Stabilized agrochemical granule

Abstract

To provide an agrochemical granule having stabilized sprayability, effectiveness, and storage preservability.SOLUTION: An agrochemical granule comprises (a) an active agrochemical ingredient, (b) polyvinyl alcohol having a saponification degree of 60 to 100 mol%, (c) a Bronsted acid having a pKa of 4 or less, and (d) a hydrous layered silicate mineral having a swelling degree of 2 to 5 mL / 2 g as measured by a swelling test (JBAS-104-77).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a technology applicable to pesticide granules that are directly sprayed onto seedling boxes, cell trays, paddy fields or fields, etc., and relates to pesticide granules that are difficult to adhere to the surface of plants where water droplets are present when sprayed, and that, after spraying, gradually disintegrate due to the moisture in the soil, thereby exerting a sufficient effect, and that do not disintegrate or turn into powder due to vibration during transportation and storage, and thus have excellent sprayability, effectiveness and storage properties. [Background technology]

[0002] Known formulations of pesticides include granules, powders, wettable powders, tablets (jumbo), packs, flowables, water-soluble, liquids, and emulsions. Among them, granules are widely used because they can be produced relatively inexpensively, there is little drift during application, and it is easy to apply the appropriate amount. Furthermore, in recent years, there has been a demand for pesticide granules that are not only economical but also reduce the burden on the environment by suppressing drift, saving labor, and reducing the use of pesticides. As means for solving such problems, there are improvements in the formulation hardness, control of the dissolution of pesticide active ingredients, and long-term storage stability, and research has been conducted so far, as exemplified below.

[0003] JP 2016-210763 A (Patent Document 1) proposes an agrichemical granule containing propyrisulfuron and a solid carrier, in which the pH at 25°C when 10 grams of the agrichemical granule is mixed with 90 grams of ion-exchanged water is in the range of 7.0 to 9.0, thereby allowing the sufficient effect of propyrisulfuron to be maintained for a long period of time starting immediately after application.

[0004] WO 2014 / 024625 (Patent Document 2) proposes a solid pesticide composition containing tricyclazole and bentonite, in which the bentonite content in the solid pesticide composition is 40% by weight or more, and the pH of a 20% by weight aqueous dispersion of the solid pesticide composition is set to 4.5 or less, thereby controlling the dissolution of tricyclazole.

[0005] Japanese Patent Application Laid-Open No. 2000-143403 (Patent Document 3) proposes a pesticide granule that contains a pesticide active ingredient, sodium lignin sulfonate, polyoxyethylene polyoxypropylene styryl phenyl ether sodium sulfate, sodium carboxymethylcellulose, and a carrier, and that promotes the dissolution of the poorly water-soluble pesticide active ingredient.

[0006] Japanese Patent Application Laid-Open No. 7-179302 (Patent Document 4) proposes an agricultural chemical granule which contains an agricultural chemical active ingredient, sodium montmorillonite, sodium carboxymethylcellulose, and one or more surfactants selected from the group consisting of alkylbenzene sulfonate, sulfosuccinic acid diester type surfactants, and polycarboxylic acid type surfactants, and which reduces the decrease in particle hardness when stored under high humidity conditions.

[0007] Japanese Patent Application Laid-Open No. 2003-95806 (Patent Document 5) proposes a granular pesticide composition which contains a rice blast control active ingredient, bentonite, a nonionic surfactant, a nonionic water-soluble polymer and a mineral carrier, and which has both immediate effectiveness at the time of treatment and long-term residual effectiveness, and can exert a high control effect for a long period of time starting immediately after treatment with the control agent.

[0008] In the above-mentioned patent documents, bentonite and polyvinyl alcohols are used as water-soluble polymeric substances for the purpose of improving hardness or imparting a dissolution control function. However, bentonite has a high water swelling property, and the granules are easily dissolved when they come into contact with water, and polyvinyl alcohols are highly hydrophilic and become adhesive when they absorb water. This property causes a problem that when the granules are sprayed under conditions where there are many water droplets on the surface of the plant body, the granules adhere to the plant body and come into contact with the drug at a high concentration, causing phytotoxicity. Furthermore, the weather conditions when spraying the pesticide granules may be high temperature and humidity conditions, and under such conditions, the granules are particularly likely to adhere to the plant body, further increasing the risk of phytotoxicity. In other words, the above-mentioned patent documents left room for improvement in terms of a pesticide granule that is well-balanced in terms of storage stability, effectiveness, and sprayability derived from adhesion to the plant body. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] JP 2016-210763 A [Patent Document 2] International Publication No. 2014 / 024625 [Patent Document 3] JP 2000-143403 A [Patent Document 4] Japanese Patent Application Publication No. 7-179302 [Patent Document 5] JP 2003-95806 A Summary of the Invention [Problem to be solved by the invention]

[0010] In view of the above-mentioned conventional drawbacks, the present invention aims to provide an agrochemical granule with excellent applicability, effectiveness and storage stability, which does not powder when sprayed because the reduction in formulation hardness is suppressed even under hot and humid conditions where water droplets are present on the surface of the plant body, and in which the granules themselves do not adhere to the plant body due to the moisture on their surface, has water-based disintegrability so that they gradually disintegrate in the moisture in the soil after spraying, and has the ability to withstand impacts during transportation and storage. [Means for solving the problem]

[0011] The present inventors have conducted extensive research to solve the above problems. As a result, they have found that the problems can be solved by an agricultural chemical granule comprising an agricultural chemical active ingredient, polyvinyl alcohol with a degree of saponification of 60-100 mol%, a Bronsted acid with a pKa of 4 or less, and a hydrous layered silicate mineral with a swelling degree of 2-5 mL / 2 g in the swelling power test (JBAS-104-77). Furthermore, they have found that in the above agricultural chemical granule, it is more preferable that the degree of saponification of the polyvinyl alcohol is 80-90 mol%, the average degree of polymerization is 500-2000, and a C10-18 aliphatic hydrocarbon-based anionic surfactant is contained, and thus the present invention has been completed.

[0012] That is, the gist of the present invention is as follows. [1] A pesticide granule comprising (a) an active pesticide ingredient, (b) polyvinyl alcohol having a degree of saponification of 60 to 100 mol%, (c) a Bronsted acid having a pKa of 4 or less, and (d) a hydrous layered silicate mineral having a swelling degree of 2 to 5 mL / 2 g in a swelling power test (JBAS-104-77). [2] (b) The pesticide granule according to [1], characterized in that the polyvinyl alcohol has a degree of saponification of 80 to 90 mol % and an average degree of polymerization of 500 to 2,000. [3] (e) The pesticide granule according to [1] or [2], characterized by containing a C10-18 aliphatic hydrocarbon anionic surfactant. Effect of the Invention

[0013] The pesticide granules of the present invention maintain their formulation hardness even after humidification and do not disintegrate when left stationary in water, so that even under high temperature and humidity conditions where a large amount of water droplets are present on the surface of the plant body, the formulation hardness is suppressed from decreasing, so that they do not powder when sprayed, and the sprayed granules themselves are not easily attached to the plant, making them excellent in sprayability. On the other hand, the granules gradually disintegrate under stirring conditions in water, so that the granules gradually disintegrate due to the moisture in the soil after spraying, allowing the pesticide active ingredient to exert a sufficient effect. In addition, the formulation hardness is hard, so that it does not disintegrate or powder due to vibration during transportation or storage, and exposure to the user or drift during spraying is suppressed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The pesticide granules of the present invention will be described in more detail below. In this specification, the expression "A to B" (A and B are numerical values) means "greater than or equal to A and less than or equal to B," which is a numerical range including both ends. <(a) Pesticide active ingredients> Examples of pesticide active ingredients that can be used in the present invention include the following.

[0015] Examples of insecticidal active ingredients include organophosphates (MEP, diazinon, etc.), carbamates (BPMC, carbosulfan, etc.), metadiamides and isoxazolines (fluxamethamide, broflanilide, etc.), oxadiazines (indoxacarb, etc.), semicarbazones (metaflumizone, etc.), pyrethroids (cycloprothrin, etc.), nereistoxins (thiocyclam, etc.), sulfoximines (sulfoxaflor, etc.), mesoions (triflumezopyrim, etc.), neonicotinoids (imidacloprid, thiamethoxam, clothianidin, dinotefuran, etc.), pyridine azomethine, These include benzoylureas (pymetrozine, etc.), benzoylureas (teflubenzuron, etc.), METIs (tolfenpyrad, etc.), carboxanilides (biflubumid, etc.), β-ketonitriles (cyenopyrafen, etc.), diamides (flubendiamide, chlorantraniliprole, cyantraniliprole, etc.), phenylpyrazoles (fipronil, ethiprole, etc.), spinosyns (spinosad, spinetoram, etc.), diacyl-hydrazines (tebufenozide, chromafenozide, methoxyfenozide, buprofezin, etc.), and other synthetic insecticides (flupirimine, dinpropylidaz, etc.).

[0016] Examples of fungicidal active ingredients include inorganic copper, organic copper, inorganic sulfur, organic sulfur, acylalanine (metalaxyl, etc.), isoxazole (hydroxyisoxazole, etc.), organophosphorus (IBP, etc.), benzimidazole (benomyl, thiophanate methyl, etc.), N-phenylcarbamate (diethofencarb, etc.), phenylurea (pencycuron, etc.), pyridinylbenzamide (fluopicolide, etc.), benzoylpyridine (pyriophenone, etc.), pyrimidineamine (diflumetrim, etc.), phenylbenzamide (mepronil, flumethamine, etc.), tolanil, etc.), phenyloxoethylthiophenamides (isofetamide, etc.), thiazolecarboxamides (thifluzamide, etc.), pyrazole-4-carboxamides (furametpyr, penflufen, fluxapyroxad), pyridinecarboxamides (boscalid, etc.), pyrazinecarboxamides (pyradiflumide, etc.), methoxyacrylates (azoxystrobin, etc.), methoxyacetamides (mandestrobin, etc.), methoxycarbamates (pyraclostrobin, etc.), oxyiminoacetic acids (trifloxystrobin, etc.), oxyiminoacetates Amidoamides (e.g., metominostrobin), oxazirinediones (e.g., famixadone), dihydrooxazines (e.g., fluoxastrobin), benzylcarbamates (e.g., pyribencarb), cyanoimidazoles (e.g., cyazofamid), sulfamoyltriazoles (e.g., amisulbrom), triazolopyrimidineamines (e.g., amethoctrazine), anilinopyrimidines (e.g., mepanipyrim), phenylpyrroles (e.g., fludioxonil), carbamates (e.g., propamocarb hydrochloride), piperazines (e.g., triforine), pyrimidines (e.g., fenarimol) , imidazoles (pefurazoate, ipconazole, triflumizole, etc.), triazoles (imibenconazole, simeconazole, tebuconazole, metconazole, etc.), hydroxyanilides (fenhexamid, etc.), aminopyrazolines (fenpyrazamine, etc.), thiocarbamates (pyributicarb, etc.), acid amides (dimethomorph, mandipropamid, etc.), isobenzofuranones (fthalide, etc.), pyrroloquinolinones (pyroquilon, etc.), triazolobenzothiazoles (tricyclazole, etc.), propionamides (fenoxanil, etc.),These include trifluoroethyl carbamates (tolprocarb, etc.), thiadiazoles (thiadinil, etc.), isothiazoles (probenazole, isotianil, etc.), dithiocarbamates (ziram, thiuram, mancozeb, etc.), phthalimides (captan, etc.), antibiotics (kasugamycin, validamycin, etc.), and other synthetic fungicides (diclobenzazox, flutianil, flusulfamide, cymoxanil, ferimzone, ipflufenoquin, tebufloquin, etc.).

[0017] Examples of herbicidal active ingredients include phenoxy acids (MCPA thioethyl, MCPB ethyl, clomeprop, triclopyr, etc.), allyloxypropionic acid esters (cyhalofop butyl, metamifop, quizalofop ethyl, etc.), cyclohexanediones (clethodim, sethoxydim, etc.), imidazolinones (imazaquin, imazapyr isopropylamine salt, etc.), pyrimidinylthiobenzoates (pyriminobac-methyl, pyriftalid, etc.), sulfonylureas (imazosulfuron, cyclosulfamuron, nicosulfuron, halosulfuron-methyl, Propyrisulfuron, Metazosulfuron, Bensulfuron-methyl, Flucetosulfuron, etc.), Triazolopyrimidines (Penoxsulam, etc.), Sulfonanilides (Triafamone, Pyrimisulfan, etc.), Benzamides (Propyzamide, etc.), Dinitroanilines (Trifluralin, Oryzalin, Pendimethalin, etc.), Phosphoramidates (Butamifos, etc.), Carbamates (IPC, etc.), Phenylcarbamates (Desmedipham, Phenmedipham, etc.), Pyridazinones (Chloridazon, etc.), Triazines (Atrazine, Cyanazine, Cymetho, etc.), phosphorus, prometryn, etc.), triazinones (metamitron, hexazinone, etc.), triazolinones (amicarbazone, etc.), uracils (bromacil, lenacil, etc.), ureas (DCMU, linuron, etc.), benzothiadiazinones (bentazone, etc.), pyridinecarboxamides (diflufenican, etc.), N-phenylphthalimides (flumioxazin, etc.), oxadiazoles (oxadiazone, etc.), oxazolidinediones (pentoxazone, etc.), phenylpyrazoles (pyraflufenethyl, etc.), thiadiazoles (fluthiacet-methyl, etc.), thiadiazoles (fluthiacet-methyl, etc.), Riazolinones (carfentrazone ethyl, etc.), azolylcarboxamides (ipfencarbazone, cafenstrole, fentrazamide, etc.), benzofurans (benfuresate, etc.), isoxazolines (pyroxasulfone, etc.), oxiranes (indanofan, etc.), thiocarbamates (esprocarb, benthiocarb, etc.), α-chloroacetamides (dimethenamid, thenylchlor, pretilachlor, butachlor, etc.), oxyacetamides (mefenacet, etc.), bipyridyliums (diquat, etc.), pyrazoles (pyrazolate,benzofenap, etc.), triketones (tefuryltrione, benzobicyclon, mesotrione, etc.), alkylazines (triaziflam, etc.), benzamides (isoxaben, etc.), nitriles (dichlobenil, etc.), triazolocarboxamides (flupoxam, etc.), benzyl ethers (methiozoline, etc.), pyridazinediones (cyclopyrimorate, etc.), and other synthetic herbicides (oxaziclomefone, dymron, pyributicarb, propanil, lancotrione Na salt, tetflupyrorimet, florpyrauxifen benzyl, dimesulfazate, etc.).

[0018] The specific herbicidal active ingredients contained in these are described, for example, in "Pesticide Handbook 2021 Edition" (published by Japan Plant Protection Association), "SHIBUYA INDEX 13th Edition" (published by SHIBUYA INDEX Research Group), and "The Pesticide Manual Sixteenth Edition" (published by British Crop Protection Council).

[0019] Examples of plant growth regulators include ethylene-based (ethephon, etc.), auxin-based (indolebutyric acid, ethychlozate, dichlorprop, etc.), cytokinin-based (benzylaminopurine, etc.), gibberellin-based (gibberellin, etc.), and other synthetic types (chlormequat, daminozide, flurprimidol, mepiquat chloride, trinexapac-ethyl, etc.).

[0020] In addition, the pesticide active ingredient used in the present invention may be any other pesticide active ingredient that has been publicly known or will be developed in the future, as long as it achieves the same purpose as the present invention and is applicable as a water-floating pesticide formulation.

[0021] The above-mentioned pesticide active ingredients may be used alone or in combination of two or more kinds without any problem. The amount of each ingredient added is usually 0.01 to 60% by weight, preferably 0.05 to 50% by weight in the formulation.

[0022] <(b) Polyvinyl alcohol with a saponification degree of 60 to 100 mol %> In the pesticide granules of the present invention, polyvinyl alcohol contributes to hardness development and disintegrability in water when left to stand. Polyvinyl alcohol is a water-soluble synthetic polymer with very strong hydrophilicity. It develops adhesive properties when in contact with water, and after drying, it forms a strong film-like adhesive layer, so it is often used as a binder for adhesives (rewetting, lamination, office glue), construction and civil engineering (cement, mortar, gypsum), inorganic binders (ferrite, zirconium, alumina, etc.), synthetic leather, seedling soil, and binders for agricultural chemical granules. In addition, since it exhibits protective colloid functions when in aqueous solution, it may also be used as an emulsifier for emulsion polymerization of vinyl acetate and acrylic emulsions, and as a dispersant for suspension polymerization of PVC. The manufacturing method is generally industrially produced by a polymerization reaction process to polyvinyl acetate using vinyl acetate monomer as a raw material, followed by a saponification reaction process in which polyvinyl acetate is hydrolyzed with acid or alkali and converted into polyvinyl alcohol, and by controlling the conditions of these reactions, it is possible to produce polyvinyl alcohol with a variety of properties such as water solubility and adhesiveness (film strength). Polyvinyl alcohol has average polymerization degree and saponification degree as parameters that indicate its structural properties. The average degree of polymerization indicates the number of vinyl acetate molecules connected, and is adjusted by controlling the polymerization reaction conditions. The higher the average degree of polymerization, the higher the molecular weight, which leads to reduced water solubility and stronger adhesion. On the other hand, the lower the average degree of polymerization, the lower the molecular weight, which leads to improved water solubility and reduced adhesion. The degree of saponification is expressed as the percentage (mol%) of hydroxyl groups relative to the total number of acetate groups and hydroxyl groups, and is adjusted by controlling the saponification reaction conditions. Depending on the value of the degree of saponification, it is broadly divided into two types: fully saponified type, with a saponification degree of 98 mol% or more, where almost only hydroxyl groups are present, and partially saponified type, with a saponification degree of less than 98 mol%, where hydroxyl groups and acetate groups coexist.

[0023] The degree of saponification of the polyvinyl alcohol used in the present invention must be 60-100 mol%. If the degree of saponification is less than 60 mol%, the water solubility decreases, and the desired preparation hardness or disintegrability in water cannot be obtained. The average degree of polymerization is preferably about 300-3000. In particular, from the viewpoint of ease of water solubility, the degree of saponification is more preferably 80-90 mol% and the average degree of polymerization is more preferably 500-2000. The polyvinyl alcohol usable in the present invention may be used alone or in combination of two or more kinds. The amount added is usually 0.1 to 10% by weight, preferably 1 to 5% by weight, in the preparation, and one or more kinds from the above may be used.

[0024] <(c) Bronsted acids with pKa below 4> In the pesticide granule of the present invention, the Bronsted acid contributes to hardness development and disintegrability in water under static and stirring conditions. A Bronsted acid is defined based on the Bronsted-Lowry acid-base theory and refers to a substance that has the ability to donate a proton. The ability to donate a proton, i.e., the strength of an acid, is expressed by the acid dissociation constant (pKa). The smaller this value, the higher the proton donating ability and the stronger the acid is evaluated to be. It is essential that the pKa of the Bronsted acid used in the present invention is 4 or less. If the pKa exceeds 4, the ability to release protons is weak, and the synergistic effect with the polyvinyl alcohol and the hydrous layered silicate mineral described below cannot be obtained.

[0025] Examples of Bronsted acids having a pKa of 4 or less that can be used in the present invention include the following. For example, inorganic acids include hydrochloric acid (pKa-3.7), formic acid (pKa 3.8), oxalic acid (first pKa 1.3), nitric acid (pKa-1.8), sulfuric acid (first pKa-5.0, second pKa 2.0), phosphoric acid (first pKa 1.8), etc., and organic acids include citric acid (first pKa 3.1), glycine (first pKa 2.4), salicylic acid (pKa 3.0), lactic acid (pKa 3.8), phthalic acid (first pKa 2.9), etc. ), fumaric acid (first pKa 3.0), malonic acid (first pKa 2.8), maleic acid (first pKa 1.9), malic acid (first pKa 3.4), etc. are particularly preferred, as solid acids with a pKa that is not too low and high in water solubility, for the reasons that they dissolve quickly in water during granule production, are less likely to volatilize when dried, and it is easy to prevent deterioration of materials when mixed with other materials. The Bronsted acids that can be used in the present invention may be used alone or in combination of two or more kinds, and the amount added is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, in the preparation.

[0026] <(d) Hydrous layered silicate minerals with swelling levels of 2-5 mL / 2 g> In the pesticide granule of the present invention, the hydrous layered silicate mineral contributes to hardness development and disintegrability in water under static conditions and stirring conditions. Hydrous layered silicate minerals are formed by stacking two types of layered structures: tetrahedral sheets, which are formed by successive tetrahedral structures consisting of four oxygen atoms at the center of silicon, and octahedral sheets, which are formed by successive octahedral structures consisting of six hydroxyl groups at the center of either aluminum, magnesium, or iron ions. Minerals with a 1:1 type layered structure consisting of one tetrahedral sheet and one octahedral sheet are called kaolin minerals. Minerals with a 2:1 type layered structure consisting of one octahedral sheet sandwiched between two tetrahedral sheets include smectite, vermiculite, and mica clay minerals. These substances have small particle sizes, so they exhibit characteristic properties such as colloidal behavior, cation exchange capacity, water swelling, and the ability to form complexes with organic matter and other substances. These characteristics vary depending on the layered structure, and 2:1 type structures have high cation exchange capacity and high swelling power. Taking advantage of this property, bentonite with a high smectite content is used as a soil improvement material or a muddy water conditioner for soil excavation. On the other hand, the 1:1 type structure is the opposite, with both cation exchange capacity and swelling power being low.

[0027] Among these clay properties, the swelling power can be evaluated by the swelling test method for bentonite (powdered) (JBAS-104-77) established by the Japan Bentonite Industry Association. This method is carried out as described below. 2.0 g of sample adjusted to 8.0% moisture is added in about 10 separate additions to a 100 mL stoppered measuring cylinder containing 100 mL of distilled water. The next addition is made after the previous additive has settled to the bottom of the measuring cylinder. After leaving it to stand for 24 hours, the apparent volume of the swollen sample mass at the bottom of the measuring cylinder is read from the graduated cylinder scale and expressed as swelling power (mL / 2g). The general swelling power of sodium bentonite, which has a high swelling power, is 15 or more, and even calcium bentonite, which has a low swelling power, is about 6. The swelling power of the hydrous layered silicate mineral used in the present invention must be 2 to 5 mL / 2 g according to the swelling test method (JBAS-104-77). If the swelling power is less than 2 mL / 2 g, the swelling of the particles when absorbing water is too small, so that the disintegration in water under stirring conditions is reduced, and the particles are difficult to disintegrate, leading to a decrease in efficacy. On the other hand, if the swelling power exceeds 5 mL / 2 g, the swelling of the particles when absorbing water is large, which leads to powdering when sprayed due to a decrease in the formulation hardness under humidified conditions, and the particles are easily disintegrated in water under stationary conditions, leading to a decrease in sprayability, which leads to a decrease in sprayability. The amount of the hydrous layered silicate mineral that can be used in the present invention to be added is 5 to 90% by weight, preferably 10 to 50% by weight, in the preparation.

[0028] <(e) C10-18 Aliphatic Hydrocarbon Anionic Surfactants> In the pesticide granule of the present invention, the C10-18 aliphatic hydrocarbon anionic surfactant brings about the effect of improving each of the efficacies of hardness development, static conditions, and water disintegration properties under stirring conditions. In this anionic surfactant, the aliphatic hydrocarbon moiety having 10 to 18 carbon atoms imparts wettability, and the anion moiety imparts dispersibility. As a result, when moisture is absorbed during production or after formulation, the water circulation in the formulation is made more efficient, and the interaction between each component described below is promoted.

[0029] Examples of C10-18 aliphatic hydrocarbon-based anionic surfactants that can be used in the present invention include the following. Examples of the alkyl naphthalene sulfonate include C10-18 alkyl naphthalene sulfonate, C10-18 alkyl benzene sulfonate, C10-18 alkyl sulfate, C10-18 alkyl sulfonate, C10-18 alkyl phosphate, C10-18 alkenyl sulfonate, polyoxyethylene C10-18 alkyl ether sulfate, polyoxyalkylene C10-18 alkyl ether sulfate, polyoxyethylene C10-18 alkyl ether sulfonate, polyoxyalkylene C10-18 alkyl ether sulfonate, polyoxyethylene C10-18 alkyl ether phosphate, polyoxyalkylene C10-18 alkyl ether phosphate, and N-C10-18 acyl methyl taurine salt, and C10-18 alkenyl sulfonate is particularly preferred. The amount of the C10-18 aliphatic hydrocarbon anionic surfactant usable in the present invention may be one or more than one in combination, and is preferably 0.05-10% by weight, more preferably 0.1-5% by weight in the formulation.

[0030] <Synthetic effect of polyvinyl alcohol, Bronsted acid, and hydrous layered silicate minerals> In the pesticide granules of the present invention, it was found that an unexpected synergistic effect can be obtained by blending (b) polyvinyl alcohol with a saponification degree of 60 to 100 mol%, (c) a Bronsted acid with a pKa of 4 or less, and (d) a hydrous layered silicate mineral with a swelling degree of 2 to 5 mL / 2 g in the swelling power test (JBAS-104-77). Due to its high hydrophilicity, polyvinyl alcohol swells and dissolves when in contact with water, causing the granules to disintegrate and exhibit adhesiveness to the plant body, but by combining (b) polyvinyl alcohol with a saponification degree of 60 to 100 mol%, (c) a Bronsted acid with a pKa of 4 or less, and (d) a hydrous layered silicate mineral with a swelling degree of 2 to 5 mL, the degree of swelling is adjusted, and the pesticide granules can be given underwater disintegrability that does not disintegrate under static conditions in water but disintegrates under stirring conditions. This prevents adhesion due to the collapse of the granules even when sprayed under high temperature and humidity conditions where a large amount of water droplets adhere to the granules, and after spraying, the granules gradually lose strength and collapse as they absorb water in the field or through irrigation, thereby exerting their effect. It is generally known that acidic substances suppress the swelling of hydrous layered silicate minerals with a large degree of swelling, but the degree of swelling is excessive in both cases, and it is not possible to impart disintegrability in water that simultaneously satisfies the requirements of non-disintegrability when left standing and disintegrability when stirred. In this study, the combined use of (b) polyvinyl alcohol with a saponification degree of 60 to 100 mol%, (c) a Bronsted acid with a pKa of 4 or less, and (d) a hydrous layered silicate mineral with a swelling degree of 2 to 5 mL / 2 g made it possible to control disintegration in water by adjusting the swelling degree.

[0031] The mechanism by which the agrochemical granules of the present invention are capable of controlling disintegration in water is unclear, but due to their chemical structures, both the hydrous layered silicate mineral and polyvinyl alcohol may be cationized by the addition of protons derived from Bronsted acids. It is presumed that the degree of swelling and dissolution rate of each substance are controlled by electrostatic interaction between some of the cationized hydrous layered silicate minerals or polyvinyl alcohol and non-cationized hydrous layered silicate minerals or polyvinyl alcohol, or by hydrogen bonds or electrostatic interaction between polyvinyl alcohol molecules, which contributes to improving the performance of the formulation hardness and disintegration in water. In addition, (e) the use of a C10-18 aliphatic hydrocarbon anionic surfactant in combination improves the formulation hardness and disintegration in water, and this is also presumably due to the interaction between the anionic portion of the surfactant and the cationized hydrous layered silicate mineral and polyvinyl alcohol.

[0032] <About solid carriers> Examples of solid supports that can be used in the present invention include those listed below. For example, natural minerals such as clay, quartz, calcite, sepiolite, dolomite, chalk, kaolin, pyrophyllite, sericite, halloysite, metahaloysite, wood-bush clay, frog-eye clay, pottery stone, ziglite, allophane, shirasu, kira, talc, pumice, hectorite, zeolite and diatomaceous earth; calcined products of natural minerals such as calcined clay, perlite, shirasu balloon, vermiculite, attapulgus clay and calcined diatomaceous earth; magnesium carbonate, calcium carbonate, sodium carbonate, etc. , inorganic salts such as sodium bicarbonate, ammonium sulfate, sodium sulfate, magnesium sulfate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and potassium chloride; sugars such as glucose, fructose, sucrose, and lactose; polysaccharides such as starch, powdered cellulose, and dextrin; organic substances such as urea, urea derivatives, benzoic acid, and salts of benzoic acid; plants such as wood flour, corn cobs, walnut shells, and tobacco stalks; fly ash, white carbon, and the like. Among these, clay is more preferred in terms of the balance between disintegrability in water and preparation hardness. The amount of the solid carrier that can be used in the present invention to be added is 5 to 95% by weight, preferably 10 to 90% by weight, in the preparation.

[0033] <Other supplements> In addition to the above-mentioned essential components, the pesticide granules of the present invention may contain the following components as adjuvants to the extent that the effect of the present invention is not lost. For example, the surfactant may be a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant.

[0034] Examples of nonionic surfactants include polyoxyethylene alkylaryl ethers, polyoxyalkylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyalkylene aryl aryl ethers, polyoxyethylene alkanediols, polyoxyethylene alkyl esters, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene hydrogenated castor oil, sucrose fatty acid esters, polyoxyethylene-polyoxypropylene block polymers, and alkyl glucosides.

[0035] Examples of the anionic surfactant include a condensate of naphthalenesulfonic acid and formalin or a salt thereof, a condensate of alkylnaphthalenesulfonic acid and formalin or a salt thereof, ligninsulfonate, monoalkylsulfosuccinate, dialkylsulfosuccinate, polyoxyethylene alkylsulfosuccinate, polyoxyalkylene alkylsulfosuccinate, polyoxyethylene alkylphenyl ether phosphate, polyoxyalkylene alkylphenyl ether phosphate, polyoxyethylene arylphenyl ether phosphate, polyoxyalkylene arylphenyl ether phosphate, polyoxyethylene alkylphenyl ether sulfate, polyoxyalkylene alkylphenyl ether sulfate, polyoxyethylene arylphenyl ether sulfate, and polyoxyalkylene arylphenyl ether sulfate.

[0036] Examples of the cationic surfactant include alkyl trimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, and alkyl pyridinium salts.

[0037] Examples of amphoteric surfactants include dialkylaminoethyl betaine and alkyldimethylbenzyl betaine.

[0038] The surfactants that can be used in the present invention are not limited to these examples, and one or more of them may be used in combination. The content of the surfactant in the preparation is preferably 0.1 to 20% by weight.

[0039] Examples of the auxiliary binder include, but are not limited to, processed starches such as dextrin (roasted dextrin, enzyme-modified dextrin, etc.), acid-decomposed starch, oxidized starch, pregelatinized starch, etherified starch (carboxymethyl starch, hydroxyalkyl starch, etc.), esterified starch (starch acetate, starch phosphate, etc.), crosslinked starch, and grafted starch; natural substances such as sodium alginate, gum arabic, gelatin, tragacanth gum, locust bean gum, and casein; cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, methyl cellulose, ethyl cellulose, and acetyl cellulose; polyethylene oxide, alginates, polyvinylpyrrolidone, polyethylene glycol, etc., and there is no problem even if one or more of these are used in combination. The content of the binder in the pesticide granules is preferably 0.1 to 10% by weight.

[0040] Examples of preservatives and antiseptics include potassium sorbate, p-chloro-m-xylenol, butyl p-oxybenzoate, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, etc.; examples of pH adjusters include hydrochloric acid, sulfuric acid, citric acid, phosphoric acid, magnesium carbonate, etc.; and examples of stabilizers for pesticide active ingredients include antioxidants, ultraviolet light protectors, and crystal precipitation inhibitors, but are not limited to the adjuvants exemplified here.

[0041] <Manufacturing method of pesticide granules> The pesticide granules of the present invention are produced by extrusion granulation, which is advantageous in terms of economy and production efficiency. In the manufacturing process, the pesticide active ingredient, polyvinyl alcohol with a degree of saponification of 60 to 100 mol%, Bronsted acid with a pKa of 4 or less, hydrous layered silicate mineral with a swelling degree of 2 to 5 mL / 2 g in the swelling power test (JBAS-104-77), C10-18 aliphatic hydrocarbon-based anionic surfactant, and various auxiliary agents are added as necessary, and mixed uniformly using a juice mixer, hammer mill, Loedige mixer, ribbon mixer, Nauta mixer, etc. Water is added to this mixture and kneaded using a double-arm kneader or ribbon mixer, etc. Note that, for reasons such as mixing accuracy, if the pesticide active ingredient is wet-pulverized and added as a slurry, a solution dissolved in a solvent is added, or a solution of polyvinyl alcohol dissolved in water is added, it is added together with water during kneading. Next, this mixture is granulated using an extrusion granulator such as a basket granulator or a screw granulator. The extrusion hole diameter during granulation is usually in the range of 0.3 to 5 mm, preferably 0.5 to 2 mm. The resulting granules are sized using a marumerizer or a pin mill, dried using a fluidized bed dryer or a bed dryer, and then sieved to obtain the pesticide granules used in the present invention.

[0042] <How granular pesticides are used> The pesticide granules produced by the above-mentioned method are used by directly spraying them on paddy fields, fields, orchards, lawns, non-agricultural land, etc., according to known methods of use. Specifically, there are methods of spraying foliage by means of hand spreading, a granulator, a backpack-type powered sprayer, a sprayer for simultaneous rice planting treatment, an industrial unmanned helicopter, an industrial multirotor, etc., methods of spraying at the base or side stripes of plants, methods of mixing with soil, methods of spraying on the soil surface, methods of spraying on the water surface in a flooded state, and methods of box treatment. The amount of the pesticide granule of the present invention used varies depending on the type and content of the pesticide active ingredient contained, but is usually about 10 to 5000 g, preferably about 30 to 3000 g per 10 ares.

[0043] [Examples 1 to 36, Comparative Examples 1 to 32] Agricultural chemical granules were produced based on the compositions shown in the following Tables 1 to 8 (Tables 1, 3, 5, and 7 for Examples, and 2, 4, 6, and 8 for Comparative Examples). In the examples and comparative examples, all parts are by weight. The detailed manufacturing method of the pesticide granules containing various pesticide active ingredients is as follows.

[0044] <Imidacloprid 1% granules> [Examples 1 to 9, Comparative Examples 1 to 8] Imidacloprid (insecticidal component), polyvinyl alcohol (in Examples 1 to 9, one with a saponification degree of 60 to 100 mol% was used, and in Comparative Examples 1 to 8, one with a saponification degree of 60 to 100 mol%, or one with a saponification degree of less than 60 mol% was used or not added), Bronsted acid (in Examples 1 to 9, one with a pKa of 4 or less, and in Comparative Examples 1 to 8, one with a pKa of 4 or less, or one with a saponification degree of more than 4 was used or not added), hydrous layered silicate mineral (in Examples 1 to 9, one with a swelling degree of 2 to 5 mL / 2 g in the swelling power test (JBAS-104-77) was used, and in Comparative Examples 1 to 8, one with a swelling degree of 2 to 5 mL / 2 g, less than 2 mL / 2 g, or more than 5 mL / 2 g was used or not added), C10-18 aliphatic hydrocarbon-based anionic surfactant, and other auxiliary agents (binders, solid carriers) were roughly mixed in a vinyl bag, and then pulverized and mixed with a hammer mill (Sample Mill KIIW-1, Dalton Co., Ltd.). The obtained powder mixture was put into a twin-arm kneader (KDHJ, manufactured by Dalton Co., Ltd.), and after adding an appropriate amount of water, it was kneaded for 15 minutes. Next, the water-added kneaded product was granulated using an extrusion granulator (basket type granulator FY-KS-2 type, manufactured by Fuji Yakuhin Kikai Co., Ltd.) equipped with a basket type screen with a hole diameter of 1.0 mm. The obtained granulated product was sized and then dried using a fluidized bed dryer (midget dryer MDB-400, manufactured by Dalton Co., Ltd.). This was sieved at 1700 μm to 850 μm to obtain an agricultural chemical granule.

[0045] <Kasugamycin 6% Granules> [Examples 10 to 18, Comparative Examples 9 to 16] Kasugamycin (bactericidal component), Bronsted acid (pKa 4 or less in Examples 10 to 18, pKa 4 or less in Comparative Examples 9 to 16, or more than 4 was used or no addition was made), hydrous layered silicate mineral (pKa 4 or less in Examples 10 to 18, or more than 4 was used or no addition was made, or no addition was made, or no addition was made, or no addition was made, or no addition was made, or no addition was made, or no addition was made, or no addition was made, or no addition was made, or no addition was made, and ... The obtained powder mixture was put into a twin-arm kneader (KDHJ, manufactured by Dalton Co., Ltd.), and after adding a 15% aqueous solution of polyvinyl alcohol (saponification degree of 60-100 mol% was used in Examples 10-18, and saponification degree of 60-100 mol% or less than 60 mol% was used or not added in Comparative Examples 9-16) and appropriate water, the mixture was kneaded for 15 minutes. Next, the water-kneaded mixture was weighed and granulated with an extrusion granulator (basket type granulator FY-KS-2 type, manufactured by Fuji Yakuhin Kikai Co., Ltd.) equipped with a basket type screen with a hole diameter of 0.8 mm. The obtained granulated product was sized and then dried with a fluidized bed dryer (midget dryer MDB-400, manufactured by Dalton Co., Ltd.). This was sieved at 1400 μm to 500 μm to obtain an agricultural chemical granule.

[0046] <Thifluzamide 3% Granules> [Examples 19 to 27, Comparative Examples 17 to 24] Thifluzamide (bactericidal component), polyvinyl alcohol (Examples 19 to 27 use one with a saponification degree of 60 to 100 mol%, Comparative Examples 17 to 24 use one with a saponification degree of 60 to 100 mol%, or one with a saponification degree of less than 60 mol% or no addition), Bronsted acid (Examples 19 to 27 use one with a pKa of 4 or less, Comparative Examples 17 to 24 use one with a pKa of 4 or less, or one with a saponification degree of more than 4 or no addition), hydrous layered silicate mineral (Examples 19 to 27 use one with a swelling degree of 2 to 5 mL / 2 g in the swelling power test (JBAS-104-77), or one with a swelling degree of 2 to 5 mL / 2 g, less than 2 mL / 2 g, or more than 5 mL / 2 g or no addition in Comparative Examples 17 to 24), C10-18 aliphatic hydrocarbon-based anionic surfactant, and other auxiliary agents (binders, solid carriers) were roughly mixed in a vinyl bag, and then pulverized and mixed with a hammer mill (Sample Mill KIIW-1, Dalton). The obtained powder mixture was put into a twin-arm kneader (KDHJ, manufactured by Dalton Co., Ltd.), and after adding an appropriate amount of water, it was kneaded for 15 minutes. Next, the water-added kneaded product was granulated using an extrusion granulator (basket type granulator FY-KS-2 type, manufactured by Fuji Yakuhin Kikai Co., Ltd.) equipped with a basket type screen with a hole diameter of 1.0 mm. The obtained granulated product was sized and then dried using a fluidized bed dryer (midget dryer MDB-400, manufactured by Dalton Co., Ltd.). This was sieved at 1700 μm to 850 μm to obtain an agricultural chemical granule.

[0047] <Simetryn 4.5% + Benfuresate 5% Granules> [Examples 28 to 36, Comparative Examples 25 to 32] Simetryne (herbicidal component), benfuresate (herbicidal component), polyvinyl alcohol (Examples 28 to 36 use one with a saponification degree of 60 to 100 mol%, Comparative Examples 25 to 32 use one with a saponification degree of 60 to 100 mol%, or one with a saponification degree of less than 60 mol% or no addition), Bronsted acid (pKa 4 or less in Examples 28 to 36, or one with a pKa 4 or less, or one with a pKa greater than 4 or no addition in Comparative Examples 25 to 32), hydrous layered silicate mineral (Examples 28 to 36 use one with a saponification degree of 60 to 100 mol%, or ... less than 60 mol% or no addition), In Comparative Example 6, the swelling degree in the swelling power test (JBAS-104-77) was 2 to 5 mL / 2 g, and in Comparative Examples 25 to 32, the swelling degree was 2 to 5 mL / 2 g, less than 2 mL / 2 g, or more than 5 mL / 2 g, or no addition was used), C10-18 aliphatic hydrocarbon-based anionic surfactant, and other auxiliary agents (binder, solid carrier) were roughly mixed in a vinyl bag, and then pulverized and mixed with a hammer mill (Sample Mill KIIW-1, Dalton). The obtained powder mixture was charged into a double-arm kneader (KDHJ, Dalton), and after adding an appropriate amount of water, the mixture was kneaded for 15 minutes. Next, the water-added kneaded product was granulated with an extrusion granulator (basket type granulator FY-KS-2, Fuji Yakuhin Kikai Co., Ltd.) equipped with a basket type screen with a hole diameter of 1.2 mm. The obtained granulated product was sized and then dried with a fluidized bed dryer (Midget Dryer MDB-400, Dalton). This was sieved through a 1700 μm to 1000 μm sieve to obtain pesticide granules.

[0048] Next, the usefulness of the pesticide granules of the present invention will be demonstrated by test examples. This test was conducted for the purposes of evaluating the dispersibility (disintegrability in water under static conditions, formulation hardness after storage at high temperature and humidity), efficacy (disintegrability in water under stirring conditions) and storage stability (formulation hardness at the time of preparation).

[0049] <Testing the water disintegration of granules under static conditions> 500 mL of 10 degree hard water was placed in a 15 cm diameter glass petri dish, and the water temperature was adjusted to 35° C. using a thermohygrostat (ESPEC, LHU-114). After adjusting the water temperature, 500 mg of granules were added and allowed to stand for another hour at 35° C. The disintegration of the granules after standing was observed with the naked eye, and evaluated based on the following criteria.

[0050] <Evaluation criteria for disintegration in water under static conditions> A: No collapse, no change in appearance B: Non-disintegrating, particles swell but retain their original shape C: Non-disintegrating, cracks appear on the grain surface but the original shape is maintained D: Coarse grain collapse, grains lose their original shape E: Completely disintegrated, no trace of the grain remains The ratings A, B, and C were deemed acceptable (difficult to adhere to plant body), while D and E were deemed unacceptable (easy to adhere to plant body). The test results are shown in Tables 1, 3, 5 and 7 (Examples) and Tables 2, 4, 6 and 8 (Comparative Examples).

[0051] <Testing the water disintegration of granules under stirring conditions> After placing 200 mL of 10 degree hard water and a stirrer (φ3 cm) in a 300 mL glass beaker, adjust the water temperature to 35°C using a thermohygrostat (ESPEC, LHU-114). After adjusting the water temperature, adjust the rotation speed of a magnetic stirrer so that the vortex is about 1 cm above the water surface, then add 500 mg of granules and stir for 30 minutes at 35°C. The disintegration of the granules after stirring was observed with the naked eye and evaluated based on the following criteria.

[0052] <Evaluation criteria for underwater disintegration under stirring conditions> A: Completely disintegrated, no trace of the grain remains B: Most of the particles have collapsed, and the remaining particles are no longer of their original shape. C: About half of the particles have collapsed, and the remaining particles are no longer intact. D: Most of the particles did not disintegrate, and the remaining particles still retain their original shape. E: Non-disintegrating, particles are intact and hard Evaluations A, B, and C were deemed acceptable (excellent disintegratability after spraying), while D and E were deemed unacceptable (insufficient disintegratability after spraying). The test results are shown in Tables 1, 3, 5 and 7 (Examples) and Tables 2, 4, 6 and 8 (Comparative Examples).

[0053] <Granule hardness evaluation test> For the purpose of evaluating the risk of granules collapsing in more detail, hardness was measured under stricter operating conditions based on the Zennoh method (the method for testing the physical properties of pesticide formulations stipulated by the National Federation of Agricultural Cooperative Associations). The outline is given below. 1) The granules were thoroughly sieved through a standard mesh sieve with 500 μm openings, and the samples were those with almost no residue remaining on the mesh. 2) 100 g of the sample was precisely weighed and placed in a magnetic pot (inner diameter 100 mm, inner depth 100 mm) for a ball mill containing three magnetic balls (total weight 105 g) with a diameter of 30±2 mm and a weight of 35±3 g. 3) This magnetic pot for the ball mill was placed on a variable roller and rotated at a rotation speed of 75 revolutions per minute for 30 minutes. 4) The sample was removed from the magnetic pot and thoroughly sieved through a 500 μm standard sieve. The weight of the fine powder that passed through the sieve was precisely weighed, and then the hardness (disintegration rate) was calculated using the following formula. The samples used were granules immediately after preparation and granules that had been subjected to the following abuse test.

[0054] <High temperature and humidity abuse test for granules> 1 kg of granules was packed into a 2-pack craft bag (bottom dimensions 6 cm x 12 cm) and packaged. The top of the package was flattened, a 6 cm x 12 cm plastic plate was placed on top of it, and a 7.2 kg weight was placed evenly across the entire plastic plate, so that the load on the granules was 100 g / cm. 2 The package was placed in a thermohygrostat (ESPEC, LHU-114) adjusted to 35°C and 80% relative humidity, and after 30 days, it was taken out and subjected to a hardness evaluation test.

[0055]

number

[0056] [Table 1]

[0057] [Table 2]

[0058] [Table 3]

[0059] [Table 4]

[0060] [Table 5]

[0061] [Table 6]

[0062] [Table 7]

[0063] [Table 8]

[0064] From the test results in Tables 1 to 8, it was proven that the formulation of (b) polyvinyl alcohol with a saponification degree of 60 to 100 mol%, (c) Bronsted acid with a pKa of 4 or less, and (d) hydrous layered silicate with a swelling degree of 2 to 5 mL / 2 g in the swelling power test (JBAS-104-77) is essential for the expression of all of the effects of disintegration in water under static conditions, formulation hardness (spreadability) under high temperature and humidity conditions, disintegration in water under stirring conditions (effect expression), and formulation hardness at the time of preparation (storage stability). Examples 1 to 36 (Tables 1, 3, 5, and 7) of the present invention, which contain all of the components (b) to (d), met the pass criteria in all test examples. On the other hand, Comparative Examples 1 to 32, which do not contain any one of the components (b) to (d), did not meet the pass criteria in any of the test examples, and the performance was insufficient.

[0065] Specifically, in Comparative Examples 1 to 3, 9 to 11, 17 to 19, and 25 to 27, which did not use polyvinyl alcohol, used one with a saponification degree of less than 60 mol%, or used other water-soluble polymers such as polyvinylpyrrolidone, starch phosphate, dextrin, and sodium alginate, the disintegration in water (under static or stirred conditions) and the hardness of the formulation (at the time of preparation and after storage at high temperature and humidity) decreased. Regarding Bronsted acid, in Comparative Examples 4, 5, 12, 13, 20, 21, 28, and 29 in which no Bronsted acid was used or a Bronsted acid with a pKa of more than 4 was used, the disintegration in water (static conditions) and the hardness of the preparation (at the time of preparation and after storage at high temperature and humidity) decreased. In Comparative Examples 6-8, 14-16, 22-24, and 30-32, which did not use hydrous layered silicate mineral or used layered silicate mineral with a swelling degree of more than 5mL / 2g or less than 2mL / 2g in the swelling power test (JBAS-104-77), the water disintegration property (static condition or stirring condition) and the preparation hardness (at the time of preparation and after storage at high temperature and humidity) were decreased. That is, the results of this test suggest that when the formulation does not contain any of (b) polyvinyl alcohol with a saponification degree of 60-100 mol%, (c) Bronsted acid with a pKa of 4 or less, or (d) hydrous layered silicate with a swelling degree of 2-5mL / 2g in the swelling power test (JBAS-104-77), it is impossible to maintain the balance of the water disintegration property (static condition, stirring condition) and the preparation hardness (at the time of preparation and after storage at high temperature and humidity), and the simultaneous formulation of these components brings about a synergistic effect.

[0066] In addition, the use of polyvinyl alcohol with a saponification degree of 80-90 mol% and an average polymerization degree of 500-2000, the use of malic acid, glycine or citric acid as a Bronsted acid, and (e) the use of a C10-18 aliphatic hydrocarbon anionic surfactant (particularly a C10-18 alkenylsulfonate) resulted in further improvements in the performance of disintegration in water (static conditions, stirring conditions) and formulation hardness (at the time of preparation and after storage at high temperature and humidity). Examples 8, 9, 17, 18, 26, 27, 35, and 36, which combine these elements, are superior among the Examples, and Examples 9, 18, 27, and 36 are particularly superior.

[0067] From the above, in order to obtain an agrochemical granule having excellent applicability, effect expression, and storage stability, which does not disintegrate during transportation and storage, has a formulation strength that does not powder when sprayed even under conditions where a large amount of water droplets are present on the surface of the plant body, and has water disintegrability such that adhesion to the plant body is suppressed while gradually disintegrating with moisture in the field or irrigation after spraying, it has been found that an effective means is to contain (b) polyvinyl alcohol with a saponification degree of 60 to 100 mol%, (c) a Bronsted acid with a pKa of 4 or less, and (d) a hydrous layered silicate mineral with a swelling degree of 2 to 5 mL / 2 g in the swelling power test (JBAS-104-77), and further, that the saponification degree of the polyvinyl alcohol is 80 to 90 mol%, the average polymerization degree is 500 to 2000, and further, a C10-18 aliphatic hydrocarbon-based anionic surfactant is added.

Claims

1. A pesticide granule comprising (a) a pesticide active ingredient, (b) polyvinyl alcohol having a degree of saponification of 60 to 100 mol%, (c) a Bronsted acid having a pKa of 4 or less, and (d) a hydrous layered silicate mineral having a swelling degree of 2 to 5 mL / 2 g in a swelling power test (JBAS-104-77).

2. 2. The pesticide granule according to claim 1, wherein the polyvinyl alcohol (b) has a degree of saponification of 80 to 90 mol % and an average degree of polymerization of 500 to 2,000.

3. 3. The pesticide granule according to claim 1, further comprising: (e) a C10-18 aliphatic hydrocarbon anionic surfactant.

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