JP2007308413A - Agrochemical granular formulation and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an agrochemical granular formulation that controls release of agrochemical active ingredient in a control direction and does not cause phytotoxicity in the whole application periods of agrochemical including applications of sowing period and seedling raising period of field crop by coating agrochemical active ingredient-containing granules with a specific coating material, as a result, performs labor saving, reduction in environmental loading and drift prevention and phytotoxicity prevention in agrochemical application and to provide a method for producing the same. <P>SOLUTION: The agrochemical granular formulation is obtained by coating agrochemical active ingredient-containing granules with a coating material comprising a copolymer of methacrylic acid and an acrylic acid alkyl ester (especially a copolymer of methacrylic acid and ethyl acrylate). The method for producing the agrochemical granular formulation comprises a process for coating agrochemical active ingredient-containing granules with a coating material composed of a copolymer of methacrylic acid and an acrylic acid alkyl ester. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is characterized in that a particulate material containing an agrochemical active ingredient is coated with a coating material containing a copolymer of methacrylic acid and an alkyl acrylate, and the release of the agrochemical active ingredient is controlled in a restraining direction. The present invention relates to an agrochemical granular preparation which can be applied and has no problem of phytotoxicity even when applied during the sowing and / or raising period of crops.

Labor saving and reduction of environmental burden are regarded as important in recent agricultural chemical application. Agricultural chemicals and application technologies that do not require large-scale spraying equipment have been developed in labor-saving situations. In the environment load reduction scene, it is desired to reduce the application amount and the frequency of application of agricultural chemicals. In such agrochemical development, the goal is to obtain the maximum medicinal effect by simply applying a minimum amount of pesticide to the control target. More recently, in the case of spraying diluted liquids or powders, the so-called “drift” has become a big problem that the chemicals are scattered outside the controlled area. For example, in urban areas, the impact on the living environment Has pointed out the effect on surrounding crops.
Under such circumstances, as a method of applying agricultural chemicals in paddy rice cultivation, the agricultural chemicals that have been applied in Honda until now are applied to the sowing and / or seedling season in the nursery box before transplanting to Honda. After transplanting, a nursery box application has been widely established in Honda. As a method for applying agricultural chemicals in the cultivation of horticultural crops such as vegetables, cell tray application similar to paddy rice cultivation seedling box application is in the process of spreading and expanding. Both application methods are ideal for saving labor and reducing environmental impact, and without worrying about drift. From the standpoint of drift prevention, the granular formulation is more suitable for the purpose than the liquid or powder as the form of the agricultural chemical.
However, in normal granular preparations, depending on the type of pesticidal active ingredient, the pesticidal active ingredient may be released into water or soil in a short period of time, causing phytotoxicity and shortening the duration of medicinal effects. There was a case. In particular, in the case of paddy rice seedling box application or cell tray application, it is generally necessary to apply at a high concentration in order to exert the effects in the main field or the main field, and as a result, it is easy to cause phytotoxicity, and even when applied at a high concentration, it is effective. In some cases, the duration of the above is not sufficiently extended.
In order to solve such problems, various attempts have been made to control the release of pesticidal active ingredients in a restraining direction and to extend the release period, and in particular, particulates containing pesticidal active ingredients are not water-soluble. Many agrochemical granular formulations coated with a water-soluble or poorly water-soluble coating material have been developed.

As coating materials, waxes, synthetic resins and synthetic rubbers are often used. For example, paraffin wax, carnauba wax, microcrystalline wax, montanic acid wax and the like 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 characteristics such as excellent water resistance and water permeation resistance, good low-temperature film-forming properties, and little deterioration with time.
In Patent Document 3, as a conventional acrylic resin, a homopolymer of acrylic acid, alkyl acrylate ester, methacrylic acid, alkyl methacrylate ester, two or more types of these copolymers, or these monomers It is described that a copolymer with at least one monomer selected from ethylene, vinyl chloride, vinyl acetate, vinyl alcohol, vinylidene chloride, butadiene, styrene, acrylonitrile and the like is known.

As an agrochemical granular preparation in which a granular material containing an agrochemical active ingredient is coated with a water-insoluble or poorly water-soluble coating material, specifically, for example, in Patent Document 1, the surface of a granular carrier containing an agrochemical ingredient is coated with an alkaline substance. A coated granular pesticide is disclosed in which a first coating layer is formed, and a second coating layer made of a mixture of an olefin polymer and an alkaline water-soluble polymer is formed on the surface of the first coating layer. . Patent Document 2 discloses a sustained-release granular material obtained by coating a granule-forming nucleus composed of an agricultural chemical active ingredient and a solid diluent with a wax and an acrylic resin. Further, Patent Document 3 discloses a coated granular agricultural chemical composition comprising a granular material containing an agrochemical active ingredient, a binder, and a solid carrier, and an acrylic silicone resin that covers the granular material.
JP-A-6-9304 JP-A-60-202801 JP 2002-121101 A

As a result of intensive research, the present inventors have applied a conventional pesticidal granular preparation in which a granular material containing an pesticidal active ingredient is coated with a water-insoluble or poorly water-soluble coating material in the sowing period and seedling period of agricultural crops (for example, When using rice (especially paddy rice) in seedling boxes or horticultural crop cell trays, etc., there may be cases where phytotoxicity may occur despite the controlled release of agrochemical active ingredients. It was found that the cause of this is that the coating material itself adversely affects the germination and rooting of crop seeds or the growth of seedlings. In addition, the present inventors have reported that the occurrence of phytotoxicity due to the coating material itself is applied at the sowing time and the early stage of raising the seedling rather than immediately before or at the time of transplanting the seedlings of crops to Honda or the mainland. We obtained the knowledge that it is remarkable.
From the above knowledge, the present inventors have found that in order to achieve labor saving, reduction of environmental burden, prevention of drift and prevention of chemical damage in application of agricultural chemicals, in the formulation design of agricultural chemicals, in the direction of suppressing release of agricultural chemical active ingredients by coating. Is controlled and does not cause phytotoxicity during the entire application period of agricultural chemicals including application of seeding and seedling periods of agricultural crops (for example, application of seedling boxes for rice (especially paddy rice) and cell tray application of horticultural crops) We focused on the need to select a coating material. So far, no prior art in which a coating resin has been selected based on such knowledge has been found.

  The present invention can control the release of the pesticidal active ingredient in a restraining direction by coating the granular material containing the pesticidal active ingredient with the specific coating material of the present invention to be described later, and the sowing time and seedling of the agricultural crop. Do not cause phytotoxicity during the entire application period of the agricultural chemicals including the application of the season (eg, seedling box application of rice (especially paddy rice), cell tray application of horticultural crops, etc.), resulting in labor saving and reduction of environmental burden Another object of the present invention is to provide an agrochemical granular preparation capable of achieving drift prevention and chemical damage prevention.

As a result of intensive studies to solve the above problems, the present inventors have found that among acrylic resins, a copolymer of methacrylic acid and an alkyl acrylate ester, in particular, a copolymer of methacrylic acid and ethyl acrylate. Preparation and sowing of seedling boxes for rice seedlings (especially paddy rice) The seedling and seedling period from planting to seedling right before the transplantation of seedlings, and seedling and seedling period from horticultural crop cell tray preparation and sowing to seedling transplanting to the seedling in the field, etc. Even if the coating material itself does not cause phytotoxicity, it is possible to control the release of active ingredients of agricultural chemicals in a restraining direction. It found that deactivator is possible, and completed the present invention by further studying.
The agrochemical granular preparation of the present invention is further a weight average molecular weight, a minimum film forming temperature and a glass transition temperature (hereinafter abbreviated as Tg) as a copolymer of methacrylic acid and alkyl acrylate contained in the coating material. )) Within the specific range described later, the release of the pesticidal active ingredient can be more efficiently controlled in the suppression direction with an economical coating amount.

That is, the present invention
[1] Agrochemical granular preparation comprising a granular material containing an agrochemical active ingredient, coated with a coating material containing a copolymer of methacrylic acid and alkyl acrylate,
[2] Agrochemical granular preparation according to the above [1], which is applied during the sowing and / or raising period of agricultural crops,
[3] The agricultural chemical granular preparation according to the above [2], wherein the agricultural product is rice.
[4] The agricultural chemical granular preparation according to the above [2], wherein the agricultural crop is a horticultural crop,
[5] The agricultural chemical granular preparation according to any one of [1] to [4], wherein the copolymer is a copolymer of methacrylic acid and ethyl acrylate,
[6] The agricultural chemical granular material according to the above [5], wherein the copolymer is a copolymer obtained by copolymerizing methacrylic acid and ethyl acrylate in a ratio of 1: 0.7 to 1: 1.3. Formulation,
[7] The granular agricultural chemical formulation according to any one of [1] to [6] above, wherein the content of the coating material in the granular agricultural chemical formulation is 0.1 to 60% by weight,
[8] The agricultural chemical granular preparation according to any one of [1] to [7] above, wherein the agricultural chemical active ingredient is thiazinyl.
[9] A method for producing an agricultural chemical granular preparation, comprising a step of coating a granular material containing an agricultural chemical active ingredient with a coating material containing a copolymer of methacrylic acid and an alkyl acrylate ester,
[10] The method further includes the step of polymerizing methacrylic acid and alkyl acrylate in an aqueous solution containing polyoxyethylene sorbitan oleate and sodium lauryl sulfate to obtain a copolymer contained in the coating material. The production method according to the above [9], and
[11] The production method according to [9] or [10] above, wherein the agrochemical granular preparation is an agrochemical granular preparation for application during the sowing and / or seedling raising period of agricultural crops.

A granular material containing an agrochemical active ingredient is coated with a coating material containing a copolymer of methacrylic acid and an alkyl acrylate ester. The granular agricultural chemical formulation of the present invention is capable of releasing an agrochemical active ingredient into water. Germination of seeds of agricultural crops (for example, rice (especially paddy rice), horticultural crops, etc.), which is a copolymer of methacrylic acid and alkyl acrylate contained in the coating material, which can be controlled in the direction of inhibition.・ Because it does not adversely affect rooting and seedling growth, it is generally applied during the sowing and seedling seasons of crops that are prone to phytotoxicity for reasons such as applying a large amount of pesticide preparation (especially in seedling boxes or cell trays). Can also be applied without causing any phytotoxicity. Therefore, the phytotoxicity is applied over the entire application period of pesticides such as sowing and seedling application before transplanting to Honda or Honpo, and application after transplanting to Honda or Honjo. It is avoided. In addition, since the release of the pesticidal active ingredient into water can be appropriately controlled in the direction of suppression, the pesticidal granular preparation of the present invention exhibits excellent effects (controlling performance and the like) over a long period of time. As described above, according to the agrochemical granular preparation of the present invention, (1) planting seedling box application or cell tray application of crops that enables labor saving of pesticide application, reduction of environmental burden and prevention of drift, the problem of phytotoxicity of the coating material itself (2) Since the release of the pesticidal active ingredient can be controlled in a restraining direction, phytotoxicity due to the release of the pesticidal active ingredient in a short period of time can be prevented. By using it for the application of seedling boxes or cell trays for agricultural crops, it is possible to save labor, reduce environmental impact, prevent drifting and prevent chemical damage when applying agricultural chemicals.
Furthermore, the granular agricultural chemical preparation of the present invention is a copolymer of methacrylic acid and alkyl acrylate ester contained in the coating material, having a weight average molecular weight, a minimum film forming temperature and a Tg within the specific ranges described later. By using it, it is possible to more efficiently control the release of the pesticidal active ingredient in a restraining direction with an economical coating amount.

Next, the agrochemical granular preparation of the present invention and the production method thereof will be specifically described.
The agrochemical active ingredient used in the present invention is not particularly limited, and examples thereof include insecticides, fungicides, disease control agents, herbicides, plant growth regulators, and the like, and one or two or more of them are added at the same time. Can do. Specifically, for example, an insecticide or a fungicide is mainly used, and in some cases, a herbicide, a plant growth regulator, or the like is added thereto.
The content of the pesticidal active ingredient in the pesticidal granular preparation of the present invention varies depending on the type of the pesticidal active ingredient and is not particularly limited, but is preferably 0.01 to 60 wt. Part, more preferably 0.1 to 50 parts by weight. For example, when thiazinyl described later is used as the agrochemical active ingredient, thiazinyl is preferably 0.01 to 60 parts by weight, more preferably 0.1 to 50 parts by weight, more preferably 100 parts by weight of the agricultural chemical granular preparation. What is necessary is just to make it contain in the ratio of 1-30 weight part.

  Specific agrochemical active ingredients (generic names) include, for example, phenylazole insecticides such as fipronil, acetoprole, imidacloprid, acetamiprid, nitenpyram, dinotefuran dinotefuran), thiacloprid, thiamethoxam, clothianidin and other neonicotinoid insecticides, flonicamid and other nicotinoid insecticides, spinosad and other macrolide insecticides, benfuracarb Carbamate insecticides such as (benfuracarb), phthalic acid diamide insecticides such as flubendiamide, various insecticides such as organophosphorus insecticides such as acephate, thiadinyl, probenazole , Acibenzola Plant resistance-inducing disease control agents such as ru-S-methyl (acibenzolar-S-methyl), BYF-1047 (development code), isoprothiolan, carpropamid, diclocymet, pyroquilon , Bactericides such as orysastrobin, azoxystrobin, tricyclazole, furametpyr, furtolanil, thifluzamide, but are not limited to these Absent. Thiazinyl is preferably used as the agrochemical active ingredient in the present invention.

  The granular material of the pesticidal granular preparation of the present invention includes those containing an pesticidal active ingredient and further containing a solid carrier and / or a binder. 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 the semi-synthetic system include dextrin, soluble starch, oxidized starch, pregelatinized starch, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like. , Polyacrylamide, polyvinyl pyrrolidone, sodium polyacrylate, ethylene-acrylic acid copolymer, maleic anhydride copolymer, polyethylene glycol and the like, but are not limited thereto. Further, the binder can be used alone or in combination of two or more, and its content is usually 0.1 to 20% by weight, preferably based on the total amount of the agricultural chemical granular preparation. Is 0.3 to 10% by weight. As the binder, for example, polyvinyl alcohol is preferable.

  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, kenaf powder, and water-soluble solid carriers such as inorganic salts such as ammonium sulfate, sodium chloride, potassium chloride, glucose, sucrose, fructose, lactose, etc. Saccharides, urea, urea formalin condensates, organic acid salts, water-soluble amino acids and the like, but are not limited thereto. These solid carriers may be used alone or in combination of two or more. The content 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 agricultural chemical granular preparation. As the solid carrier, for example, hydrous silicic acid, clay and the like are preferable.

  In addition, the granular agricultural chemical formulation of the present invention, to maximize the medicinal effects of the contained agricultural chemical active ingredient, or to improve the quality of the agricultural chemical granular formulation, if necessary, surfactant, solvent, Various auxiliary components such as a grinding aid, an absorbent, a decomposition inhibitor, and a pigment may be added. Moreover, what is necessary is just to determine those selections and compounding ratios so that it may suit the property of the pesticidal active ingredient to be used.

  As the surfactant, polyoxyethylene alkyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, polyoxyethylene sorbitan alkenyl ester (for example, polyoxyethylene sorbitan oleate) Nonionic surfactant such as alkyl naphthalene sulfonate, alkyl sulfate (eg, sodium lauryl sulfate), polyoxyethylene alkyl ether sulfate, polyoxyethylene polystyryl phenyl ether sulfate, polyoxyethylene polystyryl phenyl ether Anionic surfactants such as phosphate and dioctyl sulfosuccinate are exemplified. As the surfactant, for example, polyoxyethylene alkyl ether is preferable.

As described above, the agglomerated active ingredient, the binder, the solid carrier, and the granular material containing the auxiliary ingredient blended for various purposes are generally known as extrusion granulation method, rolling granulation method, rolling It can be produced by a fluidized bed granulation method, a fluidized bed granulation method, a stirring mixed granulation method or the like. For example, when obtaining a columnar granular material, extrusion granulation method is preferred, agrochemical active ingredient, binder, solid carrier and various auxiliary ingredients are mixed, kneaded with an appropriate amount of water, basket type granulator, Granulate using an extrusion granulator such as a disk rotary granulator, screw-type horizontal granulator, screw-type forward granulator, twin dome gran (made by Fuji Powder Co., Ltd.), etc. It can be manufactured by cutting, drying and sieving.
In order to obtain a spherical granular material, the tumbling granulation method and the stirring mixed granulation method are preferable. The agrochemical active ingredient, the solid carrier, the binder, and various auxiliary components are mixed, and this mixture is granulated vessel granulator. After rotating the stirring blade in a stirring and rolling state, dripping or spraying water and / or a binder aqueous solution, etc., and growing the particles to an appropriate size, granulating, drying and sieving Can be manufactured.
As for the drying temperature after granulation, about 20 to 150 degreeC is mentioned as a temperature of blowing air, and the drying time is about 5 to 150 minutes.

  The coating material in the present invention contains a copolymer of methacrylic acid and acrylic acid alkyl ester. The copolymer does not adversely affect the germination and rooting of crop seeds and the growth of seedlings. Examples of the acrylic acid alkyl ester include acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms and having a linear or branched alkyl group. Specific examples include methyl acrylate and acrylic acid. Examples include ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and dodecyl acrylate. In the present invention, as the copolymer of methacrylic acid and alkyl acrylate, a copolymer of methacrylic acid and ethyl acrylate is used from the viewpoint of controlling the release of agricultural chemical active ingredients, causing no phytotoxicity, and industrially available. It is particularly preferable because of its ease.

The molar ratio (methacrylic acid: alkyl acrylate (especially ethyl acrylate)) of methacrylic acid and alkyl acrylate (especially ethyl acrylate) in the copolymer is preferable from the viewpoint of controlling the release of the agrochemical active ingredient. Is 1: 0.7-1: 1.3, more preferably 1: 0.8-1: 1.2.
Specific examples of the copolymer of methacrylic acid and ethyl acrylate include the following formula (1):

[Wherein, n and m represent integers. ] Etc. The molar ratio (n: m) between n and m in the formula (1) is preferably 1: 0.7 to 1: 1.3, more preferably 1: 0. 8 to 1: 1.2.

  The weight-average molecular weight [measured by GPC (gel permeation chromatography) using polyethylene glycol as a standard] of the copolymer of methacrylic acid and alkyl acrylate used in the present invention is preferably 100,000 to 500, 000, more preferably 100,000 to 300,000. The minimum film forming temperature of the copolymer used in the present invention is preferably 1 to 22 ° C. The Tg of the copolymer used in the present invention is preferably 55 to 100 ° C, more preferably 75 to 100 ° C. In the present invention, if the weight average molecular weight, minimum film-forming temperature, and Tg of the copolymer are within the above ranges, it is possible to efficiently control the release of the pesticidal active ingredient in a restraining direction with a more economical coating amount. it can.

The method for producing a copolymer of methacrylic acid and acrylic acid alkyl ester used in the present invention is not particularly limited, and can be carried out, for example, by a normal radical polymerization method. Examples of the radical polymerization include emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization. The copolymer is obtained as an emulsion, solution or solid containing the copolymer by a polymerization method. From the viewpoint of easy handling of the resulting copolymer, an emulsion is preferred. An emulsion containing a copolymer of methacrylic acid and an alkyl acrylate used in the present invention is specifically an emulsifier (for example, the above-described nonionic surfactant, anion, etc.) used in ordinary emulsion polymerization. It can be obtained by emulsion polymerization of methacrylic acid and alkyl acrylate ester by adding a polymerization initiator in an aqueous solution containing a surfactant or the like).
The obtained emulsion containing a copolymer of methacrylic acid and alkyl acrylate can be used as it is or mixed with other coating materials described below for the production of the agricultural chemical granular preparation of the present invention. .

In the present invention, methacrylic acid and an acrylic acid alkyl ester are emulsion-polymerized in an aqueous solution containing polyoxyethylene sorbitan oleate and sodium lauryl sulfate, and the methacrylic acid and the acrylic acid alkyl ester contained in the coating material are mixed. It is preferable to obtain a copolymer. An emulsion containing a copolymer of methacrylic acid and alkyl acrylate is obtained by emulsion polymerization in an aqueous solution containing polyoxyethylene sorbitan oleate and sodium lauryl sulfate. To preferred. The polyoxyethylene sorbitan oleate used in the present invention is not particularly limited, and any of those used as an emulsifier for ordinary emulsion polymerization can be used. For example, sorbitan monooleate, sorbitan trioleate Oleic acid sorbitan ester polyoxyethylene ether (ethylene oxide (EO) added mole number is about 5 to 30), specifically, for example, monooleic acid polyoxyethylene sorbitan (20E.O. ) (Polysorbate 80 (Tween 80)), polyoxyethylene sorbitan trioleate (20E.O.) (polysorbate 85), polyoxyethylene sorbitan monooleate (6E.O.) and the like, and polysorbate 80 is preferred. As the oleic acid polyoxyethylene sorbitan, commercially available products can be used. Examples of commercially available products include sorbon T-80 (trade name, polysorbate 80, manufactured by Toho Chemical Industry Co., Ltd.), sorbon T-85 (trade name, polysorbate 85). , Manufactured by Toho Chemical Co., Ltd.), Rheodor TW-O106V (trade name, polyoxyethylene sorbitan monooleate (6EO), manufactured by Kao Corporation), Rheodor TW-O120V (trade name, Polysorbate 80, Kao Corporation) Product), Rheodor TW-O320V (trade name, polysorbate 85, manufactured by Kao Corporation) and the like.

As the copolymer of methacrylic acid and ethyl acrylate used in the present invention, for example, “methacrylic acid copolymer LD” classified as an enteric coating agent in the Pharmaceutical Additive Standard 2003 of the Ministry of Health, Labor and Welfare is particularly preferable. PA-30S "(weight average molecular weight = about 220,000, minimum film-forming temperature = about 15 ° C., Tg = about 87 ° C., manufactured by Sanyo Chemical Industries, Ltd.).
Since the polykid PA-30S (manufactured by Sanyo Chemical Industries Co., Ltd.) has a weight average molecular weight, a minimum film-forming temperature and a Tg within the above-mentioned ranges, the copolymer of methacrylic acid and ethyl acrylate is included in the present invention. When used, it is particularly preferred in that the release of the pesticidal active ingredient can be efficiently controlled in a restraining direction with an economical coating amount.

  A copolymer of methacrylic acid and alkyl acrylate (especially ethyl acrylate) having a weight average molecular weight, a minimum film-forming temperature, and a Tg within the above-mentioned ranges is, for example, according to JP-A-2004-51578. Can be manufactured by the following methods.

In addition, the coating material in the present invention is the above-mentioned methacrylic acid and alkyl acrylate ester, as long as it is a combination of methacrylic acid and alkyl acrylate ester alone, as long as it is a combination that does not cause phytotoxicity as an agricultural chemical granular preparation It may be a mixture of a copolymer and another coating material.
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. Examples thereof include acrylic resins other than the above-mentioned copolymer of methacrylic acid and alkyl acrylate.

Examples of the acrylic resin other than the copolymer of methacrylic acid and alkyl acrylate in the present invention include acrylic acid, alkyl acrylate ester, methacrylic acid, methacrylic acid alkyl ester homopolymer, or monomers thereof. And a copolymer of ethylene, vinyl chloride, vinyl acetate, 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 of the total weight of the coating material of the copolymer of methacrylic acid and alkyl acrylate in the present invention, from the viewpoint of controlling the release of the agrochemical active ingredient. Preferably, it is about 5% by weight or more.

The content of the coating material in the present invention is preferably 0.1 to 60% by weight, more preferably 0.5 to 50% by weight, more preferably 1 to 35% by weight as the content in the agricultural chemical granular preparation. It is. When the content is less than 0.1% by weight, the coating is incomplete or the thickness of the coating is not sufficient, resulting in insufficient control in the direction of suppressing the release of the agrochemical active ingredient, Drug damage will occur or the sustainability of the control effect will be insufficient. On the other hand, if the content exceeds 60% by weight, the coating is too thick and almost no agrochemical active ingredients are released, 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.
In the agricultural chemical granular preparation of the present invention, when a copolymer of methacrylic acid and alkyl acrylate contained in the coating material is used, those having a weight average molecular weight, minimum film forming temperature and Tg within the above-mentioned ranges Thus, it is possible to obtain an agrochemical granular preparation having a desired coating thickness in a short time.

  By controlling the mixing ratio of the above-mentioned copolymer of methacrylic acid and alkyl acrylate ester in the coating material and the amount of the coating material in the pesticidal granular preparation of the present invention, the degree of suppression of release of the pesticidal active ingredient is controlled. be able to.

The pesticidal granular preparation of the present invention can be produced by coating the granular material containing the above-mentioned pesticidal active ingredient with a coating material containing the above-mentioned copolymer of methacrylic acid and alkyl acrylate.
Examples of a method for coating the above-mentioned granular material containing an agrochemical active ingredient with a coating material containing the above-mentioned copolymer of methacrylic acid and alkyl acrylate ester include, for example, in a fluidized bed or rotating under a heated air current. The coating material (preferably an emulsion containing the above-mentioned copolymer of methacrylic acid and alkyl acrylate) is sprayed continuously or intermittently on the granular material being rolled on a pan or rotating drum. Alternatively, a method of dripping and drying, and a granular material and the coating material (preferably an emulsion containing a copolymer of the aforementioned methacrylic acid and alkyl acrylate ester) by a Nauter mixer or a ribbon mixer. Although the method of mixing and absorbing and fluidized bed drying is shown, of course, it is not limited to these.
Examples of the heating / drying temperature include about 20 ° C. to 150 ° C. as the temperature of the blown air, and examples of the heating / drying time include about 5 to 150 minutes.
The pesticide granular preparation of the present invention thus obtained is preferable in that it can be prevented from drifting with less scattering to the outside of the control target area compared to a powdery or liquid pesticide preparation.

  The application target of the agrochemical granular preparation of the present invention is not particularly limited, but general agricultural crops such as rice (especially paddy rice), horticultural crops (such as cereals (eg rice, barley, wheat, rye, oats, corn) ), Beans (eg, soybeans, red beans, broad beans, peas, peanuts, etc.), fruit trees / fruits (eg, apples, citrus fruits, pears, grapes, peaches, plums, cherry peaches, walnuts, almonds, bananas, Strawberry, etc.), vegetables (eg, cabbage, tomato, spinach, broccoli, lettuce, onion, leek, bell pepper, etc.), root vegetables (eg, carrot, potato, sweet potato, radish, lotus root, turnip), processing crops (For example, cotton, hemp, Japanese mulberry, mitsumata, rapeseed, beet, hops, sugar cane, sugar beet, olives, rubber, coffee, tobacco, tea, etc.), moss (for example, pumpkin , Cucumbers, watermelons, melons, etc.), pastures (eg, orchard grass, sorghum, timothy, clover, alfalfa, etc.), turf (eg, Korean turf, bentgrass, etc.), crops for fragrances (eg, lavender, rose, etc.) Marie, thyme, parsley, pepper, ginger, etc.), flower plants (for example, chrysanthemum, rose, orchid, etc.)) and the like.

The granular pesticide preparation of the present invention can be applied to all scenes in pesticide application, but particularly in scenes where it is applied at the stage of germination and rooting of crops or seedling growth, so-called sowing and / or seedling periods. Useful in that it can be applied. The sowing period and the seedling period of the crop are not strictly separated, and the seeding period and / or the seedling period of the crop are not particularly limited, but generally from the preparation period of the seedling culture soil before sowing, This refers to the period of time after sowing and raising seedlings until the grown seedlings are transplanted to Honda or this farm. The sowing period and / or the seedling period of rice (especially paddy rice) is, for example, the period from the seedling period to the time just before rice planting, when mixed with the seedling culture soil, before sowing or after covering. Application of the agrochemical granular preparation of the present invention is not limited to these periods, and can also be applied to the field of simultaneous rice planting application that has been developed in recent years. The sowing period and / or the seedling period of the horticultural crop corresponds to, for example, the period from the seedling period to the time of transplanting to the main field after mixing the seedling culture soil, before sowing at the time of sowing or after covering. The application of the agrochemical granular preparation of the present invention is not limited to these periods, and the application period for horticultural crops is particularly preferably applied during sowing and young seedling periods, and planting holes at the time of transplantation.
In addition, although raising seedling culture soil is normally used for cultivation of a seeding period and / or a seedling raising period, it is applicable also in cultivation other than cultivation soils, such as a seedling mat and a sheet.

In the pesticide granular preparation of the present invention, the seedling box application is preferable for the application of rice (particularly, paddy rice) at the sowing and / or raising period. In general, seedling box application of rice (especially paddy rice) means sowing time and / or seedling time in a seedling box before transplanting to Honda (for example, when mixing seedling culture soil, before sowing or after covering soil, It is a method of applying agrochemicals applied during the period from the season to rice planting.
A seedling box is a container for raising seedlings in general with seedling culture soil (for example, growing seedlings and temporary seedlings), and the size and shape of the container is not particularly limited as long as it is suitable for raising seedlings. However, for example, a seedling box of about 60 cm × about 30 cm in rectangle and about 3 cm in height is generally used for raising rice seedlings.
Moreover, in the agrochemical granular preparation of the present invention, cell tray application is preferred for application of the horticultural crops (vegetables, etc.) during the sowing period and / or the seedling raising period. Cell tray application of horticultural crops generally means sowing time and / or raising seedling period (for example, period from seeding time to transplanting time, for example, mixing seedling culture soil, sowing, etc.) It is an application method of an agrochemical to be applied before or after soil covering, during the period from the seedling stage to the time of transplanting in this field.
Cell trays are generally containers for raising seedling culture soil, etc., mainly for raising horticultural crops (for example, raising seedlings and temporary seedlings). The size and shape of the containers are suitable for raising seedlings. The shape is not particularly limited, and examples of the shape include a tray shape obtained by connecting inverted cones or inverted square pyramid pots. The size of the cell tray varies depending on the type of plant to be cultivated and the cultivation period, but generally, a rectangular tray having a size of about 55 cm × about 30 cm and having tens to hundreds of pot holes is mainly used.

  The seedling box application of rice (especially paddy rice) and the cell tray application of horticultural crops by the pesticide granular preparation of the present invention can be performed without worrying about phytotoxicity, and the seedlings can be applied by applying them in the seedling box or cell tray. Or, after transplanting to the mainland, the effect can be exhibited in the mainland or the mainland, so labor saving in the spraying of agricultural chemicals and reduction of the environmental load are achieved, and there is a problem of drift that becomes a problem in the conventional spraying of agricultural chemicals in the mainland or mainland. This is preferable in that it can be avoided.

As a method of spraying (sprinkling) the agrochemical granular preparation of the present invention, it can be sprayed by the same method as a normal agrochemical granular preparation, for example, direct powdering by hand, human-powered granulator, electric motor Aerodynamic granulators such as granulators, back-loaded power granulators, traveling power granulators, tractor-equipped granulators, rice transplanter-equipped granulators, side-line application medicines, unmanned helicopters Etc.
In particular, when applying rice seedlings (especially paddy rice) in seedling boxes, for example, scooping up a specified amount of agrochemical granular preparation with a measuring cup, sprinkle it on the seedling box, put it in a special seedling box spraying container and disperse it in the seedling box. A method of granulating, a method of directly spraying into a seedling box from a discharge port or a hole provided in a packaging container in the case of a packed agricultural chemical granular preparation, a large number of seedling boxes arranged extensively using a power type granulator Examples of methods include a method of graining, a method of graining in a seedling box with a dedicated device at the time of sowing, a method of mixing with seedling soil, and the like. The cell tray application of horticultural crops may be performed in accordance with the application of the nursery box.

  In order to appropriately perform the above-described spraying, it is preferable that the physical properties of the granular agricultural chemical formulation of the present invention are within a certain range with respect to various items as exemplified below. For example, the apparent specific gravity of the agricultural chemical granular preparation of the present invention 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 particles of the agricultural chemical granular preparation of the present invention is preferably 20 or less, more preferably 10 or less in the whole agricultural ball mill method. The particle size of the pesticidal granular preparation of the present invention is preferably 90% by weight or more of the entire pesticidal granular preparation, 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 the particle | grains of the agrochemical granular formulation of this invention are cylindrical, the diameter of a cross-sectional circle becomes like this. Preferably it is 0.3-2.0 mm, More preferably, it is 0.5-1.5 mm. Moreover, when the grain of the agricultural chemical granular preparation of the present invention is cylindrical, the grain length corresponding to the height of the cylinder is usually preferably 0.5 to 6 times the diameter of the cross-sectional circle. When spraying using a dedicated device at the time of work, for example, a vibratory seedling box application chemical spraying device (made by Bizen, model KS-10: shutter type dusting machine) or a seedling box drug dispensing hopper (manufactured by Tintech, model SDP- 33S: Roller-type granulator), particles having a particle length of 2.5 times or more with respect to the diameter of the cross-sectional circle are preferably 50% by weight or less, more preferably 10%, of the whole agricultural chemical granular preparation. -40% by weight.

In addition, although the application amount at the time of applying the pesticidal granular preparation of the present invention varies depending on the type of the pesticidal active ingredient, etc., in the case of paddy field or field, it is usually 0.1-20 kg per 10 ares, preferably 0.2. In the case of application of a seedling box for rice (especially paddy rice), it is usually 10 to 200 g, preferably 10 to 100 g per seedling box (usually 0.16 m ² ). In this case, it is usually 1 to 2000 g, preferably 5 to 1000 g per cell tray (usually 0.15 m ² ).
Even when thiazinyl is used as the agrochemical active ingredient of the agrochemical granular preparation of the present invention, it can be applied at the same application rate as described above.

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”, and “%” means “% by weight”.
In the following examples, “apparent specific gravity” is a value according to the official agricultural chemical inspection method, “hardness” is a value according to the whole agricultural ball mill method, and “particle size (300 to 1700 μm) (%)” is a sieve having an opening of 1700 μm. It is the ratio (%) of the whole of the granular formulation of agricultural chemicals that passes through the sieve with an opening of 300 μm, and “grains more than 2.5 times the cross-sectional circle diameter (%)” The height of the cylinder when it is made is the grain length, and it is the ratio (%) to the whole agricultural chemical granular preparation of grains whose grain length is 2.5 times or more with respect to the diameter of the cross-sectional circle of the cylinder.

Example 1 Thiazinyl 13.3 parts, polyvinyl alcohol 2.0 parts, polyoxyethylene alkyl ether 0.5 parts, hydrous silicic acid 10.0 parts and clay 74.2 parts were mixed with a double-arm kneader (manufactured by Fuji Powder Co., Ltd.). ), And 30.0 parts of water was added and kneaded sufficiently. Next, the hydrated kneaded product was granulated by a basket type extrusion granulator 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. 90.0 parts of this granular material is put into a sugar-coated bread (manufactured by Kikusui Seisakusho Co., Ltd.) and "Polykid PA-30S" (copolymer emulsion of methacrylic acid and ethyl acrylate, containing 30% pure, Sanyo Chemical Industries) The liquid which mixed 33.3 parts and 1.7 parts of water was sprayed. The coated granular material (wet material) was taken out from the sugar-coated bread and then dried with a fluidized bed dryer to obtain a coated agricultural chemical granular preparation. The content of the copolymer of methacrylic acid and ethyl acrylate in the granular agricultural chemical preparation is 10.0%.
The physical properties of this coated agrochemical granular formulation were an apparent specific gravity of 0.85, a hardness of 1, a particle size (300 to 1700 μm) of 98%, and a grain size of at least 2.5 times the cross-sectional circle diameter of 31%.

Example 2 1 arm part of thiazinyl, 2.0 part of polyvinyl alcohol, 0.5 part of polyoxyethylene alkyl ether, 10.0 part of hydrous silicic acid and 74.5 part of clay were mixed with a double arm kneader (manufactured by Fuji Powder Co., Ltd.). 30.5 parts of water was added and kneaded sufficiently. Next, the hydrated kneaded product was granulated by a basket type extrusion granulator 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 "Polykid PA-30S" (a copolymer emulsion of methacrylic acid and ethyl acrylate, containing 30% pure, Sanyo Chemical Industries) The liquid which mixed 25.0 parts and 7.5 parts of water was sprayed. The coated granular material (wet material) was taken out from the sugar-coated bread and then dried with a fluidized bed dryer to obtain a coated agricultural chemical granular preparation. The content of the copolymer of methacrylic acid and ethyl acrylate in the agrochemical granular preparation is 7.5%.
The physical properties of this coated agrochemical granular formulation were an apparent specific gravity of 0.84, a hardness of 1, a particle size (300 to 1700 μm) of 97%, and a particle size of 2.5% or more of the cross-sectional circle diameter of 32%.

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.). ), 31.0 parts of water was added and kneaded sufficiently. Next, the hydrated kneaded product was granulated by a basket type extrusion granulator 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 parts of this granular material is placed in a sugar-coated bread (manufactured by Kikusui Seisakusho Co., Ltd.) and "Polykid PA-30S" (a copolymer emulsion of methacrylic acid and ethyl acrylate, containing 30% pure, Sanyo Chemical Industries, Ltd.) (Manufactured) A mixture of 16.7 parts and 13.3 parts of water was sprayed. The coated granular material (wet material) was taken out from the sugar-coated bread and then dried with a fluidized bed dryer to obtain a coated agricultural chemical granular preparation. The content of the copolymer of methacrylic acid and ethyl acrylate in the agricultural chemical granular preparation is 5.0%.
The physical properties of this coated agrochemical granular formulation were an apparent specific gravity of 0.83, a hardness of 1, a particle size (300 to 1700 μm) of 98%, and a particle size of 2.5% or more of the cross-sectional circle diameter of 33%.

Example 4 Thiazinyl 13.0 parts, polyvinyl alcohol 2.0 parts, polyoxyethylene alkyl ether 0.5 parts, hydrous silicic acid 10.0 parts and clay 74.5 parts were mixed with a double-arm kneader (manufactured by Fuji Powder Co., Ltd.). ), 28.0 parts of water was added and kneaded sufficiently. Next, the hydrated kneaded product was granulated by a basket type extrusion granulator 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. 90 parts of this granular material is put in a sugar-coated bread (manufactured by Kikusui Seisakusho Co., Ltd.) and "Polykid PA-30S" (copolymer emulsion of methacrylic acid and ethyl acrylate, containing 30% pure, Sanyo Chemical Industries, Ltd.) (Manufactured) 5.0 parts, "New Coat 4111" (acrylic resin emulsion, 46% pure content, Shin-Nakamura Chemical Co., Ltd.) 18.5 parts and water 11.5 parts mixed was sprayed. . The coated granular material (wet material) was taken out from the sugar-coated bread and then dried with a fluidized bed dryer to obtain a coated agricultural chemical granular preparation. The content of the copolymer of methacrylic acid and ethyl acrylate in the agricultural chemical granular preparation is 1.5%, and the content of the acrylic resin in the agricultural chemical granular preparation is 8.5%.
The physical properties of this coated agrochemical granular formulation were an apparent specific gravity of 0.85, a hardness of 1, a particle size (300 to 1700 μm) of 98%, and a particle size of 30% or more 2.5 times the cross-sectional circle diameter.

Comparative Example 1 In Example 1, 25.6 parts of “Polykid PA-30S” 25.6 parts of a polylactic acid resin emulsion (trade name: Prasema L110, containing 39% pure content, manufactured by Daiichi Kogyo Seiyaku) A coated agrochemical granular preparation was obtained in the same manner as in Example 1 except that the amount of water mixed with this was changed to 9.4 parts. Content in the agrochemical granular formulation of the said polylactic acid-type resin is 10.0%.
Comparative Example 2 In Example 1, 33.3 parts of “Polykid PA-30S” was replaced with 22.2 parts of vinyl acetate resin emulsion (trade name: Movinyl M110, containing 45% pure content, manufactured by Hoechst). A coated agrochemical granular preparation was obtained in the same manner as in Example 1 except that the amount of water mixed with this was changed to 12.8 parts. The content of the vinyl acetate resin in the agricultural chemical granular preparation is 10.0%.

Comparative Example 3 In Example 1, 33.3 parts of “Polykid PA-30S” was added to 21. of an ester ether resin emulsion (trade name: Superflex 126, 46% pure content, manufactured by Daiichi Kogyo Seiyaku). A coated agrochemical granular preparation was obtained in the same manner as in Example 1 except that the amount of water mixed with 7 parts was changed to 13.3 parts. The content of the ester ether resin in the agricultural chemical granular preparation is 10.0%.
Comparative Example 4 In Example 1, 33.3 parts of “Polykid PA-30S” was added to 21 of silica / acrylic resin emulsion (trade name: PM541-3426, 47% pure content, manufactured by Daiichi Kogyo Seiyaku). A coated agrochemical granular preparation was obtained in the same manner as in Example 1 except that the amount of water mixed with this was changed to 13.7 parts. The content of the silica-acrylic resin in the granular agricultural chemical formulation is 10.0%.

Comparative Example 5 In Example 1, 23.3 parts of “Polykid PA-30S” in a carbonate resin emulsion (trade name: Superflex 420, containing 50% pure, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) A coated agrochemical granular preparation was obtained in the same manner as in Example 1 except that the amount of water mixed with this was changed to 15.0 parts. The content of the carbonate-based resin in the agricultural chemical granular preparation is 10.0%.
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 (Fuji Powdal Co., Ltd.). ), And 30.0 parts of water was added and kneaded sufficiently. Next, the hydrated kneaded product was granulated by a basket type extrusion granulator equipped with a screen having a pore diameter of 1.2 mm. The obtained granulated product was dried with a fluid bed dryer (manufactured by Okawara Seisakusho Co., Ltd.), and then sieved with a sieve shaker equipped with sieve screens having openings of 500 μm and 1400 μm to obtain an agrochemical granular preparation.

The agricultural chemical granular preparations prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were tested by the following method.
Test Example 1 Underwater release test 100 ml of hard water was poured into a 225 ml mayonnaise bottle (glass container) and allowed to stand. Samples prepared according to Examples 1 to 4 and Comparative Examples 1 to 6 were precisely weighed and then dropped uniformly into 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 a light-isothermal condition, 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.
From the results shown in Table 1, the agrochemical granular preparation of the present invention (Examples 1 to 4) is compared with the agrochemical granular preparation of Comparative Example 6 that is not coated with a water-insoluble or poorly water-soluble coating material. It was shown that thiazinyl release was controlled in the direction of inhibition at both 6 hours and 24 hours. Moreover, compared with the pesticidal granular formulation of Comparative Example 6, the release of thiazinyl is also controlled in the suppression direction in the pesticidal granular formulations of Comparative Examples 1 to 5 coated with a water-insoluble or poorly water-soluble coating material. .

Test Example 2 Paddy rice phytotoxicity test Rice bran (variety: Hitomebore) was soaked in a disinfectant (Sportac Starna SE, manufactured by Nissan Chemical Industries, Ltd., diluted 200-fold) for 24 hours, air-dried, and seeded at 15 ° C for 6 days. Germination was carried out at 30 ° C. for 24 hours and used for the test. Newspaper, 2.2 kg of floor soil (Kumiai Ube Culture No. 2, Ube Industries Agricultural Materials Co., Ltd.) was laid on the bottom of the standard nursery box, and 150 g of persimmon seeds were sown. After sowing, a disinfectant (Daconil 1000, manufactured by Kumiai Chemical Industry Co., Ltd., 800-fold dilution) was sprayed with a 500 ml shower per box, and soil disinfection was performed. 50 g of the agricultural chemical granular preparations prepared in Examples 1 to 4 and Comparative Examples 1 to 5 were sprayed per nursery box, and the soil was covered from above (1.1 kg). After germination for 72 hours by stacking in a thermostatic apparatus at 30 ° C., cultivation was carried out in a greenhouse (25 to 18 ° C. setting) for 21 days. After 21 days of cultivation, the phytotoxicity to rice was-(no phytotoxicity: no phytotoxicity was observed on plants), ± (minor: slight phytotoxicity was observed on plants, but the phytotoxicity was not problematic in practice. Yes), + (Mild: Mild phytotoxicity is recognized on plants, and this phytotoxicity has practical problems), ++ (Medium: Obvious phytotoxicity is recognized on plants, and this phytotoxicity is practically problematic And ++++ (severe: serious phytotoxicity was recognized on plants, and this phytotoxicity has a practical problem). The results are shown in Table 2.
From the results shown in Table 2, the agricultural chemical granular preparations of the present invention (Examples 1 to 4) did not cause phytotoxicity even when applied during the sowing and seedling periods of rice, and germination and rooting of rice seeds and It was shown not to adversely affect the growth of seedlings. On the other hand, although the agrochemical granular preparations of Comparative Examples 1 to 5 are controlled in the direction of inhibition of thiazinyl release from the results of Test Example 1, phytotoxicity is caused by application during the sowing and seedling periods of rice. It was shown to occur.

Claims (11)

An agrochemical granular preparation comprising a granular material containing an agrochemical active ingredient coated with a coating material containing a copolymer of methacrylic acid and alkyl acrylate. The agrochemical granular preparation according to claim 1, which is applied during the sowing and / or raising period of agricultural crops. The pesticide granular preparation according to claim 2, wherein the agricultural product is rice. The pesticide granular preparation according to claim 2, wherein the agricultural crop is a horticultural crop. The agricultural chemical granular preparation according to any one of claims 1 to 4, wherein the copolymer is a copolymer of methacrylic acid and ethyl acrylate. The granular agricultural chemical formulation according to claim 5, wherein the copolymer is a copolymer obtained by copolymerizing methacrylic acid and ethyl acrylate in a ratio of 1: 0.7 to 1: 1.3. The pesticidal granular preparation according to any one of claims 1 to 6, wherein the content of the coating material in the pesticidal granular preparation is 0.1 to 60% by weight. The agrochemical granular preparation according to any one of claims 1 to 7, wherein the agrochemical active ingredient is thiazinyl. The manufacturing method of an agricultural chemical granular formulation including the process of coat | covering the granular material containing an agricultural chemical active ingredient with the coating material containing the copolymer of methacrylic acid and an acrylic acid alkylester. The method further comprises a step of polymerizing methacrylic acid and alkyl acrylate in an aqueous solution containing polyoxyethylene sorbitan oleate and sodium lauryl sulfate to obtain a copolymer contained in the coating material. The manufacturing method as described. The manufacturing method according to claim 9 or 10, wherein the pesticide granular preparation is a pesticide granular preparation for application during the sowing and / or seedling raising period of agricultural crops.