JP2009029797A - Granular agrochemical composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a granular agrochemical composition in which an elution pattern of an agrochemically active ingredient in water is properly controlled thereby exhibiting excellent biological effectiveness over a long period of time, with no adverse effects on germination/rhizogenesis of paddy seeds or growth of seedling thereof due to a three component copolymer described below, and capable of reducing the frequency of spraying of agricultural chemicals thereby realizing reduction of quantity of works, and load of farm work and mitigation of environmental burden caused by chemical substances. <P>SOLUTION: The granular agrochemical composition for application during a period of seeding and raising of seedling comprises coating granules comprising an agrochemically active ingredient, a binder and a solid support with a coating material containing a three component copolymer of glycidyl methacrylate, methacrylic acid and an alkyl acrylate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention comprises a particulate material comprising an agrochemical active ingredient, a binder, and a solid carrier, which is coated with a coating material containing a ternary copolymer of glycidyl methacrylate, methacrylic acid and an alkyl acrylate ester. It is related with the agrochemical granular composition for the sowing seedling raising period control which controlled the elution pattern of the. Further, the seedling raising seedling characterized by covering a granular material comprising an agrochemical active ingredient, a binder and a solid carrier with a coating material containing a ternary copolymer of glycidyl methacrylate, methacrylic acid and alkyl acrylate. The present invention relates to a method for producing a granular composition for agrochemicals for seasonal application.

In recent agricultural chemical application, reduction of human burden (labor saving) and reduction of environmental burden are regarded as important. Pesticide dosage forms and pesticide application technologies that do not require large-scale spraying equipment are being developed in labor-saving situations. In the environment load reduction scene, it is desired to reduce the amount and frequency of use of agricultural chemicals, and the development of agricultural chemicals corresponding to that is being promoted. In such agrochemical development, the goal is to obtain a maximum medicinal effect by simply applying a minimum amount of pesticide to the control target. More recently, the so-called “drift” has become a major problem in the spraying of liquid dilution, powder spraying, etc., because the chemicals are scattered outside the area to be controlled. For example, it has been pointed out that the effects of drug scattering on residential environments in urban areas and surrounding crops in rural areas are pointed out.
Under such circumstances, in paddy rice cultivation, the application of a seedling box that applies the agricultural chemicals that have been applied in Honda until now in the sowing and seedling season and exerts its effect in Honda after transplanting has become widespread and established. Also in the cultivation of horticultural crops such as vegetables, cell tray application similar to paddy rice seedling box application is in the process of spreading and expanding. Both applications are ideal for saving labor and reducing environmental impact, and without worrying about drift. As the form of the agricultural chemical used at that time, the granular composition is particularly suitable for the purpose.
However, depending on the type of agrochemical active ingredient, even if paddy rice seedling boxes or horticultural crop cell trays are applied as a granular composition, the agrochemical active ingredient is eluted in water or soil in a short period of time, resulting in phytotoxicity. Or the duration of the medicinal effect is shortened. In order to solve such problems, various attempts have been made to control the elution of the pesticidal active ingredient to prolong the elution period, and in particular, the granular composition containing the pesticidal active ingredient is not water-soluble or difficult. Many agrochemical granular compositions coated with water-soluble coating materials have been developed.

As coating materials, waxes, synthetic resins, and synthetic rubbers are often used. For example, paraffin wax, carnauba wax, microcrystalline wax, and montanic acid wax are used for waxes, and polyvinyl acetate resin is used for synthetic resins. Polyurea resin, polyurethane resin, polycarboxylic acid resin, xylene resin, acrylic resin, rosin ester, and the like are used.
Among them, the acrylic resin is suitable as a coating material because it has features such as excellent water resistance and water permeability, good low-temperature film-forming properties, and little deterioration with time.
As general acrylic resins, acrylic acid, alkyl acrylate ester, methacrylic acid, methacrylic acid alkyl ester homopolymers, copolymers of these two or more, or these monomers and ethylene, vinyl chloride, Copolymers with one or more monomers selected from vinyl acetate, vinyl alcohol, vinylidene chloride, butadiene, styrene, acrylonitrile, polymerizable unsaturated silicones, and the like are known. Agrochemical particles coated with these acrylic resins A number of compositions have been disclosed (see, for example, Patent Documents 1, 2, or 3).

JP-A-6-9304 JP-A-60-202801 JP 2002-121101 A

When applying the coated pesticide granular composition to nursery boxes or cell trays, phytotoxicity may occur despite the suppression of elution of pesticidal active ingredients, and this is based on the coating material itself. Became clear. In addition, the occurrence of such phytotoxicity due to the coating material itself was more remarkable in the application at the time of sowing and the application at the early stage of raising seedling than the application at the time of transplanting in general and at the time of transplanting.
In this way, even if controlled release of agricultural chemical active ingredients by coating is achieved, for application to paddy rice seedling box application and cell tray application, it is necessary to select a coating material that does not cause phytotoxicity from seeding to treatment time, So far, no prior art in which a coating resin has been selected based on such knowledge has been found.

  The present invention is for paddy rice seedling box application and / or horticultural crop cell tray application in which release of agricultural chemical active ingredients is controlled by coating with a specific resin that does not cause phytotoxicity when applied to seedling boxes or cell trays. It is an object to provide a granular composition for agricultural chemicals. That is, in paddy rice seedling box cultivation, coating that does not cause phytotoxicity even if it is treated from seeding time to transplanting time from seeding time to transplanting, from seeding time to transplanting time, before seeding or after soiling, when seedling culture is mixed It is an object to provide an agrochemical granular composition coated with a material and a method for producing the same.

  As a result of intensive studies to solve the above problems, the inventors of the present invention, in an agricultural chemical granular composition coated with a ternary copolymer of glycidyl methacrylate, methacrylic acid and alkyl acrylate among acrylic resins, Even if it is applied at any time of paddy rice seedling period from paddy rice seedling box preparation to just before Honda transplanting, or cell tray seedling seedling period from sowing of horticultural crops to mainland transplanting, the coating material itself does not cause phytotoxicity and economical coating The inventors have found that the elution of the agrochemical active ingredient can be efficiently controlled by the amount, and completed the present invention.

That is, the present invention
[1] A method of coating a granular material containing an agrochemical active ingredient, a binder and a solid carrier with a coating material containing a three-component copolymer consisting of glycidyl methacrylate, methacrylic acid, and alkyl acrylate. Agrochemical granular composition for sowing and seedling application, characterized by
[2] The agricultural chemical granular composition according to [1], wherein the content of the coating material in the agricultural chemical granular composition is 0.1 to 60% by weight,
[3] The sowing and seedling application period is paddy rice seedling box application, and the application period is the period from the germination period to the transplanting period when the seedling culture soil is mixed, before sowing or after covering, at the time of sowing. The described agrochemical granular composition,
[4] The agrochemical granular composition according to [1] or [2], wherein the sowing and seedling application is a horticultural crop cell tray application, and the application time is a period from the sowing time to the transplanting time,
[5] The pesticidal active ingredient is selected from the group consisting of thiazinyl, probenazole, acibenzoral-S-methyl, isothianyl, orizastrobin, pyroxylone, isoprothiolane, azoxystrobin, furametopil, imidacloprid, thiacloprid, acetamiprid, dinotefuran, clothianidin, thiamethoxam. The agrochemical granular composition according to any one of [1] to [4], which is one type or two or more types,
[6] The pesticidal granular composition according to any one of [1] to [4], wherein the pesticidal active ingredient is thiazinyl.
[7] Seeding and raising seedling period characterized by coating granular material containing agrochemical active ingredient, binder and solid carrier with coating material containing copolymer of glycidyl methacrylate, methacrylic acid and alkyl acrylate ester A method of producing an agrochemical granular composition for application,
About.

  A coating material containing a ternary copolymer of glycidyl methacrylate, methacrylic acid and alkyl acrylate is coated with a particulate material containing an agrochemical active ingredient, a binder and a solid carrier. In the agrochemical granular composition of the present invention for application to, for example, paddy rice seedling boxes, the elution pattern of the agrochemical active ingredient in water is appropriately controlled. As a result, the agrochemical granular composition of the present invention exhibits an excellent biological effect over a long period of time. In addition, the ternary copolymer of glycidyl methacrylate, methacrylic acid and alkyl acrylate itself does not adversely affect the germination and rooting of rice seeds or the growth of seedlings, avoiding the rice seedling raising period and phytotoxicity after transplanting to Honda Is done. With such performance, it is possible to reduce the number of spraying of agricultural chemicals. Moreover, the burden of farm work can be reduced especially by reducing the amount of work in paddy field Honda. At the same time, the environmental impact of chemical substances can be reduced.

Next, the granular agrochemical composition of the present invention and the production method thereof will be specifically described.
As the agrochemical active ingredient, insecticides and fungicides are mainly used, but in some cases, herbicides, plant growth regulators and the like can be blended, and these can be blended in one kind or two or more kinds at the same time. The blending amount is preferably 0.01 to 60% by weight, more preferably 0.1 to 50% by weight, based on 100% by weight of the total amount of the agricultural chemical granular composition.

  Specific agrochemical active ingredients (generic names) include, for example, phenylpyrazole insecticides such as fipronil, acetoprole, imidacloprid, acetamiprid, nitenpyram, dinotefuran dinotefuran, thiacloprid, thiamethoxam, clothianidin and other neonicotinoid insecticides, macrolide insecticides such as spinosad, carbamate insecticides such as benfuracarb, acephate Organophosphorus insecticides such as (acephate), various insecticides such as flonicamid, flubendiamide, chlorantraniliprole, tiadinil, probenazole, acibenzoral-S Plant resistance-induced disease control agents such as methyl (acibenzolar-S-methyl) and isothianyl (development code: BYF-1047), isoprothiolan, carpropamid, diclocymet, pyroquilon, oryastrobine (Orysastrobin), azoxystrobin, tricyclazole, furametpyr, furtolanil, flutolanil, thifluzamide and the like, but are not limited to these. As the active ingredient of the agricultural chemical in the present invention, for example, thiazinyl, probenazole, acibenzoral-S-methyl and isotianil used as plant resistance-induced disease control agents for paddy rice, orisatrobin and pyroxylone used as paddy rice fungicides , Isoprothiolane, azoxystrobin and furametopil, imidacloprid, thiacloprid, acetamiprid, dinotefuran, clothianidin and thiamethoxam, which are used as insecticides for paddy rice, are preferred, and thiazinyl is particularly preferred.

A binder and a solid carrier are indispensable for forming an agrochemical granular composition. The binders are classified into natural, semi-synthetic and synthetic polymers. For example, natural ones include starch, arabic gum, tragacanth gum, guar gum, mannan, pectin, sorbitol, xanthan gum, dextran, gelatin , Casein and the like. Examples of semi-synthetic systems include dextrin, soluble starch, oxidized starch, pregelatinized starch, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose. Synthetic systems include polyvinyl alcohol. , Polyacrylamide, polyvinyl pyrrolidone, sodium polyacrylate, ethylene-acrylic acid copolymer, maleic anhydride copolymer, polyethylene glycol and the like, but are not limited thereto. Moreover, it is also possible to use 1 type individually or to use 2 or more types together, The addition amount is 0.1 to 20 weight% normally with respect to a granular agrochemical composition whole quantity, Preferably it is 0.00. 3 to 10% by weight.

  On the other hand, solid carriers are classified into water-insoluble solid carriers and water-soluble solid carriers. Examples of water-insoluble solid carriers include clay, calcium carbonate, talc, bentonite, calcined diatomaceous earth, uncalcined diatomaceous earth, hydrous silica. Examples include acid, cellulose, pulp, rice bran, wood powder, and kenaf powder. Examples of the water-soluble solid carrier include inorganic salts such as ammonium sulfate, sodium chloride, and potassium chloride, sugars such as glucose, sucrose, fructose, and lactose, urea, urea formalin condensate, organic acid salt, and water-soluble amino acids. Etc. These extenders (solid carriers) may be used alone or in combination of two or more. The addition amount of these solid carriers is usually 0.5 to 99.79% by weight, preferably 20 to 98% by weight, based on the total amount of the granular agrochemical composition.

  In addition, the agrochemical granular composition according to the present invention maximizes the medicinal effects of the agrochemical active ingredient contained therein, or to improve the quality of the agrochemical granular composition. Various auxiliary components such as a solvent, a grinding aid, an absorbent, a decomposition inhibitor, and a pigment are added. Moreover, it is necessary to determine those selections and compounding ratios so as to be compatible with the properties of the agricultural chemical active ingredients to be used.

  Surfactants include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, alkyl naphthalene sulfonate, alkyl sulfate, polysulfate Examples include anionic surfactants such as oxyethylene alkyl ether sulfate, polyoxyethylene polystyryl phenyl ether sulfate, polyoxyethylene polystyryl phenyl ether phosphate, and dioctyl sulfosuccinate.

As described above, granulates containing an agrochemical active ingredient, a binder, and a solid carrier that are blended in accordance with various purposes are generally known as extrusion granulation method, rolling granulation method, rolling fluidized bed granulation method. It can be produced by a granulation method, a fluidized bed granulation method, a stirring mixed granulation method, or the like. For example, in the case of obtaining a cylindrical granulated product, the extrusion granulation method is preferable. After mixing the agrochemical active ingredient with a binder, a solid carrier and various auxiliary ingredients, kneading with an appropriate amount of water, a basket type granulator , Granulated using an extrusion granulator such as a disk rotary granulator, screw-type horizontal granulator, screw-type forward granulator, twin dome gran (manufactured by Fuji Paudal), etc. It can be manufactured by cutting, drying, and sieving.
In order to obtain a spherical granulated product, the tumbling granulation method and the stirring mixed granulation method are preferable. The agrochemical active ingredient, solid carrier, binder and other auxiliary ingredients are mixed, and this mixture is granulated by a granulator. Rotating the stirring blade in the vessel to make it agitated and rolled, then dripping or spraying water and / or binder aqueous solution, etc. to grow the particles to an appropriate size, granulating, drying and sieving Can be manufactured.

The coating material in the present invention contains a three-component copolymer composed of glycidyl methacrylate, methacrylic acid, and alkyl acrylate. The copolymer does not adversely affect seed germination / rooting or seedling growth. As the acrylic acid alkyl ester, the alkyl group having 1 to 12 carbon atoms and a linear or branched alkyl group, for example, methyl acrylate, ethyl acrylate, propyl acrylate,
Examples include butyl acrylate, hexyl acrylate, octyl acrylate, and dodecyl acrylate. The form of the coating material is not particularly limited, but an aqueous emulsion obtained by an emulsion polymerization method using a surfactant is preferred. Examples of commercially available products include “Banazol KB660” and “Vanazol K-3608HN” (Shin Nakamura Chemical Co., Ltd.).

The coating material in the present invention may be the above copolymer alone or a mixture with other coating materials as long as it is a combination that does not cause phytotoxicity as an agrochemical particulate.
Other coating materials include waxes, synthetic resins and synthetic rubbers.
Examples of waxes include paraffin wax, carnauba wax, microcrystalline wax, and montanic acid wax. Synthetic resins include polyvinyl acetate resin, polyurea resin, polyurethane resin, polycarboxylic acid resin, xylene resin, rosin ester, and the like. An acrylic resin other than the above-mentioned copolymer in the present invention is used.

Examples of the acrylic resin other than the copolymer in the present invention include acrylic acid, alkyl acrylate ester, methacrylic acid, homopolymer of methacrylic acid alkyl ester or these monomers and ethylene, vinyl chloride, vinyl acetate, And a copolymer with at least one monomer selected from vinyl alcohol, vinylidene chloride, butadiene, styrene, acrylonitrile, polymerizable unsaturated silicone, and the like.
When mixed and used, the mixing ratio is at least about 2% by weight, preferably about 5% by weight or more of the total weight of the coating material of the copolymer in the present invention, from the viewpoint of controlling the release of the pesticidal active ingredient. is there.

  The amount of the coating material used in the present invention is usually 0.1 to 60% by weight, preferably 0.5 to 50% by weight, more preferably 1 to 35% by weight as the content in the granular agrochemical composition. is there. When the amount used is less than 0.1% by weight, the coating is incomplete, the coating thickness is not sufficient, and as a result, the release control of the agrochemical active ingredient becomes insufficient, resulting in phytotoxicity, Sustained control effect is insufficient. On the other hand, if the amount used exceeds 60% by weight, the coating is too thick and the pesticidal active ingredient is hardly eluted, and the desired control effect cannot be obtained. There's a problem. A desirable coating thickness is about 0.3 to 900 μm, preferably about 1 to 500 μm.

  Examples of a method for coating a coating material containing the copolymer on a granular material containing an agrochemical active ingredient, a binder, and a solid carrier include, for example, rolling in a fluidized bed under a heated air stream, rotating pan, or rotating drum. The emulsion of the copolymer is sprayed or dripped continuously or intermittently on the granular material in the inside and dried, or the granular material and the emulsion of the copolymer are mixed with a Nauta mixer or drum mixer. -Although the method of making it absorb and fluidized bed drying etc. is shown, of course, it is not limited to these.

The granular pesticidal composition of the present invention can be applied to all scenes in pesticide application, but is particularly effective in the so-called sowing and seedling season when it is applied at the seed germination / rooting stage or the seedling growth stage. For example, in the case of paddy rice seedling seedling, when it is mixed with seedling culture soil, before sowing at the time of sowing or after covering, application during the period from the germination period to just before transplanting has been developed, and in recent years, simultaneous transplanting has also been developed. Application is also possible. In addition, cell tray raising seedlings such as vegetables can be similarly applied from the time of mixing seedling culture soil to the time of transplanting, and particularly preferred are application at the time of sowing and germination, and the treatment of planting holes at the time of transplanting.
In the sowing and seedling raising period, usually a seedling culture soil is used, but it can also be applied to other cultures such as seedling mats and sheets.

As an application method, it can be applied by the same method as a normal granular agrochemical composition. For example, direct hand granulation, human-powered granulator, electric granulator, back-loaded power granulation Examples thereof include a method using an air granulator such as a machine, a traveling power granulator, a tractor-equipped granule mill, a rice transplanter-equipped granule mill, a sideline application medicine, an unmanned helicopter.
For example, in paddy rice seedling box medicine, scooping granular pesticide composition with a measuring cup that can measure a predetermined amount, sprinkling it on the seedling box, putting it in a special seedling box spraying container, spraying it into the seedling box, pesticide granular composition A method of directly spraying seedling boxes from the outlets and holes provided on the product packaging container, a method of spraying a large number of seedling boxes placed over a wide area using a power-type granulator, and a dedicated seeding operation Examples thereof include a method of granulating the seedling box in the apparatus and a method of mixing with the seedling soil.

  In order to properly perform the above-described spraying, the physical properties of the agrochemical granular composition of the present invention are preferably within a certain range for various items. For example, the apparent specific gravity is preferably 0.3 to 2.0, more preferably 0.5 to 1.5 in the official agricultural chemical inspection method. The hardness of the grains is preferably 20 or less, more preferably 10 or less in the whole agricultural ball mill method. It is preferable that the particle size is 90% by weight or more of the whole granular composition which passes through a sieve having an opening of 1700 μm and does not pass through a sieve having an opening of 300 μm. Moreover, when a particle | grain is cylindrical, the diameter of a cross-sectional circle has preferable 0.3-2.0 mm, More preferably, it is 0.5-1.5 mm. The grain length corresponding to the height of the cylinder is preferably 0.5 to 6 times the circular diameter of the cross section. However, when spraying using a dedicated device at the time of sowing, for example, a seedling box-applied drug spraying device (beauty Good, model KS-25: Roller-type granulator), seedling box medicine hopper (Suzutec, model SDP-33S, SDP-103S: Roller-type granulator), pot seedling box medicine device (Minoru Industry Co., Ltd.) Manufactured, type MPA-21: roller type granulator), particles having a grain length of 2.5 times or more with respect to the cross-sectional circle diameter should be 50% by weight or less of the whole granular composition. Is more preferable, and more preferably 10 to 40% by weight.

In addition, the application amount at the time of applying the granular agrochemical composition of the present invention is 0.1-20 kg per 10 ares, preferably 0.2 kg-5 kg in the case of paddy fields and upland fields, The seedling box (usually 0.16 m ² ) is 10 to 200 g, preferably 10 to 100 g per sheet. For example, when applied to a cell tray, an application amount of about 30 g per cell tray (128 holes) may be used.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by weight”.

Example 1
13.3 parts of thiazinyl, 2.0 parts of polyvinyl alcohol, 0.5 part of polyoxyethylene alkyl ether, 10.0 parts of hydrous silicic acid and 74.2 parts of clay were mixed with a double arm kneader (manufactured by Fuji Powder Co., Ltd.). Thereafter, 30.0 parts of water was added and sufficiently kneaded. Next, this hydrated kneaded product was granulated with a basket type extrusion granulator (manufactured by Kikusui Seisakusho Co., Ltd.) equipped with a screen having a pore diameter of 1.2 mm. The obtained granulated material was dried with a fluidized bed dryer (manufactured by Ogawara Seisakusho Co., Ltd.), and then sieved with a sieve shaker equipped with sieve screens having openings of 500 μm and 1400 μm to obtain a granular material. 90.0 parts of this granular material is put in a sugar-coated bread (manufactured by Kikusui Seisakusho Co., Ltd.), 30.3 parts of a copolymer emulsion of glycidyl methacrylate, methacrylic acid, and alkyl acrylate (pure content 33%) and water The mixed liquid of 4.7 parts was sprayed. After removing the coated granular material (wet material) from the sugar-coated bread, it is dried with a fluid bed dryer and coated with 10% copolymer of glycidyl methacrylate, methacrylic acid, and alkyl acrylate ester. I got a thing.
The physical properties of this coated agrochemical granular composition were an apparent specific gravity of 0.93, a hardness of 1, a grain size (300 to 1700 μm) of 98%, and a grain size of 21% that was 2.5 times or more of the cross-sectional circle diameter.

Example 2
13.0 parts of thiazinyl, 2.0 parts of polyvinyl alcohol, 0.5 part of polyoxyethylene alkyl ether, 10.0 parts of hydrous silicic acid and 74.5 parts of clay were mixed with a double arm kneader (manufactured by Fuji Powder Co., Ltd.). Thereafter, 30.0 parts of water was added and sufficiently kneaded. Next, this hydrated kneaded product was granulated with a basket type extrusion granulator (manufactured by Kikusui Seisakusho Co., Ltd.) equipped with a screen having a pore diameter of 1.2 mm. The obtained granulated material was dried with a fluidized bed dryer (manufactured by Ogawara Seisakusho Co., Ltd.), and then sieved with a sieve shaker equipped with sieve screens having openings of 500 μm and 1400 μm to obtain granular materials. 92.5 parts of this granular material is placed in a sugar-coated bread (manufactured by Kikusui Seisakusho Co., Ltd.), and 22.7 parts of a copolymer emulsion of glycidyl methacrylate, methacrylic acid and alkyl acrylate (pure content 33%) and water The liquid in which 12.3 parts were mixed was sprayed. After removing the coated granular material (wet material) from the sugar-coated bread, it was dried with a fluidized bed dryer and coated with 7.5% glycidyl methacrylate, methacrylic acid, alkyl acrylate copolymer. A granular composition was obtained.
The physical properties of this coated granular agricultural chemical composition were an apparent specific gravity of 0.92, a hardness of 1, a particle size (300 to 1700 μm) of 97%, and a grain size of 24% that was 2.5 times or more of the cross-sectional circle diameter.

Example 3
12.6 parts of thiazinyl, 2.0 parts of polyvinyl alcohol, 0.5 part of polyoxyethylene alkyl ether, 10.0 parts of hydrous silicic acid and 74.9 parts of clay were mixed with a double-arm kneader (manufactured by Fuji Powder Co., Ltd.). Thereafter, 30.0 parts of water was added and sufficiently kneaded. Next, this hydrated kneaded product was granulated with a basket type extrusion granulator (manufactured by Kikusui Seisakusho Co., Ltd.) equipped with a screen having a pore diameter of 1.2 mm. The obtained granulated material was dried with a fluidized bed dryer (manufactured by Ogawara Seisakusho Co., Ltd.), and then sieved with a sieve shaker equipped with sieve screens having openings of 500 μm and 1400 μm to obtain granular materials. 95.0 parts of this granular material is put in a sugar-coated bread (manufactured by Kikusui Seisakusho Co., Ltd.), 15.2 parts of a copolymer emulsion of glycidyl methacrylate, methacrylic acid, and alkyl acrylate (pure content 33%) and water The liquid in which 19.8 parts were mixed was sprayed. After removing the coated granular material (wet material) from the sugar-coated bread, it was dried with a fluidized bed dryer and coated with 5.0% copolymer of glycidyl methacrylate, methacrylic acid and alkyl acrylate ester. A granular composition was obtained.
The physical properties of this coated granular agricultural chemical composition were an apparent specific gravity of 0.91, a hardness of 1, a particle size (300 to 1700 μm) of 98%, and a grain size of 22% that was 2.5 times or more of the cross-sectional circle diameter.

Example 4
13.5 parts of thiazinyl, 2.0 parts of polyvinyl alcohol, 0.5 part of polyoxyethylene alkyl ether, 10.0 parts of hydrous silicic acid and 74.0 parts of clay were mixed with a double arm kneader (manufactured by Fuji Powder Co., Ltd.). Thereafter, 30.0 parts of water was added and sufficiently kneaded. Next, this hydrated kneaded product was granulated with a basket type extrusion granulator (manufactured by Kikusui Seisakusho Co., Ltd.) equipped with a screen having a pore diameter of 1.2 mm. The obtained granulated material was dried with a fluidized bed dryer (manufactured by Ogawara Seisakusho Co., Ltd.), and then sieved with a sieve shaker equipped with sieve screens having openings of 500 μm and 1400 μm to obtain granular materials.
On the other hand, 30.0 parts of fipronil, 0.5 part of polyvinyl alcohol, 1.0 part of polyoxyethylene alkyl ether, 0.1 part of silicone oil, and 68.4 parts of water were mixed, and a bead stirring type wet pulverizer (Dynomill KDL) was mixed. , Manufactured by Willy et Bacofen) to obtain a suspension having an average particle diameter of 2 μm.
88.9 parts of the above granular material is put in a sugar-coated bread (manufactured by Kikusui Seisakusho Co., Ltd.), and 30.3 parts of a copolymer emulsion of glycidyl methacrylate, methacrylic acid, and alkyl acrylate (pure content 33%), A mixture of 3.4 parts of fipronil-containing suspension (1.1 parts pure) and 2.4 parts of water was sprayed. After removing the coated granular material (wet material) from the sugar-coated bread, it was dried with a fluidized bed drier and coated with 10.0% copolymer of glycidyl methacrylate, methacrylic acid and alkyl acrylate ester. A granular composition was obtained.
The physical properties of this coated granular agricultural chemical composition were an apparent specific gravity of 0.92, a hardness of 1, a grain size (300 to 1700 μm) of 98%, and a grain size of 20% that was 2.5 times or more of the cross-sectional circle diameter.

Comparative Example 1
In Example 1, 30.3 parts of a copolymer emulsion of glycidyl methacrylate, methacrylic acid and acrylic acid alkyl ester (pure 33%) was added to a polylactic acid resin emulsion (trade name: Prasema L110, pure). In the same manner as in Example 1 except that the amount of water mixed with this was changed to 20.0 parts, and 15.0 parts of water mixed therewith was coated with 10.0% polylactic acid resin. An agrochemical granular composition was obtained.
Comparative Example 2
In Example 1, 30.3 parts of a copolymer emulsion of glycidyl methacrylate, methacrylic acid, and acrylic acid alkyl ester (pure 33%) was added to a vinyl acetate resin emulsion (trade name: Mobile M110, pure). Pesticide granules coated with 10.0% vinyl acetate resin in the same manner as in Example 1 except that 18.2 parts of 55% content, made by Hoechst), and 16.8 parts of water mixed therewith were used. A composition was obtained.

Comparative Example 3
In Example 1, 30.3 parts of a copolymer emulsion of glycidyl methacrylate, methacrylic acid, and acrylic acid alkyl ester (pure 33%) was added to an ester ether resin emulsion (trade name: Superflex 126, (Ester ether resin 10.0% in the same manner as in Example 1 except that it is replaced with 33.3 parts of 30% pure content, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) A coated agrochemical granular composition was obtained.
Comparative Example 4
In Example 1, 30.3 parts of a copolymer emulsion of glycidyl methacrylate, methacrylic acid and acrylic acid alkyl ester (pure 33%) was added to a silica-acrylic resin emulsion (trade name: PM541-34). In the same manner as in Example 1, except that the amount of water mixed with this was changed to 12.8 parts. A 0% coated agrochemical granular composition was obtained.

Comparative Example 5
In Example 1, 30.3 parts of a copolymer emulsion of glycidyl methacrylate, methacrylic acid, and alkyl acrylate ester (pure 33%) was added to a carbonate resin emulsion (trade name: Superflex 420, pure). This was replaced with 31.3 parts of 32% content, made by Daiichi Kogyo Seiyaku Co., Ltd., and coated with 10.0% carbonate resin in the same manner as in Example 1 except that the amount of water mixed with this was 3.7 parts. A pesticide granular composition was obtained.
Comparative Example 6
12.0 parts of thiazinyl, 2.0 parts of polyvinyl alcohol, 0.5 part of polyoxyethylene alkyl ether, 10.0 parts of hydrous silicic acid and 75.5 parts of clay were mixed with a double arm kneader (manufactured by Fuji Powder Co., Ltd.). Thereafter, 30.0 parts of water was added and sufficiently kneaded. Next, this hydrated kneaded product was granulated with a basket type extrusion granulator (manufactured by Kikusui Seisakusho Co., Ltd.) equipped with a screen having a pore diameter of 1.2 mm. The obtained granulated product was dried with a fluidized bed dryer (manufactured by Okawara Seisakusho Co., Ltd.), and then sieved with a sieve shaker equipped with a sieve net having openings of 500 μm and 1400 μm to obtain an agrochemical granular composition. .

About the agricultural chemical granular composition prepared in Examples 1-4 and Comparative Examples 1-6, it tested by the following method.
Test Example 1 Elution test in water 100 ml of hard water was poured into a 225 ml mayonnaise bottle and allowed to stand.
Each sample prepared in Examples 1 to 4 and Comparative Examples 1 to 6 was precisely weighed and then dropped uniformly into the hard water. When the grains were floating on the water surface, they settled on the bottom of the water. The mayonnaise bottle was allowed to stand at 20 ° C. under light-shielded constant temperature conditions, and water was collected from the middle layer after 6 hours and 24 hours, and the thiazinyl concentration in the collected water sample was measured using a high performance liquid chromatograph. The results are shown in Table 1.

Test Example 2 Paddy rice phytotoxicity test and investigation method: Rice bran (variety: Hitomebore) was soaked in Sportac Stana SE (diluted 200 times) for 24 hours, air-dried, and soaked at 15 ° C. for 6 days, and germination was performed at 30 ° C. 24 The test was conducted for a period of time. Newspaper, 2.2 kg of floor soil (Kumiai Ube Culture No. 2) was laid on the bottom of the standard nursery box, and 150 g of persimmon was seeded per box. After sowing, Daconil 1000 (diluted 800 times) was sprayed with a 500 ml shower per box, and the soil was disinfected. Each drug was treated with 50 g per standard nursery box and covered with soil (1.1 kg) from the top. After budding for 72 hours in a 30 ° C. inoculation box, cultivation was performed in a greenhouse (25-18 ° C. setting) for 21 days. 21 days after the treatment, phytotoxicity against rice was investigated according to the criteria of (-: no phytotoxicity, ±: slight, + mild, ++ moderate, +++ severe; notation above + is practically problematic). The results are shown in Table 2.

Comparative Examples 1 to 5 are granules coated by the conventional technique. In contrast to Comparative Example 6, elution of the active ingredient is controlled, but chemical damage has occurred. Further, Comparative Example 6 is a granule that is not coated at all, and since the elution of the active ingredient is not controlled, there is a strong phytotoxicity caused by the active ingredient. For example, in Example 3 of the present invention, elution control is performed to the same extent as Comparative Examples 1 to 5, but no phytotoxicity is observed. This indicates that the present invention controls the elution of the active ingredient and no phytotoxicity due to the active ingredient and the coating material is found by using the coating material of the present invention.

Claims (7)

  A seedling raising seedling characterized by covering a granular material comprising an agrochemical active ingredient, a binder and a solid carrier with a coating material containing a ternary copolymer of glycidyl methacrylate, methacrylic acid and alkyl acrylate. Agrochemical granular composition for seasonal application.   The pesticidal granular composition according to claim 1, wherein the content of the coating material in the pesticidal granular composition is 0.1 to 60% by weight.   3. Agrochemical granular composition according to claim 1 or 2, wherein the sowing seedling application is paddy rice seedling box application, and the application period is a period from the germination period to the transplanting period when mixed with the seedling culture medium, before sowing or after covering at the time of sowing. object.   The pesticide granular composition according to claim 1 or 2, wherein the sowing and seedling application is a horticultural crop cell tray application, and the application time is a period from seeding to transplanting.   One or more selected from the group consisting of thiazinyl, probenazole, acibenzoral-S-methyl, isothianyl, orisatrobin, pyroxylone, isoprothiolane, azoxystrobin, flumetopil, imidacloprid, thiacloprid, acetamiprid, dinotefuran, clothianidin, thiamethoxam It is 2 or more types, The agricultural chemical granular composition of any one of Claims 1 thru | or 4.   The agrochemical granular composition according to any one of claims 1 to 4, wherein the agrochemical active ingredient is thiazinyl. Seedling and seedling application, characterized in that a granular material comprising an agrochemical active ingredient, a binder and a solid carrier is coated with a coating material containing a ternary copolymer of glycidyl methacrylate, methacrylic acid and alkyl acrylate. For producing a granular composition for agricultural chemicals.