chlorpropham; Chlorpyrifos; Chlorsulfuron; Chlorthal; cinidon-ethyl; cis-dichloropropene; clodinafop-propargyl; Clofentezine; clomazone; clopyralid; codlemon; Congo red, coniothyrium minitans; Copper, cupric ethylenediamine sulfate; copper oxide (i); carbonate-copper hydroxide (ii); copper oxide (ii); copper hydroxide; copper naphthenate; copper oxiquinolate; Copper oxychloride; copper resinate; copper silicofluoride; copper sulphate; copper thiocyanate; Cumatetralil; Cianazine; hydrocyanic acid; cyazofamid; Cycloate; Cycloxydim; cyfenothrin; Cyfluthrin; Cyhexatin; Cimoxanil; Cypermethrin; Ciproconazole; cyprodinil; cyromazine; Dalapon; d-allethrin; daminozide; dazomet; DDT; Deltamethrin; d-empenthrin; Deschlorofosfamidon; desmedifam; Desmetryri; d-fenothrin; dialkyldimethylammonium chloride; Diazinon; Diazomethane; Dicamba; Diclobenil; dichlofenthion; Dichlofluanid; dichloran; dichlorodifluoromethane; dichloropropene; Dichlorprop; Diclofop; Dicofol; didecyldimethylammonium chloride; Dieldrin; dienochlor; diethofencarb; diethyl-m-toluamide; difenacum; difenoconazole; difetialon; diflubenzuron; diflufenican; Dimedona derivatives; dimercurium dicyanide; dimethanamide; Dimethoate; Dimethomorph; dimethyl sulfate; disodium octoborate; disodium cyanodithioimidocarbonate; dinoseb; Dinoterb; Dioxane; Diquat; Diquat dibromide; Disulfoton; Dithianon; dithiocarbamate; Ditizone; diuron; d-karvon; dnoc; Dodecyldihydroxyethylbenzylammonium chloride; dodemorf; Dodine; d-tetramethrin; d-trans-Allethrin; Dustability; Edifenphos; Endosulfan; Endrin; enilconazole; Epichlorohydrin; Epoxiconazole; EPTC; Ericrome; Esfenvalerate; Ethephon; Ethiophencarb; Ethion; Ethyrimol; Ethofumesate; ethoprofos; ethyl 3- (n-n-butyl-n-acetyl) aminopropion; ethylene oxide; ethylenediaminetetraacetic acid, Etofenprox; etridiazole; etrimfos; ETU; famoxadone; fenamidone; fenamiphos; fenarimol; Fenbutatin oxide; phenclorazol-ethyl; fenhexamide; Funitrothion; fenmedifam; Fenobucarb; Fenoprop; fenothrin; fenoxaprop-p-ethyl; phenoxycarb; fenpiclonil; fenpropathrin; fenpropidin; Fenpropimorph; Fensulfothion; Fenthion Fentina; Fentin acetate, Fentin hydroxide; Fenvalerate; ferrous phosphate; Ferroin sulfate; ferrosulfate; Fipronil; flocumafen; florasulam; Fluazifop-butyl; Fluazifop-P-butyl; fluazinam; flucycloxuron; fludioxonil; flufenacet; Fluometuron; fluorglycofen-ethyl; fluoxastrobin; flurenol; fluroxypyr; Flusilazole; flutolanil; Folpet; fonofos; foramsulfuron; Formaldehyde; Formothion; fosalon; fosetyl-aluminum; phosphamidon; fosmet; Fostiazate; phoxim; fuberidazole; furalaxyl; furathiocarb; gibberelin; gibberella; Glufosinate; glufosinate-ammonium; glutaraldehyde; glycol bromoacetate; glyphosate-trimesium; Glyphosate; guazatin; haloxyfop-ethoxyethyl; haloxifop-p-methyl; heptenophos; hexadecanoic acid; Hexazinone; hexythiazox; * fenoxacrim; hydramethylnon; hydrogen sulfide; hydroxylammonium chloride; himexazole; Icaridin; Imazalil; imazamethabenz-methyl; Imidacloprid; indoxacarb; yodosulfuron-methyl-sodium; ioxinyl; iprodion; isofenphos; isoproturon; isoxaflutole; iodophor; kasugamycin; kresoxim-methyl, lambda-Cyhalothrin; lenacilo; lindane; linuron; magnesium phosphide; malathion; malein hydrazide; mancozeb; maneb; MCPA; t? -Cresol; mecoprop; mecoprop-p; mepanipyrim; mesotrione; metalaxyl; metalaxyl-m; metaldehyde; metamitron; metam-sodium; metarhizium anisopliae; metazachlor; methabenzthiazuron; methamidophos; methidathion; methiocarb; methomyl; methoprene; methoxyfenozide; methyl bromide; methyl bisthiocyanate; methylnaphtylacetamide; methylnaphthylacetic acid; metiram; metobromuron; metolachlor; methoxuron; metribuzin; metsulfuron-methyl; mevinphos, milbemectin; molinate; monobromoacetic acid; diacid monocarbamide sulfate; monolinuron; monuron; myclobutanyl; N- (2-ethylhexyl) -8,9,10-tribornen-2, 3 -dicarboxamide; n, n-diallylchloroacetamide; sodium bichromate; sodium bisulfite, sodium bromide; sodium chlorite; sodium dichloroisocyanurate; sodium fluoroacetate; sodium hydroxide; sodium hypochlorite; sodium octaborate; sodium perborate; sodium-p-toluenesulfoncloramide; nicosulfuron; nitrothal-isopropyl; n-octylbicycloheptendicarboximide; Nonylphenol ethoxylate; nuarimol; O, O-dimethyl methylphosphoramidothioate; O, O-dimethyl phosphoramidothioate; O-O-dimethyl S-methylcarbamoylmethylphosphorodithioate; O, S-dimethyl methylphosphoroamidothioate; 0, S-dimethyl 4-nitrophenylphosphorothioate; o-Cresol; octanoic acid; octylphenoxypolyethoxyethanol; octylisothiazolin-3 -one; Ometoate, Oxadixyl; oxamyl; oxy-demeton-methyl; paclobutrazol; paecilomyces fumasoroseus; paraforraaldehyde; paraquat; paraquat dichloride; parathion (ethyl); parathion-methyl; p-chloro-m-cresol; p-Cresol; penconazole; pencycuron; pendimethalin; permethrin phenoxyalkanoic herbicides; p-hydroxyphenylsalicylamide; picloram; picoxiestrobin; piperonyl butoxide; pirimicarb; pirimiphos-ethyl; pirimiphos-methyl; poly [oxyethylene (dimethyliminio) ethylene; polybutene; potassium bichromate; potassium bifluoride; potassium hydroxide; potassium n-methyldithiocarbamate; prochloraz; procymidon; profam; prohexadione-calcium; prometryn; propachlor; propamocarb-hydrochloride; propaquizafop; propetamphos; propham; propiconazole; propoxur; propizamide; prosulfocarb; protioconazole; pymetrozine; pyraclostrobin; pyrazophos; pyrethrinen; pyridaben; pyridate; pirifenox; pyrimethanil; pyriproxyfen; quinmerac; quinoclamine; quinoxifene; quizalofop-ethyl, quizalofop-p-ethyl; naba seed oil; rimsulfuron; salicylic acid; sethoxydim; simazine; s-methoprene; s-metolachlor; spinosad; spirodiclofen; Spiromesifen; streptomyces griseoviridis; streptomycin sulfate; sulcofuron; sulcotrione; sulfotep; Sulfur; tebuconazole; tebufenpyrad; teflubenzuron; tefluthrin; temephos; tepraloxydim, terbufos; terbuthylazine; terbutryn; tetra-acetylethylenediamine; tetrachlorvinfos; tetradifon; tetramethrin; thiabendazole; thiacloprid; thiamethoxam; thifensulfuron; Thiobencarb; acid oxalate of thiocyclam; thiodicarb; thiophanate-methyl; thiometon; thiram; thiuram disulfide; tolclofos-methyl; Tolilf Luanid; transfluthrin; triadimefon; triadimenol; tri-alato; triazamate; triazophos; tin-tributyl acrylate copolymer; tributyltin fluoride; tributyltin phosphate; tributyltin methacrylate; tributyltin oxide; trichlorfon; trichloroisocyanuric acid, trichoderma harzianum rifai t-22; triclopyr; tridemorf; triphenyltin fluoride; trifloxiestrobin; triflumizole; triflumuron, trifluralin; trisulfuron-methyl; triforine, trinexapac-ethyl; Urea herbicides; validamycin; vamidothion; verticillium dahliae kleb .; verticillium lecanii; saturated fatty acids; vinclozolin; warfarin; hydrogen peroxide; silver thiosulfate; zineb; zinc borate; zinc naphthenate; zinc oxalate; zinc oxide, zinc pyrithione; zinc zinc sulfide; ziram; ? - Chlorophosphamidon and the like. To ensure that the granular agrochemical composition releases essentially all of its active ingredient (i.e., greater than 90% and, preferably, greater than 99%), the core material must be released more slowly than the active ingredient. Otherwise, the residues of the active ingredient could remain in the controlled release system after the complete release of the core material. In a preferred embodiment of the present invention, the granular core material employed for the preparation of the compositions is at least partially soluble in water and can comprise any of a variety of standard, well-known NPKs, or other such fertilizer granules such as those described in the European Community (EC) Regulations No. 2003/2003. Alternatively, the core material may be a salt soluble in water or other such material, for example sodium salts or calcium salts. Also, other non-ionic materials that may be suitable for use in forming the core of the present compositions, particularly those that can provide an osmotic pressure when dissolved. Examples of such materials are the sugar and urea granules. . Typically, the materials for use in forming the core for the compositions of this invention should have a solubility of about 2 to about 800 g / 1, preferably about 120-450 g / 1. Also, the core material should be shaped as a granule having a diameter of about 0.35 to about 6 mm, preferably about 0.72-4 mm for the best product distribution. Preferably, the wax material to be used for use in the preparation of the first coating layer should have a melting point between about 50 ° C and the degradation temperature of the active ingredient or core material, preferably above approximately 80 ° C. The wax can be hydrophobic or hydrophilic. Exemplary of the waxes suitable for use here are the higher alkenes; stearamides; polyolefins such as polyethylene, oxidized polyethylenes, polypropylene, polyisobutylene, styrene-based polymers; copolymers (blocks) of polyolefins; polyesters; (block) copolymers of polyesters, polyethers, for example (poly (ethylene oxide), poly (propylene oxide), (block) copolymers of polyethers, vinyl resins such as poly (vinyl acetate), poly (alcohol) vinyl), poly (vinyl chloride), poly (vinylidene chloride), poly (vinyl pyrrolidone), poly (vinyl acetal), poly (vinyl methylacetamide); acrylic polymers; cellulose derivatives, for example cellulose acetate; polyamides; polyamines, polyimides, polycarbonates, polysulfones, polysulfides, polysaccharides, mixtures of these waxes can also be used.

In a further preferred embodiment of this invention, the biologically active ingredient or the protection product of the plant for incorporation into the wax to form the first coating layer must be selected from the group consisting of insecticides, herbicides, fertilizers, regulators, growth, pheromones, biostimulants, acaricides, miticides, nematicides, fungicides and mixtures thereof and the like. The controlled release systems of this invention make possible the economical application of a total amount of the active ingredient necessary for the extensive control of the station without the increased risk of leaching, phytotoxicity for crops and is safe for users. The active ingredient is applied without the use of a solvent. Thus, active ingredients of low solubility can be used. Significantly, the system is efficient. At most, only very limited amounts, preferably less than about 10% by weight and, even more preferably, less than about 1% by weight, of the active ingredient should be left within the system. To achieve the high efficiency of the release characteristics of the compositions of the present invention, it is preferred to adjust the water solubility of the core material to correspond to the water solubility of the active ingredient. When the solubility of the core material is too high compared to the solubility of the active ingredient, all of the core material can be released from the entire active ingredient. This leads to the fact that the residue of the active ingredient in the granules is not desirable from a commercial and environmental point of view. If the solubility of the core material is too low compared to the solubility of the active ingredient, too much of the core material can be left in the composition after the release of the active substance. This leads to inefficient use of the core material. The solubility of the active ingredient and the core material can be influenced by the additives, such as ionic and nonionic surfactants, water soluble polymers or complexing agents. Not all active ingredients show a good solubility in water. Increasing the solubility of an active ingredient, for example, by using a nonionic surfactant for the application of the active ingredient renders the active substances more soluble and can make the compositions of this invention more widely applicable. Not only the solubility of the core material, but also, the rate of dissolution of the core material against the active ingredient should be considered in the formulation of the compositions of this invention.

Typically, the ratio of the core material to the active ingredient should be from about 1000 to about 0.1, and preferably about 200-10. After the release period, less than about 10%, preferably less than 1% of the initial amount of the active ingredient must be present within the controlled release system. To achieve the longevity of the desired release of the compositions of this invention, the thickness of the coating employed must be matched with the solubility of the core material and the active ingredient. Furthermore, it should be noted that the longevity of the release of the active ingredients of the present compositions can be modified by varying the amount of the polymer coating used.

Alternatively, the permeability in the water of the polymeric coating can be changed. The polymeric coating layer can be formed from any polymeric material (semi) permeable in water, including copolymers, known in the art, such as thermosetting resins, thermoplastic resins and other polymeric materials or latex polymers and mixtures of the same. The polymer coating makes possible the slow release of the active ingredient for a period of from about 6 to about 104 weeks, preferably, approximately 3-6 months. Exemplary of polymers suitable for use in the present invention are thermoplastic coating materials such as vinyl resins such as poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinyl chloride), vinylidene), poly (vinyl pyrrolidone), poly (vinyl acetal), poly (vinyl methylacetamide); polyolefins such as polyethylene, polypropylene, polyisobutylene; styrene-based polymers; acrylic polymers; polyesters such as poly (alkylene terephthalate); poly (caprolactone); poly (oxyalkylene) s, such as poly (ethylene oxide), poly (propylene oxide); cellulose derivatives, such as cellulose acetate, polyamides; polyamines; polycarbonates; polyimides; polysulfones; polysulfides; polysaccharides and the like. The thermosetting polymeric coating materials suitable for use herein include polyesters such as modified alkyds or alkyds; epoxy resins, · urethane resins; and aminoplasts. In an even more preferred embodiment of this invention, the polymer composition for use in the formation of the second coating layer comprises a polymeric dicyclopentadiene product ("DCPD") (which contains either flaxseed oil or an alkyd resin based in a soybean oil) such as the polymeric coatings used to produce fertilizers such as those sold by the Scotts Company under the trademark Osmocote® as described in US Patent No. 3,223,518 and US Patent No. 4,657,576. In the preparation of the present compositions, the active ingredient is applied to the granular core material with a wax. Preferably, the active ingredient / wax combination is solid at room temperature and is applied to the granular core material as a liquid. The active ingredient can be mixed with a wax (melted) and applied by dripping or spraying on the granular material. The active ingredient does not need to dissolve. The mixture of the active ingredient and the wax can be applied as a dispersion. In addition, functional additives such as surfactants, which are used to modify the solubility in water, can be applied with the active ingredients. The use of ionic or nonionic surfactants makes possible the use of active ingredients in the present compositions having a low solubility in water, thus expanding their applicability. Also, waxes that are nonionic surfactants can be used here. The present invention encompasses both granular controlled release agrochemicals, and processes for the preparation thereof and solves the problems encountered with respect to the functionality of the previous compositions in terms of the release of the active ingredient over an extended period of time. . The compositions and processes of the present invention are further illustrated by the following examples. The examples serve only to illustrate the invention and should not be construed as limiting since further modifications of the disclosed invention will be apparent to those skilled in the art. All such modifications are considered to be within the scope of the invention as defined in the claims. Example 1 A sample of the granular agrochemical compositions of the present invention was prepared using a 0-2-40 fertilizer granule obtained from The Scotts Company (Howden, UK) as the granular core material. This granular core was composed predominantly of potassium sulfate. The composition of the sample was prepared by initially heating 50 g of the fertilizer granules 0-2-40 (1.7-2.0 mm) in a rotating drum at 110 ° C. Then, 0.75 g of a non-ionic surfactant wax (a polyethylene glycol-block-polyethylene, case number: [251553-55-6], hydroxyl number of 52.00 mg KOH / g, containing 20% (by weight) of polyethylene glycol, obtained from Sigma-Aldrich), were melted and 0.25 g of a biologically active ingredient (imidacloprid, obtained from Sigma-Aldrich) were mixed in the molten wax. Then, the resulting mixture of imidacloprid and wax was added to the hot fertilizer granules (potassium sulfate) to form a coating layer on the granular core. The granules with the imidacloprid and the wax coating on them, they are allowed to cool to room temperature. Subsequently, a second coating layer was applied on the imidacloprid and the wax coating layer according to the following procedure. The active impregnated granules were heated for 15 minutes in a rotary vessel in an oil bath at 95 ° C. A modified unsaturated oil copolymer based on the alkyd resin sold under the trademark Necolin S9363 by Ashland-Sudchemie-Kernfest GmbH, Germany, was added to the hot granules over a period of 40 minutes. The solids content of the added resin was 40%. Turpentine was used as a solvent and a dryer was used to improve curing. During the application process of the second polymeric coating layer, the air was purged through the system to evaporate the solvent from the resin. After coating of 5.5 pph (parts by weight percent) on the granular composition having the first coating layer on it, the resulting composition was cooled to room temperature and was ready for testing. The concentration of imidacloprid in this composition was 0.30% by weight as determined by the analytical chemical analysis techniques of High Resolution Liquid Chromatography, standards. The test sample of this Example 1 was subjected to the release test wherein the release of the active ingredient from the coated granular composition was evaluated in water in a so-called water leaching test. For this water leaching test, 200 ml of water are added to 10 g of the coated granular composition. Then the sample was stored at 21 ° C and the water was completely replaced with fresh water after 1 day and at weekly intervals after that. The water removed was analyzed on the content of the active ingredient with standard analytical methods. For example, the release of the active ingredient of imidacloprid from the test samples of Example 1 was analyzed with HPLC, column: inertsil ODS-2 150 x 4.6 mm, eluting acetonitrile / water (pH = 3 with phosphoric acid). The release profile was calculated from the concentration of the initial active ingredient in the granule. The dissolution of the core was calculated from the measured conductivity. The measured conductivity can be translated into a total amount of the nutrients released using the appropriate calibration constants. These calibration constants are specific to a particular type of fertilizer and are determined experimentally. The result of this analytical evaluation was plotted based on the percentage of release of the active ingredient against the percentage release of the water-soluble core material for a period of time up to 287 days as illustrated in Figure 1. As can be seen of the graphic display in Figure 1, the granular composition having the biologically active imidacloprid ingredient incorporated in the nonionic surfactant wax provided an effective and efficient system for the release of the active ingredient over a period greater than 30 days. Indeed, as demonstrated by the results shown in Figure 1, the compositions of this invention provided a release of about 95% (by weight) of the active ingredient over a period of 287 days from the date of initial exposure to moisture while that only about 50% (by weight) of the core material was released during this same period of time, so that approximately 50% (by weight) of the water-soluble portion of the granular core material remained within the granular composition during the 287 days of duration. Example 2 The composition produced according to this Example 2 is distinguishable from the compositions produced according to Example 1 with respect to the wax material employed in the formation of the first coating layer of the test sample of the granular agrochemical composition of the present invention. The procedure used to produce the test sample of this Example 2 was in accordance with the process of Example 1. Specifically, a fertilizer granule 0-2-40 obtained from The Scotts Company that was composed predominantly of potassium sulfate, was used as the material of the granular core for the composition of the sample that was prepared by initially heating 50 g of the fertilizer granules 0- 2-40 (1.7-2.0 mm) in a rotating drum at 110 ° C. Then, 0.75 g of a polyethylene glycol-block-polyethylene, no. of case: [95953-22-5], hydroxyl number of 55.00 mg KOH / g, · containing 50% (by weight) of polyethylene glycol, obtained from Sigma-Aldrich), were melted and 0.25 g of a biologically active ingredient (imidacloprid, obtained from Sigma-Aldrich) in the molten wax. This wax was different from the wax used in Example 1 but it possessed suitably similar surfactant characteristics for the biologically active ingredient of imidacloprid which was incorporated by mixing it into the molten wax as described in Example 1. Then, the resulting mixture of imidacloprid and wax was added to the hot fertilizer granules (potassium sulfate) to form a coating layer on the granular core. The granules with the imidacloprid and the wax coating on them, are allowed to cool to room temperature. Subsequently, the same second polymeric coating layer as described in Example 1 was applied on the imidacloprid and the wax coating layer using the same procedure as in Example 1 to produce the granular composition for the test. The concentration of imidacloprid in the composition of this Example 2 was 0.22% (by weight) as determined by the analytical chemical analysis techniques of High Resolution Liquid Chromatography, standards. The composition of this Example 2 was subjected to the release test procedure as described in Example 1 and the results of this test are illustrated in Figure 2. As can be seen from the graphic display in Figure 2, this granular composition which has the biologically active imidacloprid ingredient incorporated in the wax, provided an efficient and effective system for the release of the active ingredient for a period greater than 30 days. Indeed, as demonstrated by the results shown in Figure 2, the composition of this invention provided a release of about 96% (by weight) of the active ingredient over a period of 287 days from the date of initial exposure to moisture while that only about 65% (by weight) of the core material was released during this same period of time so that about 35% (by weight) of the water-soluble portion of the granular core material remained within the granular composition during the duration of the 287 days. Example 3 The composition produced according to this Example 3 is distinguishable from the compositions produced according to Example 2 with respect to the amount of the active ingredient that was incorporated into the wax material in the formation of the first coating layer of the test sample of the granular agrochemical composition of the present invention. The procedure used to produce the test sample of this Example 3 was in accordance with the process of Example 1. Specifically, a fertilizer granule 0-2-40 obtained from The Scotts Company which was predominantly composed of potassium sulfate was employed as the granular core material for the composition of the sample that was prepared by initially heating 50 g of the fertilizer granules 0-2-40 (1.7-2.0 mm) in a rotating drum at 110 ° C. Then, 0.75 g of a polyethylene glycol-block-polyethylene, no. of case: [97953-22-5], hydroxyl number of 55.00 mg of KOH / g, containing 50% (by weight) of polyethylene glycol, obtained from Sigma-Aldrich), were melted and 0.75 g of an ingredient were mixed biologically active (imidacloprid, obtained from Sigma-Aldrich) in the molten wax. This amount of the biologically active ingredient is higher than the amount used in Example 2. Then, the resulting mixture of imidacloprid and wax was added to the hot fertilizer granules (potassium sulfate) to form a coating layer on the granular core. The granules with the imidacloprid and the wax coating on them, are allowed to cool to room temperature. Subsequently, the same second polymeric coating layer as described in Example 1 was applied on the imidacloprid and the wax coating layer using the same procedure as in Example 1 to produce the granular composition for the test. The concentration of imidacloprid in the composition of this Example 3 was 0.95% (by weight) as determined by the analytical chemical analysis techniques of High Performance Liquid Chromatography, standards. The composition of this Example 3 was subjected to the release test procedure as described in Example 1 and the results of this test are illustrated in Figure 3. As can be seen from the graphic display in Figure 3, this granular composition which has the biologically active imidacloprid ingredient incorporated in the wax, provided an efficient and effective system for the release of the active ingredient for a period greater than 30 days. Indeed, as demonstrated by the results shown in Figure 3, the composition of this invention provided a release of about 86% (by weight) of the active ingredient over a period of 175 days from the date of initial exposure to moisture while that only approximately 67% (by weight) of the core material was released during this same period of time so that approximately 33% (by weight) of the water-soluble portion of the granular core material remained within the granular composition during the 175 days of duration. EXAMPLE 4 The composition produced according to this Example 4 is distinguishable from the compositions produced according to Example 1 with respect to the active ingredient that was incorporated in the wax material used in the formation of the first coating layer of the sample of test of the granular agrochemical composition of the present invention and with respect to the polymeric composition that was used in the formation of the second coating layer on the compositions. The procedure used to produce the test sample of this Example 4 was in accordance with the process of Example 1. Specifically, a fertilizer granule 0-2-40 obtained from The Scotts Company that was predominantly composed of potassium sulfate was employed as the granular core material for the composition of the sample that was prepared by initially heating 50 g of the fertilizer granules 0-2-40 (1.7-2.0 mm) in a rotating drum at 110 ° C. Then, 3.5 g of the nonionic surfactant wax of Example 1 (a polyethylene glycol-block-polyethylene, case number: [251553-55-6], hydroxyl number of 52.00 mg KOH / g, containing 20% ( by weight) of polyethylene glycol, obtained from Sigma-Aldrich) were melted and 3.5 g of a biologically active ingredient of Fosetilo-Aluminio obtained from Bayer CropSciences were added by mixing them in the molten wax by the same procedure described in Example 1. Then, the The resulting mixture of Fosetyl-Aluminum and wax was added to the hot fertilizer granules (potassium sulfate) to form a coating layer on the granular core. The granules with the Fosetilo-Aluminio and the wax coating on them are allowed to cool to room temperature. Subsequently, a second polymeric coating layer was applied over the Fosetyl-Aluminum and the wax by the process described in Example 1 to produce the granular composition for the test. The polymer used as the second coating layer was a modified unsaturated oil copolymer based on the alkyd resin sold under the trademark Necolin 4071 by Ashland-Sudchemie-Kernsfest GmbH, Germany. The Fosetyl-Aluminum concentration in the composition of this Example 4 was 4.75% (by weight) as determined by the analytical chemical analysis techniques of High Resolution Liquid Chromatography, standards. The composition of this Example 4 was subjected to the release test procedure as described in Example 1 except that the release of Fosetyl-Aluminum was analyzed with a column for ion chromatography: Phenomenex starion A300: 1050x4.6 mm, eluent acetone 5% in water, with 1 mM HN03 and 3 mM NaN03 and the results of this test are illustrated in Figure 4. As can be seen from the graphical display in figure 4, this granular composition having the ingredient Fosetilo-Aluminio Biologically active incorporated in the wax, provided an efficient and effective system for the release of the active ingredient for a period greater than 30 days. Indeed, as demonstrated by the results shown in Figure 4, the composition of this invention provided a release of approximately 99% (by weight) of the active ingredient over a period of approximately 267 days from the date of initial exposure to moisture while only about 50% (by weight) of the core material was released during this same period of time. Example 5 Other granular test sample compositions according to this invention were produced using a hydrophobic test material in the formation of the first coating layer. The procedure used to produce the test sample of this Example 5 was in accordance with the process of Example 1. Specifically, a fertilizer granule 0-2-40 obtained from The Scotts Company that was composed predominantly of potassium sulfate was used as the granular core material for the composition of the sample that was prepared by initially heating 50 g of the fertilizer granules 0- 2 -40 (1 .7 - 2.0 mm) in a rotating drum at 110 eC. Then, 2. 5 g of a hydrophobic wax (Novoflow 02102 obtained from Holland NovochemBV, Nieuwegein, The Netherlands) - were melted and 2 were incorporated. 5 g of a biologically active ingredient of Fosetilo-Aluminio obtained from Bayer CropSciences mixing them in the molten wax by the same procedure described in Example 1. Then, the resulting mixture of Fosetyl-Aluminum and wax was added to the hot fertilizer granules (potassium sulfate) to form a coating layer on the granular core. The granules with the Fosetilo-Aluminio and the wax coating on them are allowed to cool to room temperature. Subsequently, a second polymeric coating layer was applied over the Fosetyl-Aluminum and the wax by the process described in Example 1 to produce the granular composition for the test. The polymer used as the second coating layer was a modified unsaturated oil copolymer based on the alkyd resin sold under the trademark Necolin 4071 by Ashland-Sudchemie-Kernsfest GmbH, Germany. The Fosetyl-Aluminum concentration in the composition of this Example 5 was 3.5% (by weight) as determined by the analytical chemical analysis techniques of High Resolution Liquid Chromatography, standards. The composition of this Example 5 was subjected to the release test procedure as described in Example 1 as modified in Example 4 and the results of this test are illustrated in Figure 5. As can be seen from the graphic display in Figure 5, this granular composition having the biologically active Fosetyl-Aluminum ingredient incorporated in the hydrophobic wax, provided an efficient and effective system for the release of the active ingredient for a period greater than 30 days. Indeed, as demonstrated by the results shown in Figure 5, the composition of this invention provided a release of about 80% (by weight) of the active ingredient over a period of 266 days from the date of initial exposure to moisture while only about 36% (by weight) of the core material was released during this period. time period so that approximately 64% (by weight) of the water soluble portion of the granular core material remained within the granular composition for approximately 266 days of duration. This result demonstrates the benefits derived from the use of a hydrophobic wax which leads to a slower release product which is desirable when a highly soluble active ingredient is incorporated therein. Although the invention has been described in its preferred forms with a certain degree of particularity, it is to be understood that the present description has been made by way of example only. Those skilled in the art will recognize, or will be able to ascertain, using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are proposed to be encompassed within the scope of the following claims. All publications, patents and patent applications mentioned in this specification are incorporated herein for reference in the specification to the same extent as if each individual publication, patent or patent application were specifically and individually indicated to be incorporated herein. for reference. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (46)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A granular agrochemical composition, characterized in that it comprises: a) a granular core material that includes a water-soluble portion; b) a first coating layer comprising a wax composition having a biologically active ingredient incorporated therein, applied on the surface of the core material; and c) a second coating layer comprising a polymer composition applied on the surface of the first coating layer; d) the granular composition exhibiting a rate of controlled release of the biologically active ingredient therefrom for a period greater than about 30 days from the date of initial exposure of the granular composition to moisture so that essentially all of the ingredient The biologically active agent incorporated in the wax material of the first coating layer is released from the granular composition before the water-soluble portion of the granular core material is released from the granular composition.
2. 2. The granular agrochemical composition according to claim 1, characterized in that the water-soluble portion of the core material generates sufficient osmotic pressure within the granular composition to cause the biologically active ingredient in the first coating layer to be released. from the same when the composition is in contact with moisture 3. The granular agrochemical composition according to claim 2, characterized in that the second coating layer is structured to withstand the osmotic pressure generated by the core material. granular agrochemical composition according to claim 1, characterized in that the water-soluble core material is a fertilizer 5. The granular agrochemical composition according to claim 4, characterized in that the fertilizer is selected from the group consisting of ammonium sulfate. , pota nitrate sio, potassium sulfate, urea, ammonium nitrate, monopotassium sulfate, ammonium phosphate, superphosphate, calcium phosphates, potassium phosphate, potassium chloride, magnesium oxide, magnesium sulfate, dolomite and mixtures thereof . 6. The granular agrochemical composition according to claim 4, characterized in that the core material includes at least one secondary nutrient or micronutrient. The granular agrochemical composition according to claim 6, characterized in that the secondary nutrient is selected from the group consisting of calcium, magnesium, sulfur and mixtures thereof. 8. The granular agrochemical composition according to claim 6, characterized in that the micronutrient is selected from the group consisting of chelated or non-chelated iron, copper, zinc, manganese, boron, cobalt, chlorine, sodium, molybdenum and mixtures thereof. . 9. The granular agrochemical composition according to claim 1, characterized in that the core material includes a non-active material. 10. The granular agrochemical composition according to claim 1, characterized in that the core material has a solubility of about 2 to about 800 g / 1. 11. The granular agrochemical composition according to claim 1, characterized in that the core material is shaped as a granule having a diameter of about 0.35 to about 6 mm. 12. The granular agrochemical composition according to claim 1, characterized in that the biologically active ingredient is selected from the group consisting of pesticides, insecticides, herbicides, fungicides, fertilizers, growth regulators, pheromones, biostimulants, acaricides., miticides, nematocides and mixtures thereof. 13. The granular agrochemical composition according to claim 1, characterized in that the wax composition has a melting point greater than 50 ° C. 14. The granular agrochemical composition according to claim 13, characterized in that the wax composition is hydrophobic. 15. The granular agrochemical composition according to claim 13, characterized in that the wax composition is hydrophilic. 16. The granular agrochemical composition according to claim 1, characterized in that the wax composition is soluble in water. 17. The granular agrochemical composition according to claim 1, characterized in that the polymer composition is a (semi) permeable material in water selected from the group consisting of thermosetting resins, thermoplastic resins, latex polymers and mixtures thereof. The granular agrochemical composition according to claim 1, characterized in that more than about 90% of the biologically active ingredient incorporated in the wax composition of the first layer is released from the granular composition while a residual amount of the portion soluble in the Water of the core material remains in the granular composition. 19. A process for preparing a granular agrochemical composition that exhibits a controlled release rate of a biologically active ingredient incorporated into the granular composition for a period greater than about 30 days from the date of initial exposure of the granular composition to moisture so which essentially all of the biologically active ingredient is released from the granular composition while at least a residual amount of a core material remains in the granular composition, characterized in that it comprises: a) providing a granular core material; b) applying a first coating layer comprising a wax composition having a biologically active ingredient incorporated therein onto the surface of the core material; and c) applying a second coating layer comprising a polymeric composition on the surface of the first coating layer. The process according to claim 19, characterized in that the core material is at least partially soluble in water, whereby a sufficient osmotic pressure is generated within the granular composition to cause the biologically active ingredient in the first coating be released from it when the core material comes into contact with water. 21. The process according to claim 20, characterized in that the second coating layer is structured to withstand the osmotic pressure generated by the core material. 22. The process according to claim 20, characterized in that the water-soluble core material is a fertilizer. 23. The process according to claim 22, characterized in that the fertilizer is selected from the group consisting of ammonium sulfate, potassium nitrate, potassium sulfate, urea, ammonium nitrate, monopotassium sulfate, ammonium phosphate, phosphate, calcium phosphates, potassium phosphate, potassium chloride, magnesium oxide, magnesium sulfate, dolomite and mixtures thereof. 24. The process according to claim 22, characterized in that the core material includes at least one secondary nutrient or micronutrient. 25. The process according to claim 24, characterized in that the secondary nutrient is selected from the group consisting of calcium, magnesium, sulfur and mixtures thereof. 26. The process according to claim 25, characterized in that the micronutrient is selected from the group consisting of chelated or non-chelated iron, copper, zinc, manganese, boron, cobalt, chlorine, sodium, molybdenum and mixtures thereof. 27. The process according to claim 19, characterized in that the core material includes a non-active material. 28. The process according to claim 19, characterized in that the core material has a solubility of about 2 to about 800 g / 1. 29. The process according to claim 19, characterized in that the core material is shaped as a granule having a diameter of about 0.35 to about 6 mm. 30. The process according to claim 19, characterized in that the biologically active ingredient is selected from the group consisting of pesticides, insecticides, herbicides, fungicides, fertilizers, growth regulators, pheromones, biostimulants, acaricides, miticides, nematocides and mixtures of the same. 31. The process according to claim 19, characterized in that the wax composition has a melting point greater than 50 ° C. 32. The process according to claim 31, characterized in that the wax composition is hydrophobic. 33. The process according to claim 31, characterized in that the wax composition is hydrophilic. 34. The process according to claim 19, characterized in that the wax composition is soluble in water. 35. The process according to claim 19, characterized in that the polymer composition is a (semi) permeable material in water selected from the group consisting of thermosetting resins, thermoplastic resins, latex polymers and mixtures thereof. 36. The process according to claim 19, characterized in that more than about 90% of the biologically active ingredient incorporated in the wax composition of the first layer is released from the granular composition while an amount residual of the core material remains in the granular composition. 37. An agrochemical composition that exhibits the controlled release of a biologically active ingredient for a period greater than about 30 days from the date of initial exposure of the composition to moisture at a rate of release such that essentially all of the ingredient is biologically active is released from the composition while at least a residual amount of a water-soluble portion of a core material remains in the granular composition, characterized in that it comprises a material of the granular core having a first coating layer comprising a wax material having a protection product for the plant incorporated therein, applied on the core material and a second applied polymeric coating layer on the first coating layer. 38. The granular agrochemical composition according to claim 37, characterized in that the core material is at least partially soluble in water whereby a sufficient osmotic pressure is generated within the granular composition to cause the biologically active ingredient in the first coating layer is released from it when the agrochemical composition makes contact with water. 39. The granular agrochemical composition according to claim 37, characterized in that the second coating layer is structured to withstand the osmotic pressure generated by the core material. 40. The granular agrochemical composition according to claim 37, characterized in that the water-soluble portion of the core material is a fertilizer. 41. The granular agrochemical composition according to claim 37, characterized in that the biologically active ingredient is selected from the group consisting of pesticides, insecticides, herbicides, fungicides, fertilizers, growth regulators, pheromones, biostimulants, acaricides, miticides, nematocides and mixtures thereof. 42. The granular agrochemical composition according to claim 37, characterized in that the wax composition has a melting point greater than 50 ° C. 43. The granular agrochemical composition according to claim 42, characterized in that the wax composition is hydrophobic. 44. The granular agrochemical composition according to claim 42, characterized in that the wax composition is hydrophilic. 45. The granular agrochemical composition according to claim 37, characterized in that the polymer composition is a (semi) permeable material in water selected from the group consisting of thermosetting resins, thermoplastic resins, latex polymers and mixtures thereof. 46. The granular agrochemical composition according to claim 37, characterized in that more than about 90% of the biologically active ingredient incorporated in the wax composition of the first layer is released from the granular composition while a residual amount of the core material remains in the granular composition.