JP2009073820A - Granular agrichemical composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a granular agrichemical composition containing at least two agrichemical active components and capable of altering the extended-release performance of the agrichemical active components. <P>SOLUTION: This granular agrichemical composition contains a coated granular agrichemical composition which is formed by fixing and coating a powdery agrichemical composition containing a first agrichemical active component by a thermosetting resin, a second agrichemical active component having an aqueous solubility at 25&deg;C of not higher than 500 mg/L, a solid carrier, a binder, and a surfactant; and this granular agrichemical composition contains 0.5-30 wt.% the coated granular agrichemical composition which is formed by fixing and coating a powdery agrichemical composition containing a first agrichemical active component by a thermosetting resin, 0.1-30 wt.% the second agrichemical active component, 15-98.8 wt.% the solid carrier, 0.5-10 wt.% the binder, and 0.1-15 wt.% the surfactant. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to an agrochemical granule composition.

  Conventionally, various agrochemical formulations (hereinafter referred to as sustained-release agrochemical formulations) capable of sustained release of pesticidal active compounds have been proposed for the purpose of sustaining drug efficacy and reducing phytotoxicity. Examples of such sustained-release agrochemical formulations include microencapsulated liquids containing pesticidal active compounds (see Patent Document 1), and granules coated with pesticidal active compounds (see Patent Document 2). Are known.

JP 11-314032 A JP-A-11-005704

  To provide a pesticidal granule composition containing two or more pesticidal active ingredients and having excellent sustained release performance.

As a result of intensive studies, the present inventor has completed the present invention. That is, the present invention includes the following inventions.
[Invention 1]
A coated granular agricultural chemical composition obtained by solidifying and coating a powdered agricultural chemical composition containing a first agricultural chemical active ingredient with a thermosetting resin, and a second agricultural chemical active ingredient having a water solubility at 25 ° C. of 500 mg / L or less And an agrochemical granule composition comprising a solid carrier, a binder, and a surfactant.
[Invention 2]
The content of the coated granular agricultural chemical composition obtained by solidifying and coating the powdered agricultural chemical composition containing the first agricultural chemical active ingredient with a thermosetting resin is 0.5 to 30% by weight, and the content of the second agricultural chemical active ingredient The amount is 0.1 to 30% by weight, the solid carrier content is 15 to 98.8% by weight, the binder content is 0.5 to 10% by weight, and the surfactant content is 0.1 to 15%. The agrochemical granule composition according to invention 1, which is in weight percent.
[Invention 3]
The agrochemical granule composition according to invention 1 or 2, wherein the thermosetting resin is a urethane resin.
[Invention 4]
The agrochemical granule composition according to any one of Inventions 1 to 3, wherein the first agrochemical active ingredient is an agrochemical active ingredient having a water solubility at 25 ° C of 100 mg / L or more and 1000 mg / L or less.
[Invention 5]
The agrochemical granule composition according to any one of inventions 1 to 3, wherein the combination of the first agrochemical active ingredient and the second agrochemical active ingredient is a combination of an insecticidal active ingredient and a bactericidal active ingredient.
[Invention 6]
The first pesticidal active ingredient is (E) -N-((2-chloro-5-thiazolyl) methyl) -N′-methyl-N ″ -nitroguanidine, and the second pesticidal active ingredient is 2- Selected from the group consisting of cyano-N-[(1R)-(2,4-dichlorophenyl) ethyl] -3,3-dimethylbutanamide and 2'-cyano-3,4-dichloroisothiazole-5-carboxyanilide The agrochemical granule composition according to any one of Inventions 1 to 3, which is at least one kind.
[Invention 7]
The agrochemical granule composition according to invention 6, wherein the solid carrier is calcium carbonate or a combination of calcium carbonate and one or more other solid carriers, and the binder is pregelatinized starch.
[Invention 8]
The agrochemical granule composition according to any one of Inventions 1 to 7, wherein the surfactant is a nonionic surfactant.
[Invention 9]
The agrochemical granule composition according to any one of Inventions 1 to 8, which is for paddy rice seedling box treatment including handling at the time of sowing.
[Invention 10]
The agrochemical granule composition according to any one of Inventions 1 to 9, wherein the second agrochemical active ingredient has a water solubility at 25 ° C. of 50 mg / L or less.
[Invention 11]
(1) A coated granular pesticidal composition in which a powdery pesticidal composition containing a first pesticidal active ingredient is hardened with a thermosetting resin and coated, and a second water solubility at 25 ° C. of 500 mg / L or less A first step of kneading a mixture containing an agrochemical active ingredient, a solid carrier, a binder, a surfactant, and water; (2) a second step of extruding and granulating the kneaded product obtained in the first step. The manufacturing method of the agrochemical granule which has a process and the (3) 3rd process which dries the granulated material obtained at the 2nd process.

  The agrochemical granule composition of the present invention has excellent sustained release performance of an agrochemical granule composition containing two or more agrochemical active ingredients by appropriately changing the type and amount of the thermosetting resin used. It is possible to

  The present invention relates to a coated granular agricultural chemical composition comprising a powdered agricultural chemical composition (hereinafter referred to as the present powdered agricultural chemical composition) containing a first agricultural chemical active ingredient, which is hardened with a thermosetting resin and coated. A pesticidal granule composition comprising a second pesticidal active ingredient having a water solubility at 500 ° C. of 500 mg / L or less, a solid carrier, a binder, and a surfactant.

In the present invention, the agrochemical active ingredients generally include insecticidal compounds, fungicidal compounds, herbicidal compounds, insect growth control compounds, plant growth control compounds, insect repellents, and the like. Can be mentioned. These are solid at normal temperature (20 ° C.), but preferably have a higher melting point, for example, solid at 50 ° C. The first agrochemical active ingredient is an agrochemical active ingredient having a water solubility at 25 ° C. of usually 100 mg / L or more, preferably 100 to 1000 mg / L. Moreover, the agrochemical granule containing the coated granular agrochemical composition in which the present powdery agrochemical composition is hardened with a thermosetting resin and coated is used until 50% of the first agrochemical active ingredient is eluted in an underwater dissolution test. By adjusting the number of days to 5 to 35 days, the efficacy in paddy rice seedling box treatment can be sufficiently maintained.
The second pesticidal active ingredient may be the same as or different from the first pesticidal active ingredient as long as the water solubility at 25 ° C. is 500 mg / L or less. Each of the first pesticidal active ingredient and the second pesticidal active ingredient may be composed of a single pesticidal active compound, or may be composed of a plurality of pesticidal active compounds.
The combination of the first pesticidal active ingredient and the second pesticidal active ingredient may be, for example, a combination of an insecticidal active ingredient and a bactericidal active ingredient. The insecticidal active ingredient may contain a plurality of insecticidal compounds, and the bactericidal active ingredient may contain a plurality of bactericidal compounds.
The second pesticidal active ingredient preferably has a water solubility at 25 ° C. of 50 mg / L or less. The second pesticidal active ingredient preferably has a volume median diameter of 30 μm or less and a melting point of 100 ° C. or more.

Examples of insecticidal compounds include pyrethroid compounds such as deltamethrin, tralomethrin, acrinathrin, tetramethrin; carbamate compounds such as propoxer, isoprocarb, xylylcarb, metolcarb, XMC, carbaryl, pirimicarb, carbofuran, mesomil, phenoxycarb, chlorantraniliprole; Organophosphorous compounds such as acephate, trichlorfone, tetrachlorvinphos, dimethylvinphos, pyridafenthion, azinephosethyl, azinephosmethyl; diflubenzuron, chlorfluazuron, lufenuron, hexaflumuron, flufenoxuron, flucycloxuron, cyromazine, dia Fenthiuron, hexythiazox, novallon, teflubenzuron, triflumuron, 4-chloro-2- ( -Chloro-2-methylpropyl) -5- (6-iodo-3-pyridylmethoxy) pyridazin-3 (2H) -one, 1- (2,6-difluorobenzoyl) -3- [2-fluoro-4- (Trifluoromethyl) phenyl] urea, 1- (2,6-difluorobenzoyl) -3- [2-fluoro-4- (1,1,2,3,3,3-hexafluoropropoxy) phenyl] urea, 2-tert-Butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazon-4-one, 1- (2,6-difluorobenzoyl) -3 -Urea compounds such as [2-fluoro-4- (1,1,2,2-tetrafluoroethoxy) phenyl] urea; imidacloprid, acetamiprid, clothianidin, niten Chloromonicyl compounds such as ram and diacloden; cartap, buprofezin, thiocyclam, bensultap, phenoxycarb, phenazaquin, fenpyroximate, pyridaben, hydramethylnon, thiodicarb, chlorfenapyr, fenproximate, pymetrozine, pyrimidifene, tebufenozide, tebufenpyrado, triazamate Examples thereof include curves, sulfuramide, milbemectin, abamectin, spinosad, spimetram, boric acid, paradichlorobenzene, etoxazole and the like.
Among these, examples of the pesticidal active ingredient whose water solubility at 25 ° C. is 50 mg / L or less include etoxazole, bensultap, spimetram and the like.

Bactericidal compounds include benzimidazole compounds such as benomyl, carbendazim, thiabendazole and thiophanate methyl; phenyl carbamate compounds such as dietofencarb; dicarboximide compounds such as procimidone, iprodione and vinclozoline; diniconazole, propenazole, epoxyconazole, Azole compounds such as tebuconazole, difenoconazole, cyproconazole, flusilazole, triadimephone; acylalanine compounds such as metalaxyl; carboxyamide compounds such as flametopil, mepronil, flutlanyl, isothianyl, boscalid; Organophosphorus compounds such as pyrazophos; anilinopi such as pyrimethanil, mepanipyrim, cyprodinil Midine compounds; Cyanopyrrole compounds such as fludioxonil and fenpiclonyl; Antibiotics such as blastcidin S, kasugamycin, polyoxin, and validamycin; Methoxyacrylate compounds such as azoxystrobin, cresoxime methyl, and SSF-126; Captan, Folpet, Tricyclazole, Pyroxilone, Probenazole, Fusaride, Simoxanyl, Dimethomorph, CGA245704, Famoxadone, Oxolinic acid, Fluazinam, Ferimzone, Diclocimet, Clobenazone, Isovaradione, Tetrachloroisophthalonitrile, Thiophthalimidooxybisphenoxyarsine 3-iodo-2-propylbutyl carbamate, parahydroxybenzoate Ter, sodium dehydroacetate, potassium sorbate, 1-[(2-propenylthio) carbonyl] -2- (1-methylethyl) -4- (2-methylphenyl) -5-amino-1H-pyrazole-3- ON etc. can be mentioned.
Among these, pesticidal active ingredients having a water solubility at 25 ° C. of 50 mg / L or less include oxolinic acid, dietofencarb, diclosimet, tolcrofosmethyl, procymidone, 1-[(2-propenylthio) carbonyl] -2- ( 1-methylethyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one, isothianyl and the like.

Herbicidal compounds include: triazine compounds such as atrazine and metribudine; urea compounds such as fluometuron and isoproturon; hydroxybenzonitrile compounds such as bromoxynyl and ioxynil; 2,6-dinitroaniline compounds such as pendimesalin and trifluralin Compound; Allyloxyalkanoic acid compounds such as 2,4-D, dicamba, fluroxypyr, and mecoprop; sulfonylurea compounds such as bensulfuron methyl, methylsulfuron methyl, nicosulfuron, primsulfuron methyl, and cyclosulfamuron; imazapyr , Imidazolinone compounds such as imazaquin and imazetapyr; Bispyribac Na salt, Bisthiobac Na salt, Acifluorfen Na salt, Sulfentrazone, Paraquat, Flumetram, Trif Sulfuron methyl, phenoxaprop-p-ethyl, diflufenican, norflurazon, isoxaflutol, glufosinate ammunium salt, glyphosate, bentazone, mefenacet, propanyl, fluthiamid, full microlacpentyl, flumioxazin, bromobutide, Uniconazole P and the like can be mentioned.
Among these, examples of the pesticidal active ingredient whose water solubility at 25 ° C. is 50 mg / L or less include flumioxazin, bromobutide, uniconazole P and the like.

  Insect growth control compounds include juvenile hormone-like compounds such as 4-phenoxyphenyl 2- (2-pyridyloxy) propyl ether (hereinafter referred to as pyriproxyfen), metoprene, diflubenzuron, triflumuron, lufenuron, teflubenzuron, etc. Examples include chitin formation-inhibiting compounds, anti-juvenile hormone-like compounds, and molting hormone-like compounds.

  Examples of the plant growth regulating compound include maleic hydrazide, chlormecat, etephone, gibberellin, mepicut chloride, thiazuron, inavenfide, paclobutrazole, uniconazole and the like.

  Examples of the insect repellent include 1S, 3R, 4R, 6R-caran-3, 4-diol, dipropyl 2,5-pyridinedicarboxylate and the like.

The present pesticidal agrochemical composition may be used as it is when the first pesticidal active ingredient can be in a powder form, or may contain the first pesticidal active ingredient and diluted powder. . In this case, the amount of the first pesticidal active ingredient is usually 1 to 95% by weight, preferably 10 to 90% by weight, based on the powdery pesticide composition, and the amount of the diluted powder is based on the powdery pesticide composition. Usually, it is 5 to 99%, preferably 10 to 90%. The purpose of causing the diluted powder to be present in the powdery pesticide composition is, for example, improvement of grindability when producing a powdery pesticide composition having a volume median diameter of 1 to 100 μm, and fluidity of the powdery pesticide composition. Improvement of powder physical properties such as, and improvement of disaster prevention physical properties such as a dust explosion lower limit of the powdered agricultural chemical composition.
The volume median diameter of the diluted powder is preferably in the range of 1 to 100 μm. As the diluted powder, a powdery solid carrier generally used in agricultural chemical powders can be used, and examples thereof include mineral powders.
Examples of the mineral powders include kaolin minerals such as kaolinite, dickanite, nacrite, and halosite, montmorillonite minerals such as serpentine such as chrysotile, lizarite, anticorite, and amesite, sodium montmorillonite, calcium montmorillonite, and magnesium montmorillonite. Moisture such as smectite such as saponite, hectorite, saconite, hydelite, pyrophyllite, talc, wax, mica, fengite, sericite, illite, etc., silica such as cristobalite, quartz, water containing attapulgite, sepiolite, etc. Sulfate minerals such as magnesium silicate and gypsum, dolomite, calcium carbonate, gypsum, zeolite, zeolite, tuff, vermiculite, laponite, pumice, diatomaceous earth, acid clay, Sex clay, and the like. These mineral powders may be used alone or in combination of two or more. Further, the specific gravity is preferably large.

  In addition to the first pesticidal active ingredient and the diluted powder, the present pulverized pesticide composition is preferably 30% by weight or less, more preferably 20% by weight or less, based on the pulverized pesticide composition. Further, it may contain agrochemical adjuvants such as surfactants, stabilizers, colorants, and fragrances.

  Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl mono fatty acid ester, Polyoxypropylene glycol mono fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene fatty acid ester, higher fatty acid glycerin ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene block polymer , Polyoxyethylene fatty acid amide, alkylolamide, polyoxyethylene alkyl Nonionic surfactants such as amines, alkylamine hydrochlorides such as dodecylamine hydrochloride, dodecyltrimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylisoquinolinium salts, alkyls such as dialkylmorpholinium salts Cationic surfactants such as quaternary ammonium salts, benzethonium chloride and polyalkylvinylpyridinium salts, sodium fatty acids such as sodium palmitate, sodium ether carboxylates such as sodium polyoxyethylene lauryl ether carboxylate, sodium lauroyl sarcosine, N- Amino acid condensates of higher fatty acids such as sodium lauroyl glutamate, higher alkyl sulfonates, higher fatty acid ester sulfonates such as lauric ester sulfonate, Of dioctylsulfosuccinate of octylsulfosuccinate, higher fatty acid amide sulfonate such as oleic acid amide sulfonic acid, alkylaryl sulfonate such as sodium dodecylbenzene sulfonate, diisopropylnaphthalene sulfonate, alkylaryl sulfonate Anionic surface activity of formalin condensate, higher alcohol sulfate such as pentadecane-2-sulfate, polyoxyethylene alkyl phosphate such as dipolyoxyethylene dodecyl ether phosphate, styrene-maleate copolymer Agent, N-laurylalanine, N, N, N-trimethylaminopropionic acid, N, N, N-trihydroxyethylaminopropionic acid, N-hexyl-N, N-dimethylaminoacetic acid, 1- (2-carboxyethyl) ) Examples include amphoteric surfactants such as pyrimidinium betaine and lecithin.

  Stabilizers include, for example, phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, UV absorbers, epoxidized soybean oil, epoxidized linseed oil, epoxidized rapeseed oil, etc. Epoxidized vegetable oil, isopropyl acid phosphate, liquid paraffin, ethylene glycol and the like.

  Examples of the colorant include rhodamines such as rhodamine B and solar rhodamine, and dyes such as yellow No. 4, blue No. 1, and red No. 2, and examples of the fragrance include ethyl acetoacetate, ethyl enanthate, and cinnamic acid. Ester fragrances such as ethyl and isoamyl acetate, organic acid fragrances such as caproic acid and cinnamic acid, alcoholic fragrances such as cinnamon alcohol, geraniol, citral and decyl alcohol, aldehydes such as vanillin, piperonal and perylaldehyde, maltol, Examples thereof include ketone-based fragrances such as methyl β-naphthyl ketone, and menthol.

  The present powdery pesticide composition is obtained by mixing and pulverizing the first agrochemical active ingredient, the diluted powder as necessary, and further the agrochemical adjuvant as necessary. Moreover, it can also obtain by mixing each grind | pulverized previously to a powder form.

Examples of the thermosetting resin that hardens and coats the powdery agricultural chemical composition include urethane resin, urea resin, urethane-urea resin, and epoxy resin. In particular, the thermosetting resin used in the present invention is preferably a urethane resin.
The thermosetting resin is generally obtained by reacting two different liquid raw materials, and the coated granular agricultural chemical composition in the present invention is, for example, the first powdery agricultural chemical composition and the first raw material for the thermosetting resin. A liquid raw material is mixed, and then a second liquid raw material that is a raw material for the thermosetting resin is added to the obtained mixture, and the first liquid raw material and the second liquid raw material are reacted to produce a thermosetting resin. A granular pesticide is obtained, and the first liquid raw material and the second liquid raw material, which are raw materials for the thermosetting resin, are added simultaneously or sequentially to the obtained granular pesticide, and the first liquid raw material and the second liquid liquid are added. It can be produced by reacting the raw material and coating the granular pesticide with a thermosetting resin.
The first liquid raw material and the second liquid raw material are not necessarily limited to those composed of only one component, but may be a mixture composed of a plurality of components.

The urethane resin is a thermosetting resin using a polyol and polyisocyanate as liquid raw materials. The urethane resin is produced by reacting polyol and polyisocyanate by heating to, for example, 40 to 100 ° C. In that case, it may be made to react in presence of curing catalysts, such as an organic metal and an amine, as needed.
Examples of the polyol include condensed polyester polyols, polyether polyols, poly (meth) acrylic acid polyols, lactone polyester polyols, polycarbonate polyols, natural polyols and modified products thereof. The condensed polyester polyol is usually obtained by a condensation reaction between a polyol and a dibasic acid. The polyether polyol is usually obtained by addition polymerization of propylene oxide or ethylene oxide to a polyhydric alcohol or the like. Poly (meth) acrylic acid polyol is usually obtained by condensation reaction of poly (meth) acrylic acid and polyol, condensation reaction of (meth) acrylic acid and polyol, or polymerization reaction of (meth) acrylic acid ester monomer. It is done. The lactone polyester polyol is obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol as an initiator. Polycarbonate polyol is usually obtained by reaction of glycol and carbonate.
The polyol used in the present invention is a mixture of a branched polyol and a linear polyol so that the number of hydroxyl groups present in each polyol is in a ratio of 40:60 to 10:00. preferable. The branched polyol is a polyol having 3 or more hydroxyl groups in the molecule, and a polyol having 3 hydroxyl groups in the molecule is preferable. A linear polyol is a polyol having two hydroxyl groups in the molecule, and usually has hydroxyl groups at both ends of the molecule.
In addition, as the polyol, a linear polyol having an OH equivalent of 100 or less and a linear polyol having an OH equivalent of 100 or more, and the number of hydroxyl groups present in each polyol is 40:60 to 10:00. What mixed so that it may become a ratio is also preferable. Examples of the linear polyol having an OH equivalent of 100 or less include ethylene glycol, propylene glycol, trimethylene glycol and the like.

Examples of polyisocyanates include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, Examples thereof include 1,3- (isocyanatomethyl) cyclohexane, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, and mixtures thereof. In addition, it can replace with said polyisocyanate monomer and can also use these modified bodies and oligomers, as long as it has fluidity | liquidity.
Examples of modified products include adduct modified products, biuret modified products, isocyanurate modified products, block modified products, prepolymer modified products, and dimerized modified products. A polymethylene polyphenyl isocyanate (polymeric MDI) obtained by phosgenating a polyamine via condensation of aniline and formalin is preferable in terms of easy reaction control and low workability and excellent workability.

  Examples of the curing catalyst include dibutyltin diacetate, dibutyltin dichloride, dibutyltin dilaurate, dibutylthiostannic acid, stannous octylate, di-n-octyltin dilaurate, triethylenediamine, N-methylmorpholine, N, N-dimethyldidodecylamine, N-dodecylmorpholine, N, N-dimethylcyclohexylamine, N-ethylmorpholine, dimethylethanolamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine 1,8-diazabicyclo (5,4,0) undecene-7, isopropyl titanate, tetrabutyl titanate, oxyisopropyl vanadate, n-propyl zirconate, 1,4-diazabicyclo [2,2,2] octane, etc. Can be mentioned. Polyisocyanate and polyol, which are raw materials for urethane resins, are usually used alone.

The urea resin is a thermosetting resin using polyamine and polyisocyanate as liquid raw materials.
Examples of the polyisocyanate include the aforementioned polyisocyanates.
Examples of the polyamine include diethylenetriamine and triethylenetetraamine.

  The urethane-urea resin is a thermosetting resin that uses polyisocyanate, polyol, and polyamine as liquid raw materials.

The epoxy resin is a thermosetting resin using a curing agent and a glycidyl group-containing compound as a liquid raw material. In particular, a polyamine is preferable as the curing agent in the present invention, and a polyglycidyl ether or polyglycidylamine is preferable as the glycidyl group-containing compound.
The polyamines include diethylenetriamine, triethylenetetramine, metaxylylenediamine, isophoronediamine, methyliminobispropylamine, mensendiamine, metaphenylenediamine, diaminophenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, polyamide-modified polyamine. , Ketone-modified polyamine, epoxy-modified polyamine, thiourea-modified polyamine, Mannich-modified polyamine, Michael addition-modified polyamine, and the like.
Further, as the polyglycidyl ether, bisphenol A type polyglycidyl ether, bisphenol F type polyglycidyl ether, hydrogenated bisphenol A type polyglycidyl ether, naphthalene type polyglycidyl ether, brominated bisphenol A type polyglycidyl ether, bisphenol S type Polyglycidyl ether, bisphenol AF polyglycidyl ether, biphenyl polyglycidyl ether, fluorein polyglycidyl ether, phenol novolac polyglycidyl ether, O-cresol novolac polyglycidyl ether, DPP novolac polyglycidyl ether, trishydroxyphenyl Examples include methane type polyglycidyl ether, tetraphenylol ethane type polyglycidyl ether, and the like.
The polyglycidylamine includes tetraglycidyldiaminodiphenylmethane type polyglycidylamine, hydantoin type polyglycidylamine, 1,3-bis (N, N-diglycidylamonomethyl) cyclohexane, aniline type polyglycidylamine, and toluidine type. Examples include polyglycidylamine, triglycidyl isocyanurate type polyglycidylamine, aminophenol type polyglycidylamine, and the like.

In the urethane resin, as the first liquid raw material, either a polyol (including a mixture of two or more kinds of polyols) or a polyisocyanate (including a mixture of two or more kinds of polyisocyanates) may be used. Polyol is used as the liquid raw material, and polyisocyanate is used as the second liquid raw material. When a curing catalyst is used, the curing catalyst may be added to either the first liquid raw material or the second liquid raw material.
In the urea resin, either a polyamine (including a mixture of two or more polyamines) or a polyisocyanate (including a mixture of two or more polyisocyanates) may be used as the first liquid raw material. Polyamine is used as the first liquid material, and polyisocyanate is used as the second liquid material.
In the urethane-urea resin, a mixture of polyamine and polyol is preferably used as the first liquid raw material, and polyisocyanate is used as the second liquid raw material.
In the epoxy resin, polyamine is preferably used as the first liquid material, and polyglycidyl ether or polyglycidylamine is used as the second liquid material.

  The first liquid material and the second liquid material in the present invention usually have a viscosity of 2000 mPa · s or less. In particular, when a polyol is used as a raw material for the urethane resin in the present invention, the viscosity of the polyol is 1000 mPa · s or less, more preferably 800 mPa · s or less (B-type viscometer, 25 ° C., 12 rotations), and polyisocyanate Is used, the polyisocyanate has a viscosity of 300 mPa · s or less, more preferably 200 mPa · s or less (B-type viscometer, 25 ° C., 12 rotations).

The said coated granular agrochemical composition is manufactured as follows, for example. That is, the manufacturing method is
(1) A step of mixing the present powdery agrochemical composition and a first liquid raw material that is a raw material of the thermosetting resin,
(2) A step of adding a second liquid raw material that is a raw material of a thermosetting resin to the mixture obtained in the previous step, (3) a thermosetting reaction between the first liquid raw material and the second liquid raw material. A process of obtaining granular pesticides (inner core) by generating resin,
(4) The first liquid raw material and the second liquid raw material, which are the raw materials for the thermosetting resin, are added simultaneously or sequentially to the granular pesticide obtained in the previous step, and the first liquid raw material and the second liquid raw material are added. A step of coating the granular pesticide with a thermosetting resin,
Can be included.

In the step (1), the dry pesticidal composition is usually used as a raw material for the thermosetting resin in the container while the powdery pesticidal composition is rolled in the container under dry conditions where the present pesticidal composition is not dispersed in the liquid medium. In this step, the liquid pesticidal composition and the first liquid raw material are mixed by adding one liquid raw material to obtain a mixture of the powdered pesticidal composition and the first liquid raw material. By rolling the mixture of the present powdery pesticide composition and the first liquid raw material in a container for an appropriate time, individual particles in the present powdery pesticide composition are covered with the first liquid raw material. . Step (1) is usually performed at 0 to 100 ° C, preferably 10 to 90 ° C. From the viewpoint of safety, implementation in a nitrogen atmosphere is preferable.
Moreover, in this process (1), as a method of rolling this powdery agrochemical composition in a container on dry conditions, the method as shown below, for example is used.
a) A method of rotating a bread-shaped or drum-shaped container containing the present powdery pesticide composition around an oblique or horizontal axis;
b) In a container containing the present powdery pesticide composition, a stirring blade having the same size as the diameter of the bottom surface of the container is installed and rotated.
c) A method of applying an air flow to the present powdery pesticide composition in a container containing the present powdery pesticide composition.
In this step (1), when the first liquid raw material is added to the rolling pesticide composition in the rolling state, the first liquid raw material is placed on the surface of the individual particles of the powdery pesticide composition. It is spread and becomes a state where individual particles of the present powdery pesticide composition are covered with the first liquid raw material. Furthermore, by continuing the rolling, the first liquid raw material is usually distributed almost uniformly on the surface of all particles of the present powdery agricultural chemical composition. In this case, in order to uniformly coat all the particles of the present pesticidal composition with the first liquid raw material, it is preferable to use the first liquid raw material having a low viscosity (for example, 1000 m · Pa (25 ° C. or less)). .

In the step (2), the mixture obtained in the step (1), that is, the mixture of the powdery pesticide composition and the first liquid raw material is rolled in the container, and the thermosetting resin raw material is placed in the container. This is a step of obtaining a mixture of the powdery pesticide, the first liquid raw material, and the second liquid raw material by adding the second liquid raw material. This step (2) is usually performed at the same temperature as step (1), that is, 0 to 100 ° C., preferably 10 to 90 ° C. Moreover, implementation from a nitrogen atmosphere is preferable from a safety viewpoint.
The second liquid raw material added here usually has an equivalent of the reactive functional group in the second liquid raw material to 0 equivalent to the equivalent of the reactive functional group in the first liquid raw material added in step (1). An amount of 0.9 to 1.05, preferably 0.95 to 1.00 is used.
For example, when the thermosetting resin is a urethane resin and the first liquid raw material is a polyol, the second liquid raw material is a polyisocyanate, but the equivalent of the hydroxyl group (OH) in the polyol used in step (1). The isocyanate group (NCO) equivalent in the polyisocyanate added in step (2) is 0.8 to 1.1, preferably 0.9 to 1.1, and more preferably 0.95 to 1.05. The amount of polyisocyanate is adjusted as appropriate.
Moreover, when the 2nd liquid raw material added is mixed with the mixture of this powdery pesticide composition and a 1st liquid raw material, it is preferable that a viscosity is low, for example, 300m * Pa (25 degreeC) 2nd liquid It is preferable to use raw materials.

In step (3), the first liquid raw material and the second liquid raw material are reacted with each other while applying an appropriate shearing force to the mixture obtained in step (2) with a rotating blade or the like. Is a step of obtaining a granular pesticide in which the present powdery pesticide composition is aggregated via a thermosetting resin. In addition, when there is little quantity of the thermosetting resin produced | generated with respect to the quantity of this powdery pesticide composition, process (1)-(3) is repeated an appropriate number of times, and a granular pesticide is obtained. Although this process (3) is normally performed at 0-100 degreeC, Preferably it is 10-90 degreeC, More preferably, it is performed at 40-90 degreeC. In addition, if the said process (1) and a process (2) are performed at the same temperature, it is convenient on operation. In addition, this step (3) is also preferably performed in a nitrogen atmosphere from the viewpoint of safety.
The time required for the uncured thermosetting resin to cure varies depending on conditions such as the operation temperature in step (3), the type of thermosetting resin used, and the presence or absence of a curing catalyst. For example, when the curing rate of the thermosetting resin is sufficiently high, the first liquid raw material and the second liquid raw material in step (3) are substantially added before the addition of all of the second liquid raw material in step (2). And a part of the thermosetting resin starts to be generated. In such a case, in the step (2), while rolling the mixture of the present pesticidal composition and the first liquid raw material in the container, and further applying a shearing force to the mixture with a rotating blade or the like, It is preferable to add the second liquid raw material.
Moreover, as a method of giving shearing force to the mixture of the present pesticidal composition, the first liquid raw material, and the second liquid raw material in this step (3) with a rotating blade, specifically, the tip portion is A blade rotating in the range of 50 to 3000 m / min, preferably 100 to 2000 m / min, more preferably 200 to 1000 m / min, is used for the present pesticidal composition, the first liquid raw material and the second liquid raw material. The method of making it contact with a mixture is mentioned. At this time, the operation to give the shearing force is performed until the thermosetting resin does not exhibit tackiness, and the entire mixture of the powdery agricultural chemical composition, the first liquid raw material, and the second liquid raw material is sheared almost uniformly. It is preferable to appropriately adjust the amount of the powdery pesticide composition charged in the container, the number of rotating blade pairs, and the like so that force can be applied.

In step (4), the first liquid raw material and the second liquid raw material, which are raw materials for the thermosetting resin, are added simultaneously or sequentially while rolling the granular pesticide obtained in step (3) in a container, In this step, the first liquid raw material and the second liquid raw material are reacted while applying an appropriate shearing force to the obtained mixture with a rotating blade or the like to coat the granular agricultural chemical with a thermosetting resin. This step (4) is repeated a plurality of times as necessary until a film of an appropriate thickness of thermosetting resin is obtained. In this step (4), the first liquid raw material and the second liquid raw material are preferably added sequentially, but the first liquid raw material is first added to the granular pesticide, and then the second liquid raw material is added. Or you may add a 2nd liquid raw material previously to the said granular agrochemical, and may add a 1st liquid raw material after that.
The coated granular pesticide composition is obtained by changing the number of repetitions of the step (4) and the total amount of the first liquid raw material and the second liquid raw material in one step (4). The ratio of the thermosetting resin in the composition can be changed. That is, it is possible to adjust the sustained release performance of the pesticidal active ingredient. For example, if the raw material of the thermosetting resin is added to the granular agricultural chemical little by little, and in a more preferred embodiment, the first liquid raw material and the second liquid raw material are added separately, the elution of the agricultural chemical active ingredient is gradually released. Therefore, the agrochemical-containing particles having a relatively uniform particle size can be obtained. In addition, since the thermosetting resin film is uniformly formed, preferable sustained release performance can be obtained. Further, by repeating the step (4) a plurality of times, formation and growth of a thermosetting resin film covering the granular pesticide occurs, and in some cases, aggregation of particles of the granular pesticide occurs.

  The total amount of the first liquid raw material and the second liquid raw material added by one operation of the step (1) and the step (2) or the step (4), that is, the amount of the uncured thermosetting resin is the thermosetting. Although it can be changed according to conditions such as the type of resin, operating temperature, equipment used, etc., it is 0.3 to 15 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of powdered pesticide .

The steps (1) to (4) are preferably performed in a single container as a continuous step. In addition, it is preferable to use a container that can roll the contents with rotating blades and can give sufficient shearing force.
Examples of the container provided with such means include the following containers.
(A) A container provided with vanes that can rotate the entire pan-shaped or drum-shaped container around an oblique or horizontal axis, and further rotate at a position in contact with the contents in the container at a lower position of the container. (By rotating the container, the whole particles in the container are rolled, and the particles accumulated in the lower part of the container are given shearing force by the rotating blades);
(B) At the bottom of the substantially cylindrical container, there is a blade (hereinafter referred to as a stirring blade) having a size approximately equal to the diameter of the bottom surface provided on the bottom surface of the container. A container provided with blades that rotate around the projected horizontal axis (the stirring blade provided on the bottom surface of the container rotates to cause the entire particles in the container to roll, and the particles further protrude from the side surface. Shear force is applied by blades rotating around the horizontal axis);
(C) A container having a means for sending an air flow sufficient to move the entire contents in the container, and further provided with a rotating blade at a position in contact with the contents in the container. The whole particle is rolled, and the particle is further sheared by rotating blades installed in the container).

Hereinafter, the container (b) will be described.
The strength of the shearing force given by the rotating blades is to change the rotational speed and size of the blades rotating around the horizontal axis protruding from the side of the container (hereinafter referred to as the crushing blades). Can be adjusted. In the container (b), a shearing force can be applied also by the stirring blade. Moreover, the volume median diameter of the coated granular agrochemical composition obtained can be changed by adjusting the rotation speed of the crushing blade and the curing rate of the thermosetting resin. Specifically, when the rotational speed of the crushing blade is increased or the curing rate of the thermosetting resin is decreased, the volume median diameter of the granular agrochemical composition is decreased. As a specific container, as a device that causes circular movement of particles along the outer periphery of the container, there is a Newgra machine manufactured by Seishin Enterprise Co., Ltd. A low-speed agitator in the mixer and a high-speed chopper on the side surface are provided. As a device that mixes, disperses, and shears the input raw material in a short time by the action of both blades, a high-speed mixer manufactured by Fukae Powtech Co., Ltd. and Hi-Flex Grall can be cited. Furthermore, as a device having the same performance, a high speed mixer manufactured by Freund Sangyo Co., Ltd., a vertical granulator manufactured by Pou Lec Co., Ltd., and a new speed mill manufactured by Okada Seiko Co., Ltd. can be exemplified. For example, a device described in JP-A-9-75703 can be specifically mentioned.

  In the coated granular agrochemical composition, the amount of the thermosetting resin is usually 5 to 150 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 80 parts by weight with respect to 100 parts by weight of the powdered pesticide composition. is there. Moreover, the ratio of the thermosetting resin in the coated granular agricultural chemical composition is preferably 25 to 70% by weight. Moreover, the volume median diameter of the coated granular pesticide composition obtained is usually 2 to 20 times the volume median diameter of the powdered pesticide composition used as a raw material. The coated granular pesticidal composition is a composition in which a powdered pesticidal composition is hardened with a thermosetting resin and coated. The structure of individual particles in the coated granular pesticidal composition is roughly in the center. It is a polynuclear particle which has the aggregation part of a pesticide-like agricultural composition, and the film of a thermosetting resin is formed in the circumference | surroundings. For example, the volume median diameter of the powdered agricultural chemical composition is 1 to 100 μm, and the volume median diameter in the coated granular agricultural chemical composition is 30 to 200 μm.

In the present invention, the volume median diameter of the powdered agricultural chemical composition used is usually 1 to 100 μm, preferably 1 to 30 μm, and the volume median diameter of the coated granular agricultural chemical composition is usually 10 to 200, preferably 20-150 μm.
The volume median diameter of the coated granular agricultural chemical composition is, for example, 3 to 10 times the volume median diameter of the granular agricultural chemical used as a raw material.
In addition, these volume median diameters can be measured with a laser diffraction particle size measuring machine such as MASTERSIZER2000 manufactured by MALVERN. The shape of the coated granular pesticidal composition is generally substantially spherical, and the apparent specific gravity of the coated granular pesticidal composition is preferably 1.0 g / ml or less, more preferably 0.6 g / ml or less.

The agrochemical granule composition according to the present invention (hereinafter sometimes referred to as the present agrochemical granule composition)
(1) A coated granular agricultural chemical composition in which a powdered agricultural chemical composition containing a first agricultural chemical active ingredient is hardened with a thermosetting resin and coated, and a water solubility at 25 ° C. of 500 mg / L or less, preferably 50 mg / L A first step of kneading a mixture containing a second pesticidal active ingredient which is L or less, a solid carrier, a binder, a surfactant, and water;
(2) The kneaded product obtained in the first step can be produced through a second step of extrusion granulation, and (3) the third step of drying the granulated product obtained in the second step.
The pesticidal active ingredient, coated granular pesticidal composition, solid carrier, binder, surfactant and the like used in the first step are as described above. Further, in the second step and the third step, granulation and drying can be performed using a usual method.

  Further, the present agricultural chemical granule composition has a content of the coated granular agricultural chemical composition of 0.5 to 30% by weight, a content of the second agricultural chemical active ingredient of 0.1 to 30% by weight, and the solid carrier. Is preferably 15 to 98.8% by weight, the binder is preferably 0.5 to 10% by weight, and the surfactant is preferably 0.1 to 15% by weight.

Examples of the solid carrier used in the agrochemical granule composition include kaolin minerals such as kaolinite, dickanite, nacrite, and halosite, chrysotile, lizarite, anticorite, serpentine such as amesite, sodium montmorillonite, calcium montmorillonite, Montmorillonite minerals such as magnesium montmorillonite, saponites such as saponite, hectorite, soconite, and hydelite, pyrophyllite, talc, rholite, mica such as muscovite, fengite, sericite, illite, silica such as cristobalite, quartz, Hydrous magnesium silicate such as attapulgite and sepiolite, sulfate minerals such as gypsum, dolomite, heavy calcium carbonate, light calcium carbonate, gypsum, zeolite, zeolite, tuff, vermiki Mineral carriers such as light, laponite, pumice, diatomaceous earth, acid clay, activated clay; plant carriers such as corn cob flour, walnut shell flour, rice husk, wheat flour, wood flour, straw, bran, soybean flour; urea, Water-soluble carriers such as lactose, sucrose, sodium chloride, mirabilite, sodium tripolyphosphate, potassium pyrophosphate, ammonium sulfate and the like can be mentioned. In the present invention, a mineral-based carrier is preferable, and heavy calcium carbonate, light calcium carbonate, and wax are more preferable.
The solid carrier may be calcium carbonate or a combination of calcium carbonate and one or more other solid carriers.

  Examples of the binder used in the agrochemical granule composition include gum arabic, sodium carboxymethylcellulose, hydroxypropylmethylcellulose, methylcellulose, methylethylcellulose, hydroxypropylcellulose, sodium polyacrylate, tragacanth gum, polyvinylpyrrolidone, polyvinyl alcohol, Examples include alpha-fermented starch, dextrin, alginic acid, sodium alginate and the like, preferably sodium carboxymethylcellulose, hydroxypropylmethylcellulose, polyvinylpyrrolidone, polyvinyl alcohol and pregelatinized starch. In the present invention, when pregelatinized starch is used as a binder, agrochemical granules that are non-disintegrating when contacted with water can be produced.

  Examples of the surfactant used in the agrochemical granule composition include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid. Ester, polyoxyethylene glyceryl mono fatty acid ester, polyoxyethylene glyceryl mono fatty acid ester, polyoxypropylene glycol mono fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene castor oil derivative, higher fatty acid glycerin ester , Sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene block polymer Nonionic (nonionic) surfactants such as polyoxyethylene fatty acid amide, alkylolamide, polyoxyethylene alkylamine; fatty acid sodium, sodium polyoxyalkylene alkyl ether carboxylate, alkyl sulfonate, fatty acid ester sulfonic acid And anionic surfactants such as dialkyl sulfosuccinate, fatty acid amide sulfonate, alkyl aryl sulfonate, alkyl aryl sulfonate, formalin condensate, higher alcohol sulfate, polyoxyalkylene alkyl phosphate, etc. It is done.

  It is preferable that the thermosetting resin film in the present pesticidal granule composition is strong, hardly destroys the film during kneading and granulation, and maintains the sustained release performance of the pesticidal active compound. This agrochemical granule composition can be used by spraying directly on pests to be controlled or on plants and soil to be protected.

It is preferable that this agrochemical granule composition is for paddy rice seedling box processing including correspondence at the time of sowing.
The response to sowing is a series of steps by incorporating a seedling box treatment agent into the sowing process of floor soil → irrigation → sowing → covering soil, specifically floor soil → granule treatment → irrigation → sowing → covering soil. This is a simple spraying method that enables the seedling box treatment agent to be sprayed by sowing work. In addition, it is possible to control diseases (seedling potatoes, bacterial diseases, etc.) that occur during the seedling raising period by responding at the time of sowing.
The paddy rice seedling box is a seedling box having a size of 30 cm × 60 cm (inner diameter: 28 cm × 58 cm) and growing rice seedlings until rice planting (generally for 20 to 40 days). The paddy rice seedling box treatment is a simple control means for spraying granules to a seedling box in order to control pests that occur in the Honda after planting rice.

  In addition, description of each method, apparatus, material, etc. regarding the present invention described above describes the best mode for carrying out the present invention, and does not limit the scope of the present invention.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1
(1) Preparation of powdered agricultural chemical composition 1 70.0 parts by weight of (E) -1- (2-chloro-1,3-thiazol-5-ylmethyl) -3-methyl-2-nitroguanidine (generic name) : Clothianidin) and 30.0 parts by weight of Katsuyama Clay S (manufactured by Katsuyama Mining Co., Ltd.) are uniformly mixed and pulverized in a centrifugal crusher to a volume median diameter of 8.20 μm (Malverter MASTERSIZER 2000) (E) -1- (2-chloro-1,3-thiazol-5-ylmethyl) -3-methyl-2-nitroguanidine (hereinafter referred to as powdered pesticide composition 1) .) Was obtained.
(2) Preparation of polyol premix 1 46.3 parts by weight of Sumifene TM (branched polyether polyol made by Sumika Bayer Urethane), 52.2 parts by weight Sumifene 1600U (linear polyether polyol made by Sumika Bayer Urethane) ) And 1.5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol (manufactured by Kayaku Akzo), and a liquid mixture of polyol and catalyst (hereinafter referred to as polyol premix 1). .) Was obtained.
(3) Preparation of coated granular agricultural chemical composition 1 High-speed mixer device (LFS-GS-1J type, manufactured by Fukae Pautech Co., Ltd .; an agitator blade with a vertical line passing through the center of the bottom surface of the container portion of a round dish type as a rotational axis; 100 parts by weight of the powdered pesticide composition 1 is charged into a container of a chopper blade having a horizontal line passing through the side surface of the round dish-shaped container portion as a rotation axis, and the agitator blade (number of rotations) of the device : 170 rpm) and chopper blades (rotation number: 2500 rpm) were rotated. Next, the mixing container was heated, and 1.93 parts by weight of polyol premix 1 was added while maintaining the product temperature of the powdered agricultural chemical composition 1 at 85 ± 5 ° C. It was observed that the polyol premix 1 was wetted by the powdered agricultural chemical composition 1. After 3 minutes, 1.07 parts by weight of Sumidur 44V10 (Sumitani Bayer Urethane polymethylene polyphenyl polyisocyanate, viscosity 130 m · Pa (25 ° C.)) was added while maintaining the product temperature at 85 ± 5 ° C. . Immediately after the addition, a thickening phenomenon was confirmed, after which the viscosity decreased and hardening of the polyurethane resin was observed (for 100 parts by weight of the powdered agricultural chemical composition 1, to 3.0 parts by weight of the polyurethane resin). Equivalent). After 5 minutes, the following operation was repeated 34 times while maintaining the product temperature at 85 ± 5 ° C.
Add 1.86 parts by weight of polyol premix 1 and wait for 3 minutes, then add 1.14 parts by weight of Sumidur 44V10 and wait for 5 minutes.
During the above operation, the high-speed mixer device continued stirring and mixing with shearing force under the same conditions.
A total of 105 parts by weight of the polyurethane resin raw material was added to 100 parts by weight of the powdery agricultural chemical composition 1. Cooling the mixing container, coated granular agricultural chemical composition 1 (urethane resin raw material addition frequency: 35 times, urethane raw material addition amount per time: 3.0 parts by weight, urethane resin raw material total addition amount: 87 parts by weight, in volume (Diameter: 75 μm, apparent specific gravity: 0.41 g / ml).
(4) Preparation of agricultural chemical granule composition Coated granular agricultural chemical composition 1 4.4 parts by weight (1.5 parts by weight as an agricultural chemical active compound), 2.0 parts by weight of isothianyl (2.0 parts by weight as an agricultural chemical active compound) , Pregelatinized starch (Amylox No.1A, manufactured by Nippon Corn Starch) 5.0 parts by weight, heavy calcium carbonate (SS # 80, manufactured by Nitto Flour Industry) 10.0 parts by weight, wax (Katsumiyama clay S, Katsu About 20 parts by weight of water containing 1.0 part by weight of a surfactant (polyoxyethylene tristyryl phenyl ether, Sorpol T-20, manufactured by Toho Chemical Co., Ltd.) is added to a mixture of 77.6 parts by Mitsuyama Mining Co., Ltd. And kneaded. About 1.5 kg of the obtained kneaded product is put into a 0.9 mmφ basket-type extrusion granulator with a screen (HU-G type field granulator, Hata Seisakusho) and first granulated for 10 seconds. I drove the machine. After removing the granulated material obtained in 10 seconds, restart the operation of the granulator, obtain the granulated material obtained in 30 seconds, and dry the granulated material at 70 ° C. for 30 minutes. The pesticide granule composition of Example 1 was obtained.

Example 2
Coated granular pesticide composition 1 4.4 parts by weight (1.5 parts by weight as an agrochemical active compound), 3.0 parts by weight of dicrosimet (3.0 parts by weight as an agrochemical active compound), pregelatinized starch (Amylox No. 1A, Japan cornstarch) 5.0 parts by weight, heavy calcium carbonate (SS # 80, manufactured by Nitto Flour & Chemical Co., Ltd.) 10.0 parts by weight, wax (Katsumiyama clay S, manufactured by Katsuyama Mining Co., Ltd.) 76.6 parts About 20 parts by weight of water containing 1.0 part by weight of a surfactant (polyoxyethylene tristyryl phenyl ether, Sorpol T-20, manufactured by Toho Chemical Industry) was added to the mixture and kneaded. About 1.5 kg of the obtained kneaded product is put into a 0.9 mmφ basket-type extrusion granulator with a screen (HU-G type field granulator, Hata Seisakusho) and first granulated for 10 seconds. I drove the machine. After removing the granulated material obtained in 10 seconds, restart the operation of the granulator, obtain the granulated material obtained in 30 seconds, and dry the granulated material at 70 ° C. for 30 minutes. The agrochemical granule composition of Example 2 was obtained.

Example 3
Coated granular pesticide composition 1 4.4 parts by weight (1.5 parts by weight as an agrochemical active compound), 2.0 parts by weight of isothianyl (2.0 parts by weight as an agrochemical active compound), 3.0 parts by weight of diclosimet (agrochemical activity) 3.0 parts by weight as a compound), 5.0 parts by weight of pregelatinized starch (Amylox No.1A, manufactured by Nippon Corn Starch), 10.0 parts by weight of heavy calcium carbonate (SS # 80, manufactured by Nitto Flour Chemical), wax A mixture of 74.6 parts of stone (Katsumiyama clay S, manufactured by Katsuyama mining company) contains 1.0 parts by weight of surfactant (polyoxyethylene tristyryl phenyl ether, Sorpol T-20, manufactured by Toho Chemical Co., Ltd.) About 20 parts by weight of water to be added was added and kneaded. About 1.5 kg of the obtained kneaded product is put into a 0.9 mmφ basket-type extrusion granulator with a screen (HU-G type field granulator, Hata Seisakusho) and first granulated for 10 seconds. I drove the machine. After removing the granulated material obtained in 10 seconds, restart the operation of the granulator, obtain the granulated material obtained in 30 seconds, and dry the granulated material at 70 ° C. for 30 minutes. The agrochemical granule composition of Example 3 was obtained.

Example 4
(1) Preparation of powdery pesticide composition 2 45.5 parts by weight of 5-chloro-N- (1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl) -1,3- Dimethylpyrazole-4-carboxamide (generic name: Frametopil), 9 parts by weight Toxeal GU-N (water-containing amorphous silicon dioxide manufactured by Tokuyama Corporation) and 45.5 parts by weight Bentonite Fuji Mark (manufactured by Hojun Co., Ltd.) Mix uniformly, crush all in a centrifugal crusher, and 5-chloro-N- (1,3-dihydro-1,1,3-trimethyl-) having a volume median diameter of 5.0 μm (MASTERSIZER2000 manufactured by MALVERN) A powdery agricultural chemical composition (hereinafter referred to as powdered agricultural chemical composition 2) containing 4-isobenzofuranyl) -1,3-dimethylpyrazole-4-carboxamide was obtained.
(2) Preparation of coated granular agrochemical composition 2 High speed mixer device (LFS-GS-1J type, manufactured by Fukae Pautech Co., Ltd .; agitator blade with a vertical line passing through the center of the bottom surface of the container portion of the round dish type as a rotation axis; 100 parts by weight of the powdered pesticide composition 2 is charged into a container of a chopper blade having a horizontal axis passing through the side of a round dish-shaped container portion as a rotation axis, and the agitator blade (rotation) of the device Number: 850 rpm) and chopper blades (rotation number: 3500 rpm) were rotated. Next, the mixing container was heated, and 1.86 parts by weight of the above polyol premix 1 was added while maintaining the product temperature of the powdered agricultural chemical composition 2 at 75 ± 5 ° C. It was observed that this polyol premix 1 was wetted by the powdery pesticide composition 2. After 3 minutes, while maintaining the product temperature at 75 ± 5 ° C., 1.14 parts by weight of Sumijoule 44V10 (polymethylene polyphenyl polyisocyanate made by Sumika Bayer Urethane, viscosity 130 m · Pa (25 ° C.)) was added. . Immediately after the addition, a thickening phenomenon was confirmed, after which the viscosity decreased and the curing of the polyurethane resin was observed (corresponding to 3.0 parts by weight of the polyurethane resin with respect to 100 parts by weight of the agricultural chemical bulk powder). After 5 minutes, the following operation was repeated 6 times while maintaining the product temperature at 75 ± 5 ° C.
Add 1.86 parts by weight of polyol premix 1 and wait for 3 minutes, then add 1.14 parts by weight of Sumidur 44V10 and wait for 5 minutes.
During the above operation, the high-speed mixer device continued stirring and mixing with shearing force under the same conditions.
A total of 21 parts by weight of the polyurethane resin raw material was added to 100 parts by weight of the powdered agricultural chemical composition 2. Cooling the mixing container, coated granular agrochemical composition 2 (urethane resin raw material addition frequency: 7 times, urethane raw material addition amount per time: 3.0 parts by weight, urethane resin raw material total addition amount: 21 parts by weight, in volume (Diameter: 40 μm, apparent specific gravity: 0.37 g / ml).
(3) Preparation of agricultural chemical granule composition 4.4 parts by weight of coated granular agricultural chemical composition 1 (1.5 parts by weight as an agricultural chemical active compound), 10.6 parts by weight of the above coated granular agricultural chemical composition 2 (as an agricultural chemical active compound) 4.0 parts by weight), 2.0 parts by weight of isotianil (2.0 parts by weight as an agrochemical active compound), 3.0 parts by weight of dicrosimet (3.0 parts by weight as an agrochemical active compound), pregelatinized starch (Amylox No. 1A, made by Nippon Corn Starch) 5.0 parts by weight, heavy calcium carbonate (SS # 80, made by Nitto Flour Chemical Co., Ltd.) 10.0 parts by weight, wax (Katsumiyama Clay S, made by Katsuyama Mining Co., Ltd.) 64.0 About 20 parts by weight of water containing 1.0 part by weight of a surfactant (polyoxyethylene tristyryl phenyl ether, Sorpol T-20, manufactured by Toho Chemical Industry Co., Ltd.) was added to the part mixture and kneaded. About 1.5 kg of the obtained kneaded product is put into a 0.9 mmφ basket-type extrusion granulator with a screen (HU-G type field granulator, Hata Seisakusho) and first granulated for 10 seconds. I drove the machine. After removing the granulated material obtained in 10 seconds, restart the operation of the granulator, obtain the granulated material obtained in 30 seconds, and dry the granulated material at 70 ° C. for 30 minutes. The pesticide granule composition of Example 4 was obtained.

Example 5
Coated granular pesticide composition 1 4.4 parts by weight (1.5 parts by weight as an agrochemical active compound), 2.0 parts by weight of isotianil (2.0 parts by weight as an agrochemical active compound), 4.0 parts by weight of furametopyr (agrochemical activity) 4.0 parts by weight of compound), pregelatinized starch (Amylox No. 1A, manufactured by Nippon Corn Starch) 5.0 parts by weight, heavy calcium carbonate (SS # 80, manufactured by Nitto Flour Chemical) 10.0 parts by weight, wax Contains 1.0 parts by weight of a surfactant (polyoxyethylene tristyryl phenyl ether, Sorpol T-20, manufactured by Toho Chemical Co., Ltd.) in a mixture of 73.6 parts of stone (Katsumiyama clay S, manufactured by Katsuyama Mining) About 20 parts by weight of water to be added was added and kneaded. About 1.5 kg of the obtained kneaded product is put into a 0.9 mmφ basket-type extrusion granulator with a screen (HU-G type field granulator, Hata Seisakusho) and first granulated for 10 seconds. I drove the machine. After removing the granulated material obtained in 10 seconds, restart the operation of the granulator, obtain the granulated material obtained in 30 seconds, and dry the granulated material at 70 ° C. for 30 minutes. The pesticide granule composition of Example 5 was obtained.

Example 6
Coated granular pesticide composition 1 5.9 parts by weight (2.0 parts by weight as an agrochemical active compound), 2.0 parts by weight of isothianyl (2.0 parts by weight as an agrochemical active compound), 0.9 parts by weight of imazosulfuron (agrochemical activity) 0.9 parts by weight as a compound), 12.9 parts by weight of bromobutide thick powder (9.0 parts by weight as an agrochemical active compound), 26.9 parts of bentonite (Kunigel V1, manufactured by Kunimine Industries), calcium carbonate (Tohoku Tankar (# 250), 48.9 parts by weight of Towa Lime Industry), 2.0 parts by weight of polycarboxylic acid surfactant (Toxanone GR-31A, Sanyo Chemical Industries) and dioctyl sulfosuccinate (Neocol SW-CP) About 17 parts by weight of water containing 0.5 part of Daiichi Kogyo Seiyaku) was added and kneaded. About 1.5 kg of the obtained kneaded product is put into a 1.0 mmφ basket-type extrusion granulator with a screen (HU-G type field granulator, Hata Seisakusho), and first granulated for 10 seconds. I drove the machine. After removing the granulated material obtained in 10 seconds, restart the operation of the granulator, obtain the granulated material obtained in 30 seconds, and dry the granulated material at 70 ° C. for 30 minutes. The agrochemical granule composition of Example 6 was obtained.

Comparative Example 1
Clothianidin 1.5 parts by weight (1.5 parts by weight as an agrochemical active compound), pregelatinized starch (Amylox No. 1A, manufactured by Nippon Corn Starch) 5.0 parts by weight, heavy calcium carbonate (SS # 80, Nitto Flour Industries) ) 10.0 parts by weight, wax (Katsumiyama clay S, 82.5 parts by Katsuyama Mining) 8% by weight, surfactant (polyoxyethylene tristyryl phenyl ether, Sorpol T-20, Toho Chemical Industry) Product) About 20 parts by weight of water containing 1.0 part by weight was added and kneaded. About 1.5 kg of the obtained kneaded product is put into a 0.9 mmφ basket-type extrusion granulator with a screen (HU-G type field granulator, Hata Seisakusho) and first granulated for 10 seconds. I drove the machine. After removing the granulated material obtained in 10 seconds, restart the operation of the granulator, obtain the granulated material obtained in 30 seconds, and dry the granulated material at 70 ° C. for 30 minutes. The agrochemical granule composition of Comparative Example 1 was obtained.

*1：ブロモブチド／ベントナイト妙義＝７／３の混合物（ベントナイト妙義：ホージュン製）
*2：アミロックスNo.1A、日本コーンスターチ製
*3：重質炭酸カルシウム（ＳＳ８０、日東粉化工業製）
*4：ロウ石（勝光山クレーＳ、勝光山鉱業所製）
*5：ポリオキシエチレントリスチリルフェニルエーテル、Sorpol T-20、東邦化学工業製
*6：トキサノンＧＲ−３１Ａ、三洋化成工業製
*7：ネオコールＳＷ−ＣＰ、第一工業製薬製
*8：クニゲルＶ１、クニミネ工業製
*9：東北タンカル（＃２５０）、東和石灰工業製 Comparative Example 2
(1) Preparation of coated granular agricultural chemical composition 3 Polyvinyl alcohol (nonionic substance, trade name: Gohsenol GH-17R, manufactured by Nippon Synthetic Chemical Co., Ltd.) 0.7 parts by weight, sodium lauryl sulfate (ionic surfactant) Agent, trade name: Emar 10 powder, manufactured by Kao Corporation) is an agrochemical base that is solid at room temperature in an aqueous phase in which 0.1 part by weight is dissolved in 84.15 parts by weight of ion-exchanged water (E)- 2.5 parts by weight of 1- (2-chloro-1,3-thiazol-5-ylmethyl) -3-methyl-2-nitroguanidine (generic name: clothianidin) was dispersed. Next, 2,5′-azobis (2,4-dimethyl-4-methoxyvaleronitrile) (polymerization initiator, trade name: V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.15 wt. 12.4 parts by weight of butyl methacrylate (polymerizable monomer, manufactured by Wako Pure Chemical Industries, Ltd.) was added. While this mixture was cooled to 5 ° C., it was sonicated with an LSC homogenizer (manufactured by Yamato Kagaku Co., Ltd.) at an OUT PUT value of 2 minutes for 10 minutes, and then gently stirred with a stirrer for 1 hour, then 30 The mixture was stirred gently at 24 ° C. for 24 hours and dried at 60 ° C. to obtain a coated granular agricultural chemical composition 3.
(2) Preparation of agricultural chemical granule composition Coated granular agricultural chemical composition 3 9.4 parts by weight (1.5 parts by weight as an agrochemical active compound), pregelatinized starch (Amylox No. 1A, manufactured by Nippon Corn Starch) 5.0 parts by weight A mixture of 10 parts by weight, heavy calcium carbonate (SS # 80, manufactured by Nitto Flour Chemical Co., Ltd.) 10.0 parts by weight, and rouxite (Katsumiyama Clay S, manufactured by Katsuyama Mining Co., Ltd.) About 20 parts by weight of water containing 1.0 part by weight of oxyethylene tristyryl phenyl ether (Sorpol T-20, manufactured by Toho Chemical Co., Ltd.) was added and kneaded. About 1.5 kg of the obtained kneaded product is put into a 0.9 mmφ basket-type extrusion granulator with a screen (HU-G type field granulator, Hata Seisakusho) and first granulated for 10 seconds. I drove the machine. After removing the granulated material obtained in 10 seconds, restart the operation of the granulator, obtain the granulated material obtained in 30 seconds, and dry the granulated material at 70 ° C. for 30 minutes. The agrochemical granule composition of Comparative Example 2 was obtained.

* 1: Mixture of bromobutide / bentonite Myogi = 7/3 (Bentonite Myogi: made by Hojun)
* 2: Amilox No.1A, made by Nippon Corn Starch
* 3: Heavy calcium carbonate (SS80, manufactured by Nitto Flour Industries)
* 4: Waxstone (Katsumiyama clay S, manufactured by Katsuyama mining)
* 5: Polyoxyethylene tristyryl phenyl ether, Sorpol T-20, manufactured by Toho Chemical Industry
* 6: Toxanone GR-31A, manufactured by Sanyo Chemical Industries
* 7: Neocor SW-CP, manufactured by Daiichi Kogyo Seiyaku
* 8: Kunigel V1, manufactured by Kunimine Industries
* 9: Tohoku Tankar (# 250), manufactured by Towa Lime Industry

Test example 1
(1) Clothianidin dissolution test 450 ml of hard water of 3 degrees is weighed in a 500 ml beaker and the temperature is controlled at 25 ± 1 ° C. The agrochemical granule composition obtained in Examples 1 to 4 and Comparative Examples 1 and 2 and Example 1 were obtained while stirring 3 degree hard water at 100 rpm using a circular stirrer (diameter 25 mm, thickness 15 mm). The coated granular agrochemical composition 1 and the coated granular agrochemical composition 3 obtained in Comparative Example 2 are charged in the following amounts (clothianidin concentration in solution: 50 ppm). One to three days after the start of the test, clothianidin in the solution is quantified by the LC-IS method, and the elution rate is calculated by one formula.
Formula 1 ・ Elution rate (%) = Clothianidin in solution / Total clothianidin in sample × 100
The results are shown in Table 1.

Test example 2
(2) Clothianidin dissolution test The dissolution rate after 35 days and 84 days from the start of the test was calculated by the same clothianidin determination method as in Test Example 1. The results are shown in Tables 2-4.

Test example 3
(1) Test of phytotoxicity to rice by pre-soiling for paddy rice seeding before seeding of paddy rice seedling box (30 cm x 60 cm) before seeding sowing the test grain composition at a rate of 100 g / nursery box : Hinohikari) was sown. After germination for 3 days in a seedling device (30 ° C. all day), the seedlings were transferred to the outdoors to raise seedlings. Two weeks after sowing, the occurrence of phytotoxicity was visually examined according to the following phytotoxicity survey criteria (two-line system).
≪Chemical hazard survey standards≫
-: No symptom of phytotoxicity ±: Signs of phytotoxicity are observed but no problem for practical use +: Physiological damage is observed, there is no problem for practical use

Table 5 shows the results of the investigation for each granule composition.

  The agrochemical granule composition of the present invention has excellent sustained release performance of an agrochemical granule composition containing two or more agrochemical active ingredients by appropriately changing the type and amount of the thermosetting resin used. It is possible to

Claims (11)

A coated granular agricultural chemical composition comprising a powdered agricultural chemical composition containing a first agricultural chemical active ingredient, which is hardened with a thermosetting resin and coated;
A second pesticidal active ingredient having a water solubility at 25 ° C. of 500 mg / L or less;
A solid support, a binder, a surfactant,
Agrochemical granule composition containing The content of the coated granular agricultural chemical composition comprising the powdered agricultural chemical composition containing the first agricultural chemical active ingredient is hardened and coated with a thermosetting resin is 0.5 to 30% by weight,
The content of the second pesticidal active ingredient is 0.1 to 30% by weight,
The content of the solid carrier is 15 to 98.8% by weight,
A binder content of 0.5 to 10% by weight,
The surfactant content is 0.1 to 15% by weight,
The agrochemical granule composition according to claim 1.   The agrochemical granule composition according to claim 1 or 2, wherein the thermosetting resin is a urethane resin.   The agrochemical granule composition according to any one of claims 1 to 3, wherein the first agrochemical active ingredient is an agrochemical active ingredient having a water solubility at 25 ° C of 100 mg / L or more and 1000 mg / L or less.   The combination of a 1st agricultural chemical active ingredient and a 2nd agricultural chemical active ingredient is a combination of an insecticidal active ingredient and a bactericidal active ingredient, The agricultural chemical granule composition as described in any one of Claims 1-3. The first pesticidal active ingredient is (E) -N-((2-chloro-5-thiazolyl) methyl) -N′-methyl-N ″ -nitroguanidine,
The second pesticidal active ingredient is 2-cyano-N-[(1R)-(2,4-dichlorophenyl) ethyl] -3,3-dimethylbutanamide and 2'-cyano-3,4-dichloroisothiazole- The agrochemical granule composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of 5-carboxyanilide. The solid carrier is calcium carbonate or a combination of calcium carbonate and one or more other solid carriers;
The agrochemical granule composition according to claim 6, wherein the binder is pregelatinized starch.   A surfactant is a nonionic surfactant, The agrochemical granule composition as described in any one of Claims 1-7.   The agrochemical granule composition according to any one of claims 1 to 8, which is for paddy rice seedling box treatment including correspondence at the time of sowing.   The agrochemical granule composition according to any one of claims 1 to 9, wherein the second agrochemical active ingredient has a water solubility at 25 ° C of 50 mg / L or less. (1) A coated granular pesticidal composition in which a powdery pesticidal composition containing a first pesticidal active ingredient is hardened with a thermosetting resin and coated, and a second water solubility at 25 ° C. of 500 mg / L or less A first step of kneading a mixture containing an agrochemical active ingredient, a solid carrier, a binder, a surfactant, and water;
(2) a second step of extruding and granulating the kneaded product obtained in the first step, and (3) a third step of drying the granulated product obtained in the second step,
A method for producing an agrochemical granule comprising: