Pesticide composition and method for producing same

Abstract

To provide a technique for promoting elution of an agrochemical active ingredient using a water-soluble polymer, the present invention provides: an agrochemical composition characterized by containing a water-soluble polymer, and agrochemical active ingredient crystal particles having a volume median diameter of less than 1 μｍ; and a method for producing the same.

Description

[Technical field]

[0001] The present invention relates to a pesticide composition and a granular pesticide formulation which have improved release properties of a pesticide active ingredient, and to methods for producing the same. [Background technology]

[0002] It is necessary to control or promote the dissolution of the pesticidal active ingredient contained in the pesticide composition according to various purposes.

[0003] Known means for controlling the release of pesticide active ingredients include, for example, means for processing the pesticide active ingredient itself, such as microencapsulation described in Patent Document 1, etc., and sustained-release bulk powder described in Patent Document 2, etc., and means for structurally endowing the pesticide with release control performance, such as hydrophobic substance-coated granules described in Patent Document 3, etc., and hydrophobic substance-containing granules described in Patent Document 4, etc. However, the former two involve special processing steps, which inevitably increases costs, and the latter two require the formation of a coating structure or matrix structure using a hydrophobic substance, so that the scope of application is necessarily limited to granular pesticides that do not disintegrate in water.

[0004] On the other hand, water-soluble polymers such as polyvinylpyrrolidone are widely known, and in the agricultural chemical field, they are mainly used as physical property adjusting assistants such as binders and disintegrants, and Patent Document 5 discloses that they have the effect of preventing the decomposition of specific agricultural chemical active ingredients. Patent Document 6 also discloses that they have the effect of reducing phytotoxicity to useful plants derived from alkylbenzenesulfonic acid, a surfactant contained in aqueous formulations. Patent Document 7, which is an application by the present applicants, discloses that the dissolution of fenoxasulfone in water is controlled to prevent the occurrence of phytotoxicity due to a local increase in concentration.

[0005] However, it has not been known so far that water-soluble polymers such as polyvinylpyrrolidone can promote the dissolution of pesticide active ingredients. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2004-103481 A [Patent Document 2] Japanese Patent Application Publication No. 8-92497 [Patent Document 3] Japanese Patent Application Publication No. 10-25202 [Patent Document 4] JP 2000-26206 A [Patent Document 5] Japanese Patent Application Publication No. 5-320010 [Patent Document 6] JP 2014-196253 A [Patent Document 7] JP 2019-19062 A Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, an object of the present invention is to provide a technique for promoting the release of an agricultural chemical active ingredient by using a water-soluble polymer. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors conducted intensive research to solve the above problems and discovered that the release of the pesticide active ingredient can be promoted by reducing the volume median diameter of the pesticide active ingredient to be combined with a water-soluble polymer, thereby completing the present invention.

[0009] That is, the present invention relates to an agrochemical composition comprising crystalline particles of an agrochemically active ingredient having a volume median diameter of less than 1 μm and a water-soluble polymer.

[0010] The present invention also relates to a method for producing a pesticide composition, comprising the steps of: grinding crystalline particles of a pesticide active ingredient until the volume median diameter is less than 1 μm; and mixing the crystalline particles of the pesticide active ingredient with a water-soluble polymer before or after the grinding step. Effect of the Invention

[0011] The pesticide composition of the present invention is one in which the elution of the pesticide active ingredient is promoted by a simple technique of reducing the volume median diameter of the crystal particles of the pesticide active ingredient, and therefore can be widely used as a herbicide, plant conditioner, insecticide, fungicide, etc.

[0012] The method for producing the pesticide composition of the present invention is simple since it does not require any special steps other than the step of reducing the volume median diameter of the crystal particles of the pesticidal active ingredient. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The pesticide composition of the present invention (hereinafter referred to as "the composition of the present invention") contains crystalline particles of an pesticide active ingredient having a volume median diameter of less than 1 μm, preferably 0.2 to 0.8 μm, and a water-soluble polymer. In this specification, the volume median diameter refers to a diameter at which a powder is divided into two parts based on the volume of a certain particle diameter, and the larger side and the smaller side are equal in amount. This volume median diameter is obtained, for example, as the median diameter of the volume particle size distribution measured by a laser analysis type particle size distribution measuring device.

[0014] The pesticide active ingredient used in the composition of the present invention is not particularly limited as long as it can be crystallized. For example, the following can be mentioned, but it is not particularly limited. These pesticide active ingredients can be used alone or in combination of two or more.

[0015] [Insecticidal active ingredient] acrinathrin, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, acequinocyl, acetamiprid, acetoprole, acephate, azocyclotin, abamectin, afidopyropen, afoxolaner, amidoflumet, amitraz, alanycarb, aldicarb, aldoxycarb, arethamicarb, acetoprole ... Allethrin [including d-cis-trans- and d-trans-isomers], isazophos, isamidofos, isocarbophos, isoxathion, isofenphos-methyl, isoprocarb, ivermectin, imicyafos, imidacloprid, imiprothrin, indoxacarb, esfenvalerate, ethiofencarb, ethion, ethiprole, ethylene dibromide dibromide, etoxazole, etofenprox, ethoprophos, etrimfos, emamectin benzoate, endosulfan, empenthrin, oxazosulfyl, oxamyl, oxydemeton-methyl,Oxydeprofos, omethoate, cadusafos, kappa-tefluthrin, kappa-bifenthrin, karanjin, cartap, carbaryl, carbosulfan, carbofuran, gamma-BHC, xylylcarb, quinal quinalphos, kinoprene, chinomethionat, coumaphos, cryolite, clothianidin, clofentezine, chromafenozide, chlorantraniliprole, chlorethoxyfos, chlordane, chloropicrin (chloropicrin), chlorpyrifos, chlorpyrifos-methyl, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroprallethrin, cyanophos, diafenthiuron, diamidaphos (diamidafos), cyantraniliprole, dienochlor, cyenopyrafen, dioxabenzofos, diofenolan, cyclaniliprole, dicrotophos, diclofenthion, cycloprothrin, dichlorvos,Dichloromezotiaz, 1,3-dichloropropene, dicofol, dicyclanil, disulfoton, dinotefuran, dinobuton, cyhalodiamide, cyhalothrin [including gamma- and lambda-isomers], cyphenothrin [including (1R)-trans-isomers] [including alpha-, beta-, theta-, and zeta-forms], cyfluthrin [including beta-forms], diflubenzuron, cyflumetofen, diflovidazin, cyhexatin, cypermethrin [including alpha-, beta-, theta-, and zeta-forms], dimethylvinphos, dimefluthrin, dimethoate, silafluofen silafluofen, cyromazine, spinetoram, spinosad, spirodiclofen, spirotetramat, spiromesifen, sulcofuron-sodium, sulfluramid, sulfoxaflor, sulfotep, diazinon, Thiacloprid, thiamethoxam, tioxazafen, thiodicarb, thiocyclam, thiosultap, thionazin, thiofanox, thiometon, tetrachlorvinphos, tetradifon, tetraniliprole,tetramethylfluthrin, tetramethrin, tebupirimfos, tebufenozide, tebufenpyrad, tefluthrin, teflubenzuron, demeton-S-methyl, temephos, deltamethrin, terbufos, tralomethrin thrin, transfluthrin, triazamate, triazophos, trichlorfon, triflumuron, triflumezopyrim, trimethacarb, tolfenpyrad, naled, nitenpyram, novaluron, noviflumuron, verticillium Verticillium lecanii, hydroprene, Pasteuria penetrans spores, vamidothion, parathion, parathion-methyl, halfenprox, halofenozide, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, bistrifluron, hydramethylnon, bifenazate, bifenthrin, pyflubumide, piperonyl butoxide butoxide), pymetrozine, pyraclofos,pyrafluprole, pyridaphenthion, pyridaben, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, pirimicarb, pyrimidifen, pyriminostrobin, pirimiphos-methyl, pyrethrine, famphur, fiprole Fipronil, fenazaquin, fenamiphos, fenitrothion, fenoxycarb, fenothiocarb, phenothrin [including (1R)-trans-isomer], fenobucarb, fenthion, phenthoate, fenvalerate, fenpyroximate, fenbutanthin oxide oxide), fenpropathrin, fonofos, sulfuryl fluoride, butocarboxim, butoxycarboxim, buprofezin, furathiocarb, prallethrin, fluacrypyrim, fluazaindolizine, fluazuron, fluensulfone, sodium fluoroacetate, fluxametamide, flucycloxuron, flucythrinate, flusulfamide,Fluvalinate [containing tau-form], flupyradifurone, flupyrazofos, flupyrimin, flufiprole, flufenerim, , flufenoxystrobin, flufenoxuron, fluhexafon, flubendiamide, flumethrin, protrifenbute, prothiofos, protrifenbute, flonicamid, propaphos, propargite propargite, profenofos, broflanilide, profluthrin, propetamphos, propoxur, flometoquin, bromopropylate, hexythiazox, hexaflumuron, Paecilomyces tenuipes tenuipes, Paecilomyces fumosoroceus, heptafluthrin, heptenophos, permethrin, benclothiaz, bensultap, benzoximate, bendiocarb, benfuracarb, Beauveria tenella, Beauveria bassiana, Beauveria brongniartiibrongniartii, phoxim, phosalone, fosthiazate, fosthietan, phosphamidon, phosmet, polynactins, formetanate, phorate, malathion, milbemectin, mecarbam, mesulfenfos, methoprene, methomyl, metaflumizone, methamidophos, metham, methiocarb, methidathion, methyl isothiocyanate, methyl bromide bromide, methoxychlor, methoxyfenozide, methothrin, metofluthrin, epsilon-metofluthrin, metolcarb, mevinphos, meperfluthrin, Monacrosporium phymatophagum, monocrotophos, momfluorothrin, epsilon-momfluorothrin, litlure-A, litlure-B, aluminum phosphide, zinc phosphide phosphide, hydrogen phosphine, lufenuron, rescalure, resmethrin, lepimectin, rotenone, fenbutatin oxide, calcium nitrogencyanide, nicotine sulfate, (Z)-11-tetradecenyl acetate, (Z)-11-hexadecenal, (Z)-11-hexadecenyl acetate, (Z)-9,12-tetradecadienyl acetate, (Z)-9-tetradecen-1-ol, (Z,E)-9,11-tetradecadienyl acetate, (Z,E)-9,12-tetradecadienyl acetate, Bacillus popilliae, Bacillus subtillis, Bacillus sphaericus, Bacillus thuringiensis subsp. Aizawai), Bacillus thuringiensis subsp. Israelensis, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis, Bt proteins (Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb,Cry34 / 35Ab1), CL900167 (code number), DCIP (Bis-(2-chloro-1-methylethyl) ether), DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane), DEP (Dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate), DNOC (4,6-dinitro-o-cresol), DSP (O,O-Diethyl-O-[4-(dimethylsulfamoyl)phenyl]-phosphonate), holothionate), EPN (O-ethyl-O-4-(nitrophenyl)phenylphosphonothioate), nuclear polyhedrosis virus occlusion bodies, NA-85 (code number), NA-89 (code number), NC-515 (code number), RU15525 (code number), XMC, Z-13-icosen-10-one, ZXI8901 (code number), (RS)-2-chloro-4-fluoro-5-[5-(trifluoromethylthio)pentyloxy]phenyl 2,2,2-trifluoroethyl sulfoxide (chemical name, CAS registration number: 1472050-04-6).

[0016] [Bactericidal active ingredient] Azaconazole, acibenzolar-S-methyl, azoxystrobin, anilazine, amisulbrom, ametoctradin, aldimorph, isotianil, isopyrazam, isofetamide, isoprothiolane, ipconazole, ipfentrifluconazole, iprodione, iprovalicarb, iprobenfos, imazalil, iminoctadine-trialbesilate, iminoctadine-triacetate, imibenconazole, edifenphos, etaconazole, ethaboxam, ethirimol, ethoxyquin, etridiazole, enestroburin, enoxastrobin, epoxiconazole, organic oil oils), oxadixyl, oxazinylazole, oxathiapiprolin, oxycarboxin, oxine-copper, oxytetracycline, oxpoconazole-fumarate, oxolinic acid, copper dioctanoate, octhilinone, ofurace, orysastrobin,Orthophenylphenol, kasugamycin, captafol, carpropamid, carbendazim, carboxin, carvone, quinoxyfen, quinofumelin, chinomethionat, captan, quinconazole, quintozene, guazatine, cufraneb, coumoxystrobin, kresoxim-methyl, clozylacon, chlozolinate, chlorothalonil, chloroneb, cyazofamid, diethofencarb, diclocymet, dichlofluanid, dichlobenthiazox, diclo Diclomezine, dicloran, dichlorophen, dithianon, diniconazole, diniconazole-M, zineb, dinocap, dipymetitrone, diphenylamine, difenoconazole, cyflufenamid, diflumetorim, cyproconazole, cyprodinil, simeconazole, dimethirimol, dimethyl disulfide, dimethomorph, cymoxanil, dimoxystrobin,Ziram, silthiofam, streptomycin, spiroxamine, sedaxane, zoxamide, dazomet, tiadinil, thiabendazole, thiram, thiophanate, thiophanate-methyl hyl, thifluzamide, tecnazene, tecloftalam, tetraconazole, debacarb, tebuconazole, tebufloquin, terbinafine, dodine, dodemorph, triadimenol, triadimefone triadimefon, triazoxide, trichlamide, triclopyricarb, tricyclazole, triticonazole, tridemorph, triflumizole, trifloxystrobin, triforine, tolylfluanid, tolclofos-methyl, tolnifanide, tolprocarb, nabam, natamycin, naftifine, nitrapyrin, nitrothal-isopropyl, nuarimol, copper nonylphenolsulfonate nonyl phenol sulphonate), Bacillus subtilis (strain: QST 713), validamycin,Valifenalate, picarbutrazox, bixafen, picoxystrobin, pydiflumetofen, bitertanol, binapacryl, biphenyl, piperalin, hymexazol, pyraoxystrobin, pyraclostrobin, pyraziflumid iflumid, pyrazophos, pyrametostrobin, pyriophenone, pyrisoxazole, pyrifenox, pyributicarb, pyribencarb, pyrimethanil, pyroquilon, vinclozolin, ferbam, famoxadone, phenazine oxide oxide), fenamidone, phenaminestrobin, fenarimol, fenoxanil, ferimzone, fenpiclonil, fenpicoxamid, fenpyrazamine, fenbuconazole, fenfuram, fenpropidin, fenpropimorph, fenhexamid, folpet, phthalide, bupirimate, fuberidazole, blasticidin-S, furametpyr, furalaxyl,furancarboxylic acid, fluazinam, fluindapyr, fluoxastrobin, fluopicolide, fluopyram, fluoroimide, fluxapyroxad, fluquinconazole, fluconazole, fluconazole-cis, fludioxonil (fludioxonil), flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, flufenoxystrobin, flumetover, flumorph, proquinazid, prochloraz, procymidone , prothiocarb, prothioconazole, bronopol, propamocarb-hydrochloride, propiconazole, propineb, probenazole, bromuconazole, flometoquin, hexaconazole, benalaxyl benalaxyl, benalaxyl-M, benodanil, benomyl, pefurazoate, penconazole, pencycuron, benzovindiflupyr, benthiazole, benthiavalicarb-isopropyl, penthiopyrad,Penflufen, Boscalid, Fosetyl (aluminium, calcium, sodium), Polyoxin, Polycarbamate, Bordeaux mixture, mancozeb, mandipropamid, mandestrobin, maneb, myclobutanil, mineral oils, mildiomycin, methasulfocarb, metam, metalaxyl, metalaxyl-M, metiram, metconazole, metominostrobin, metrafenone, mepanipyrim, mefentrifluconazole, Meptyldinocap, mepronil, iodocarb, laminarin, phosphorous acid and salts, copper oxychloride, silver, cuprous oxide, copper hydroxide, potassium bicarbonate, sodium bicarbonate, sulfur, oxyquinoline sulfate, copper sulfate, (3,4-dichloroisothiazol-5-yl)methyl 4-(tert-butyl)benzoic acid ester (chemical name, CAS registration number: 1231214-23-5), BAF-045 (code number), BAG-010 (code number), UK-2A (code number), DBEDC (dodecylbenzenesulfonic acid bisethylenediamine copper complex salt [II]), MIF-1002 (code number), TPTA (triphenyltin acetate), TPTC (triphenyltin chloride), TPTH (triphenyltin hydroxide), nonpathogenic Erwinia carotovora.

[0017] [Herbicidal active ingredient] ioxynil, aclonifen, acrolein, azafenidin, acifluorfen (including salts with sodium, etc.), azimsulfuron, asulam, acetochlor, atrazine, anilofos, amicarbazone, amidosulfuron n), amitrole, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, ametryn, alachlor, alloxydim, isouron, isoxachlortole, isoxaflutole, isoxaben, isoprothrombin isoproturon, ipfencarbazone, imazaquin, imazapic (including salts with amines, etc.), imazapyr (including salts with isopropylamine, etc.), imazamethabenz-methyl, imazamox, imazethapyr, imazosulfuron, indaziflam, indazol indanofan, eglinazine-ethyl, esprocarb, ethametsulfuron-methyl, ethalfluralin, ethidimuron, ethoxysulfuron, ethoxyfen-ethyl, ethofumesate, etobenzanid,Endothal disodium salt, oxadiazon, oxadiargyl, oxaziclomefone, oxasulfuron, oxyfluorfen, oryzalin, orthosulfamuron, orbencarb, oleic acid acid), cafenstrole, carfentrazone-ethyl, karbutilate, carbetamide, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, quinoclamine, quinclorac, quinmerac, cumyluron, clacyfos, glyphosate (including its sodium, potassium, ammonium, amine, propylamine, isopropylamine, dimethylamine or trimesium salts), glufosinate lufosinate (including salts such as amine or sodium), glufosinate-P-sodium, clethodim, clodinafop-propargyl, clopyralid, clomazone, chlomethoxyfen, clomeprop, chloransulam-methyl, chloramben, chloridazon, chlorimuron-ethyl, chlorsulfuron, chlorthal-dimethyl, chlorthiamid,Chlorphthalim, chlorflurenol-methyl, chlorpropham, chlorbromuron, chloroxuron, chlorotoluron, ketospiradox (including salts of sodium, calcium, or ammonia), saflufenacil, sarmentine, cyanazine, cyanamide, diuron, diethathyl-ethyl, dicamba (including salts of amines, diethylamine, isopropylamine, diglycolamine, sodium, or lithium), cycloate, cycloxydim, diclosulam, cyclosulfamuron, cyclopyrimorate ), dichlobenil, diclofop-P-methyl, diclofop-methyl, dichlorprop, dichlorprop-P, diquat, dithiopyr, siduron, dinitramine, cinidon-ethyl, cinosulfuron, dinozeb ( dinoseb, dinoterb, cyhalofop-butyl, diphenamid, difenzoquat, diflufenican, diflufenzopyr, simazine, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P,Simetryn, dimepiperate, dimefuron, cinmethylin, swep, sulcotrione, sulfentrazone, sulfosate, sulfosulfuron, sulfometuron-methyl, sethoxydim, terbacil, daimuron, thaxtomin A A), dalapon, thiazopyr, thiaphenacyl, thiencarbazone (including sodium salt, methyl ester, etc.), thiocarbazil, thiobencarb, thidiazimin, thifensulfuron-methyl, desmedipham, desmetryne, thenylchlor, tebutam, tebuthiuron, tepraloxydim, tefuryltrione, tembotrione botrione, terbuthylazine, terbutryn, terbumeton, topramezone, tralkoxydim, triaziflam, triasulfuron, triafamone, tri-allate, trietazine, triclopyr, triclopyr-butotyl, trifludimoxazin, tritosulfuron, triflusulfuron-methyl,Trifluralin, trifloxysulfuron-sodium, tribenuron-methyl, tolpyralate, naptalam (including salts with sodium, etc.), naproanilide, naproamide, naproamide-M, nicosulfuron, neburon, Norflurazon, vernolate, paraquat, halauxifen-benzyl, halauxifen-methyl, haloxyfop, haloxyfop-P, haloxyfop-etotyl, halosafen, halosulfuron-methyl, picloram ( picloram, picolinafen, bicyclopyrone, bispyribac-sodium, pinoxaden, bifenox, piperophos, pyraclonil, pyrasulfotole, pyrazoxyfen, pyrazosulfuron-ethyl, pyrazolinate ( pyrazolynate, bilanafos, pyraflufen-ethyl, pyridafol, pyrithiobac-sodium, pyridate, pyriftalid, pyributicarb, pyribenzoxim, pyrimisulfan, pyriminobac-methyl,, pyroxasulfone, pyroxsulam, phenisopham, fenuron, fenoxasulfone, fenoxaprop (including methyl, ethyl, and isopropyl esters), fenoxaprop-P (including methyl, ethyl, and isopropyl esters), fenquinotrione, fenthiaprop-ethyl op-ethyl, fentrazamide, phenmedipham, butachlor, butafenacil, butamifos, butylate, butenachlor, butralin, butroxydim, flazasulfuron, flamprop (including methyl, ethyl, and isopropyl esters) , flamprop-M (including methyl, ethyl, and isopropyl esters), primisulfuron-methyl, fluazifop-butyl, fluazifop-P-butyl, fluazolate, fluometuron, fluoroglycofen-ethyl, flucarbazone-sodium salt odium), fluchloralin, flucetosulfuron, fluthiacet-methyl, flupyrsulfuron-methyl-sodium, flufenacet, flufenpyr-ethyl, flupropanate, flupoxame, flumioxazin,Flumiclorac-pentyl, flumetsulam, fluridone, flurtamone, fluroxypyr, flurochloridone, pretilachlor, procarbazone-sodium, prodiamine, prosulfuron, prosulfocarb, propaquizafop, propachlor, propazine, propanil, propyzamide, propisochlor, propyrisulfuron, propham, profluazol, propoxycarbazone-sodium, profoxydim, bromacil, brompyrazone, prometryn, prometon, bromoxynil (including esters of butyric acid, octanoic acid, or heptanoic acid), bromofenoxim, bromobutide, florasulam, florpyrauxifen , hexazinone, pethoxamid, benazolin, penoxsulam, heptamaloxyloglucan, beflubutamid, pebulate, pelargonic acid, bencarbazone, pendimethalin, benzfendizone, bensulide,Bensulfuron-methyl, benzobicyclon, benzofenap, bentazone, pentanochlor, pentoxazone, benfluralin, benfuresate, fosamine, fomesafen, foramsulfuron, mecoprop prop (including sodium, potassium, isopropylamine, triethanolamine, dimethylamine, etc. salts), mecoprop-P-potassium, mesosulfuron-methyl, mesotrione, metazachlor, metazosulfuron, methabenzthiazuron, metamitron, metamifop mifop, DSMA (disodium methanearsonate), methiozolin, methyldymuron, metoxuron, metosulam, metsulfuron-methyl, metobromuron, metobenzuron, metolachlor, metribuzin, mefenacet, monosulfuron monosulfuron (including methyl, ethyl, and isopropyl esters), monolinuron, molinate, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, lactofen, lancotrione,Linuron, rimsulfuron, lenacil, TCA (2,2,2-trichloroacetic acid) (including salts such as sodium, calcium, or ammonia), 2,3,6-TBA (2,3,6-trichlorobenzoic acid), 2,4,5-T (2,4,5-trichlorophenoxyacetic acid), 2,4-D (2,4-dichlorophenoxyacetic acid) (including salts such as amines, diethylamine, triethanolamine, isopropylamine, sodium, or lithium), ACN (2-amino-3-chloro-1,4-naphthoquinone), MCPA (2-methyl-4-chlorophenoxy) diacetic acid), MCPB (2-methyl-4-chlorophenoxybutyric acid) (including sodium salt, ethyl ester, etc.), 2,4-DB (4-(2,4-dichlorophenoxy)butyric acid), DNOC (4,6-dinitro-O-cresol) (including amine or sodium salt, etc.), AE-F-150944 (code number), HW-02 (code number), IR-6396 (code number), MCPA-thioethyl, SYP-298 (code number), SYP-300 (code number), EPTC (S-ethyldipropylthiocarbamate), S-metolachlor.

[0018] [Plant growth regulating active ingredient] 1-Methylcyclopropene, 1-naphthylacetamide, 2,6-diisopropylnaphthalene6-diisopropylnaphthalene, 4-CPA (4-chlorophenoxyacetic acid), benzylaminopurine, ancymidol, aviglycine, carvone, chlormequat, cloprop, cloxyfonac, cloxyfonac-potassium, cyclanilide, cytokinin s), daminozide, dikegulac, dimethipin, ethephon, epocholeone, ethychlozate, flumetralin, flurenol, flurprimidol, forchlorfenuron, gibberellins, inabenfide, indoleacetic acid acetic acid, indole butyric acid, maleic hydrazide, mefluidide, mepiquat chloride, n-decyl alcohol, paclobutrazol, prohexadione-calcium, prohydrojasmon, sintophen, thidiazuron, triacontanol, trinexapac-ethyl, uniconazole, uniconazole-P, 4-oxo-4-(2-phenylethyl)aminobutyric acid (chemical name, CAS registration number: 1083-55-2), calcium peroxide.

[0019] Among these pesticide active ingredients, those with a water solubility of 100 ppm or less are preferred, and those with a water solubility of 0.05 to 95 ppm are more preferred. The water solubility is a value measured in distilled water at 20°C. Examples of pesticide active ingredients with a water solubility of 100 ppm or less include, but are not limited to, the following examples: pyribencarb (63 ppm), benthiavalicarb isopropyl (13.1 ppm), mepanipyrim (3.1 ppm), diclobentiazox (36.0 ppm), chlorantraniliprole (1.0 ppm), tetraniliprole (1.2 ppm), cyantraniliprole (14.2 ppm), isotianil (0.5 ppm), ferimzone (20.8 ppm), fthalide. (46.2ppm), Ethiprole (9.2ppm), Spinetoram (31.9ppm), Oxazosulfil (15.6ppm), Penflufen (10.9ppm), Pencycuron (30.0ppm), Thifluzamide (1.6ppm), Azimsulfuron (48ppm), Ethoxysulfuron (10.5ppm), Oxadiazon (0.57ppm), Oxadiargyl (0.37ppm), Chlorimuron-ethyl (8.6ppm), Cyclosulfamuron (0.34ppm), Dimethicone (0.34ppm), sulphon (0.79ppm), triafamone (41ppm), halosulfuron-methyl (10.2ppm), pyraclonil (50.1ppm), pyrazosulfuron-ethyl (9.8ppm), pyriftalid (1.8ppm), pyribenzoxim (3.5ppm), pyrimisulfan (87ppm), pyriminobac-methyl (E-isomer 9.3ppm), pyroxasulfone (3.5ppm), fenoxasulfone (0.17ppm), fenquinotrione (17ppm), butachlor (16ppm) , propanil (95 ppm), propyrisulfuron (0.98 ppm), fluthiacet-methyl (0.85 ppm), pretilachlor (74 ppm), penoxsulam (4.9 ppm), bensulfuron-methyl (6.7 ppm), benzofenap (0.12 ppm), benzobicyclon (0.052 ppm), pentoxazone (0.22 ppm), pendimethalin (0.26 ppm), metamifop (0.69 ppm), and mefenacet (5.2 ppm).

[0020] The pesticide active ingredient may be used as it is so long as its volume median diameter is within the above range, or, if necessary, may be subjected to a pulverization method such as wet pulverization or dry pulverization to bring it into the above range.

[0021] The water-soluble polymer used in the composition of the present invention is not particularly limited, and examples thereof include polyvinyl alcohol, polyacrylic acid-based polymers, polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, etc. These water-soluble polymers can be used alone or in combination of two or more. Among these water-soluble polymers, polyvinylpyrrolidone is preferred because it has a high elution rate of pesticide active ingredients.

[0022] It is known that polyvinylpyrrolidone exhibits different viscosities in an aqueous solution depending on the degree of polymerization of the vinylpyrrolidone monomer that constitutes it, and an index of this viscosity can be given as the K value represented by the following formula (I).

[0023]

number

[0024] The blending amounts of the pesticide active ingredient and the water-soluble polymer in the composition of the present invention are not particularly limited, but for example, the pesticide active ingredient is 0.1 to 50.0 parts by mass, preferably 0.5 to 30.0 parts by mass, and the water-soluble polymer is 0.1 to 20.0 parts by mass, preferably 0.1 to 10.0 parts by mass, relative to 100 parts by mass of the composition of the present invention. The blending ratio of the pesticide active ingredient and the water-soluble polymer in the composition of the present invention is also not particularly limited, but for example, the mass ratio of the pesticide active ingredient and the water-soluble polymer is 1:0.05 to 100.0, preferably 0.1 to 20.0.

[0025] In addition to the above-mentioned crystalline particles of an agricultural chemical active ingredient having a volume median diameter of less than 1 μm and a water-soluble polymer, the composition of the present invention further contains solid carriers / excipients such as bentonite, clay, kaolin, sericite, talc, acid clay, pumice, zeolite, vermiculite, perlite, calcium carbonate, and silica sand; surfactants such as alkyl sulfate ester salts, aryl sulfonate salts, polyoxyethylene glycol ethers, polyhydric alcohol esters, dialkyl sulfosuccinate salts, polycarboxylic acids, polyoxyethylene nonylphenyl ether, and sodium lignin sulfonate; starch, alginic acid, glycerin, polyvinylpyrrolidone, and the like. binders such as polyvinyl alcohol, gum arabic, liquid paraffin, ethyl cellulose, and polyvinyl acetate; lubricants such as calcium stearate, talc, and silica; colorants such as dyes and pigments; benoxacor, furilazole, dichlormid, dicyclonone, DKA-24 (N1,N2-diallyl-N2-dichloroacetylglycinamide), AD-67 (4-dichloroacetyl-1-oxa-4-azaspiro[4.5] decane), PPG-1292 (2,2-dichloro-N-(1,3-dioxane-2-ylmethyl)-N-(2-propenyl)acetamide), R-29148 (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine), cloquintcet-mexyl, naphthalic anhydride (1,8-Naphthalic Anhydride, mefenpyr-diethyl, mefenpyr, mefenpyr-ethyl, fenchlorazole-O-ethyl, fenclorim, MG-191 (2-dichloromethyl-2-methyl-1,3-dioxane), cyometrinil, flurazole, fluxofenim , isoxadifen, isoxadifen-ethyl, MON4660 (code number), oxabetrinil, cyprosulfamide, lower alkyl-substituted benzoic acid, TI-35 (code number) or N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide (chemical name, CAS registration number: 129531-12-0) and other safeners may be contained. The amounts and ratios of these components in the composition of the present invention can be appropriately determined by those skilled in the art.

[0026] Preferred embodiments of the composition of the present invention include the following. Pesticide active ingredient (volume median diameter: 0.01 to less than 1.0 μm): 0.1 to 50.0 parts by mass Water-soluble polymer: 0.1 to 20.0 parts by mass Solid carrier: 0 to 30.0 parts by mass Surfactant: 0.1 to 30.0 parts by mass Excipient: 0.1 to 99.6 parts by weight Binder: 0.1 to 10.0 parts by weight Lubricant: 0 to 3.0 parts by weight Colorant: 0 to 5.0 parts by weight Safener: 0 to 40.0 parts by mass

[0027] The composition of the present invention can be produced according to a conventional method, except that it contains the above-mentioned components. The dosage form of the composition of the present invention can be a conventional one such as granules, suspension, powder, solution, etc., but the suspension and powder forms are preferred.

[0028] A preferred method for producing the composition of the present invention is, for example, a method comprising the steps of grinding crystalline particles of an agricultural chemical active ingredient until the volume median diameter is less than 1 μm, and mixing the crystalline particles of the agricultural chemical active ingredient with a water-soluble polymer before or after the grinding step (hereinafter, this is referred to as the "method of the present invention").

[0029] In the method of the present invention, the step of pulverizing the crystal particles of the pesticide active ingredient until the volume median diameter is less than 1 μm may be carried out by a pulverizing means such as dry pulverization or wet pulverization to achieve the above range.

[0030] In the process of the present invention, the step of mixing the crystalline particles of the agricultural chemical active ingredient with the water-soluble polymer, which is carried out before or after the grinding step, is carried out by mixing using a mixing means such as stirring.

[0031] Furthermore, in the method of the present invention, it is preferable to include a step of obtaining a suspension-type pesticide composition by performing the above-mentioned pulverization step as wet pulverization. The wet pulverization is not particularly limited, but is performed, for example, by adding a solvent such as water using an attritor, paint shaker, sand grinder, etc. In this way, the pesticide composition becomes a suspension, and the volume median diameter of the crystal particles of the pesticide active ingredient can be made less than 1 μm relatively easily.

[0032] In the method of the present invention, it is preferable to mix the suspension-form pesticide composition obtained above with a powder containing a solid carrier to obtain a mixture, and granulate the mixture to obtain a granular pesticide composition. The solid carrier is the same as that described above. The powder can further contain excipients, surfactants, etc., as described above.

[0033] The method and conditions for granulating the mixture are not particularly limited, and for example, known granulation methods such as extrusion granulation, fluidized bed granulation, and coating granulation can be used under known conditions.

[0034] Furthermore, the above granulated agricultural chemical composition may be further subjected to a drying step or the like, if necessary.

[0035] The composition of the present invention thus obtained has improved dissolution properties of the pesticide active ingredient in water, where improved dissolution properties mean, for example, that the dissolution properties are 2 to 6 times higher than when coarse crystal particles of the pesticide active ingredient are used, and 2 to 3 times higher than when fine crystal particles are used. EXAMPLES

[0036] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0037] In the following examples, the average particle size refers to the median diameter (volume median diameter) of the volume particle size distribution measured by a laser analysis type particle size distribution measuring device. The K value is the value obtained by measuring the viscosity of a 1% by mass aqueous solution of polyvinylpyrrolidone by a capillary viscometer at 25°C. Furthermore, the presence of crystalline particles was confirmed by taking a diffraction pattern of the pesticide composition using a powder X-ray diffraction device and finding that a peak appeared at the peak position specific to the crystalline particles of each pesticide active ingredient. Crystals of the pesticide active ingredient were present in all of the slurries obtained in the examples.

[0038] Example 1 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 5 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0), 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a predetermined amount of water were mixed to make a total amount of 100 parts. This mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.24 μm, and a chlorantraniliprole-containing slurry was obtained.

[0039] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0040] Example 2 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 10.5 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0), 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and Bronopol, and a predetermined amount of water were mixed to make a total amount of 100 parts. This mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.66 μm, and a chlorantraniliprole-containing slurry was obtained.

[0041] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0042] Example 3 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 3.2 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0), 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a predetermined amount of water were mixed to make a total amount of 100 parts. This mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.67 μm, and a chlorantraniliprole-containing slurry was obtained.

[0043] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0044] Example 4 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 5.3 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0), 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a predetermined amount of water were mixed to make a total amount of 100 parts. This mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.72 μm, and a chlorantraniliprole-containing slurry was obtained.

[0045] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0046] Example 5 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 7.2 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0), 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and Bronopol, and a predetermined amount of water were mixed to make a total amount of 100 parts. This mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.73 μm, and a chlorantraniliprole-containing slurry was obtained.

[0047] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0048] Example 6 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 5.3 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0), 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a predetermined amount of water were mixed to make a total amount of 100 parts. This mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.60 μm, and a chlorantraniliprole-containing slurry was obtained.

[0049] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0050] Example 7 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to a total amount of 95 parts. This mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.77 μm, and 5 parts of water were further added to obtain a chlorantraniliprole-containing slurry.

[0051] 3.75 parts of the slurry, 2 parts of diclobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 99.8 parts (dry basis). A predetermined amount of water in which 0.2 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0) was dissolved was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, to obtain a granular pesticide composition.

[0052] Example 8 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to make a total amount of 95 parts. This mixture was wet-pulverized using glass beads as the grinding medium until the average particle size became 0.77 μm, and 5 parts of water were further added to obtain a chlorantraniliprole-containing slurry.

[0053] 3.75 parts of the slurry, 2 parts of diclobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 99.5 parts (dry basis). A predetermined amount of water in which 0.5 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0) was dissolved was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, to obtain a granular pesticide composition.

[0054] Example 9 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to make a total amount of 95 parts. This mixture was wet-pulverized using glass beads as the grinding medium until the average particle size became 0.77 μm, and 5 parts of water were further added to obtain a chlorantraniliprole-containing slurry.

[0055] 3.75 parts of the slurry, 2 parts of diclobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 99 parts (dry basis). A predetermined amount of water in which 1 part of polyvinylpyrrolidone (K value = 27.0 to 33.0) was dissolved was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0056] Example 10 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to make a total amount of 95 parts. This mixture was wet-pulverized using glass beads as the grinding medium until the average particle size became 0.77 μm, and 5 parts of water were further added to obtain a chlorantraniliprole-containing slurry.

[0057] 3.75 parts of the slurry, 2 parts of diclobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 98.5 parts (dry basis). A predetermined amount of water in which 1.5 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0) was dissolved was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, to obtain a granular pesticide composition.

[0058] Example 11 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to make a total amount of 95 parts. This mixture was wet-pulverized using glass beads as the grinding medium until the average particle size became 0.77 μm, and 5 parts of water were further added to obtain a chlorantraniliprole-containing slurry.

[0059] 3.75 parts of the slurry, 2 parts of diclobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 98 parts (dry basis). A predetermined amount of water in which 2 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0) was dissolved was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, to obtain a granular pesticide composition.

[0060] Comparison example 1 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to make up a total of 100 parts. This mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.24 μm, to obtain a chlorantraniliprole-containing slurry.

[0061] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0062] Comparison example 2 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 5.3 parts of polyvinylpyrrolidone, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to make up a total of 100 parts. This mixture was wet-milled using glass beads as a milling medium until the average particle size became 2.08 μm, to obtain a chlorantraniliprole-containing slurry.

[0063] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0064] Comparison example 3 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 5.3 parts of polyvinylpyrrolidone, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to make up a total of 100 parts. This mixture was wet-milled using glass beads as a milling medium until the average particle size became 1.42 μm, to obtain a chlorantraniliprole-containing slurry.

[0065] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0066] Comparison example 4 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 5.3 parts of polyvinylpyrrolidone, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to make up a total of 100 parts. This mixture was wet-milled using glass beads as a milling medium until the average particle size became 1.07 μm, to obtain a chlorantraniliprole-containing slurry.

[0067] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0068] Comparison example 5 20 parts of chlorantraniliprole, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to make up a total of 100 parts. This mixture was wet-milled using zirconia beads as a milling medium until the average particle size became 0.77 μm, to obtain a chlorantraniliprole-containing slurry.

[0069] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0070] Comparison example 6 20 parts of chlorantraniliprole having an average particle size of approximately 20 μm that had been previously impact-ground, 5 parts of lignin sulfonate, 3 parts of polyoxyethylene alkyl ether sulfate, 0.2 parts of dimethylpolysiloxane, 0.2 parts of a mixture of CMIT, MIT and bronopol, and a specified amount of water were mixed to make a total amount of 100 parts, thereby obtaining a chlorantraniliprole-containing slurry.

[0071] 3.75 parts of the slurry, 2 parts of dichlorobentazox, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, 3 parts of calcium carbonate, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0072] Test Example 1 100 mg of the granular pesticide composition of Examples 1-11 and Comparative Examples 1-6 was put into 700 mL of 3 degree hard water, and the concentration of chlorantraniliprole in the water after a predetermined time was measured using high performance liquid chromatography. The measurement results are shown in Table 1.

[0073] [Table 1]

[0074] When the average particle size is less than 1 μm and PVP is contained, the elution concentration is approximately 7 times higher than when the average particle size is 1 μm or more and PVP is not contained. Also, when the average particle size is less than 1 μm but does not contain PVP, the elution concentration is approximately 4 times higher. When the average particle size is 1 μm or more and PVP is contained, the elution concentration is approximately 3 times higher, with the rate of increase being greatest when the average particle size is less than 1 μm and PVP is contained.

[0075] Example 12 4.47 parts of pyrimisulfan, 26.78 parts of fenquinotrione, 3 parts of polyoxyethylene allylphenyl ether ammonium sulfate, 10 parts of propylene glycol, 0.15 parts of xanthan gum, 0.2 parts of a mixture of CMIT, MIT and bronopol, 0.02 parts of dimethylpolysiloxane and a specified amount of water were mixed to a total amount of 100 parts. This mixture was wet-milled using zirconia beads as a milling medium until the average particle size became 0.23 μm, to obtain a slurry containing pyrimisulfan and fenquinotrione.

[0076] 11.21 parts of the slurry, 0.1 part of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, and a predetermined amount of clay were mixed to make a total amount of 99 parts (dry basis). A predetermined amount of water in which 1 part of polyvinylpyrrolidone was dissolved was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole size, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0077] Comparison example 7 4.47 parts of pyrimisulfan, 26.78 parts of fenquinotrione, 3 parts of polyoxyethylene allylphenyl ether ammonium sulfate, 10 parts of propylene glycol, 0.15 parts of xanthan gum, 0.2 parts of a mixture of CMIT, MIT and bronopol, 0.02 parts of dimethylpolysiloxane and a specified amount of water were mixed to a total amount of 100 parts. This mixture was wet-milled using zirconia beads as a milling medium until the average particle size became 0.23 μm, to obtain a slurry containing pyrimisulfan and fenquinotrione.

[0078] 11.21 parts of the slurry, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0079] Test Example 2 100 mg of the granular pesticide compositions of Example 12 and Comparative Example 7 were put into 700 mL of 3 degree hard water, and the pyrimisulfan concentration and fenquinotrione concentration in the water after one day were measured using high performance liquid chromatography. The measurement results are shown in Table 2.

[0080] [Table 2]

[0081] For both pyrimisulfan and fenquinotrione, improved elution concentrations were observed when the average particle size was less than 1 μm and PVP was included.

[0082] Example 13 47.62 parts of pyroxasulfone, 1.97 parts of formalin condensate of naphthalenesulfonate, 0.69 parts of dialkyl sulfosuccinate, 0.98 parts of polyoxyethylene tristyrylphenyl ether, 11.87 parts of propylene glycol, 0.06 parts of xanthan gum, 0.03 parts of a mixture of CMIT, MIT and bronopol, 0.24 parts of dimethylpolysiloxane and a predetermined amount of water were mixed to a total of 100 parts. This mixture was wet-milled using glass beads as a milling medium until the average particle size became 3 μm, to obtain a primary slurry.

[0083] Also, 4.09 parts of propylene glycol, 0.35 parts of xanthan gum, 0.09 parts of dimethylpolysiloxane, 0.04 parts of a mixture of CMIT, MIT and bronopol, 0.35 parts of bentonite and a specified amount of water were mixed to prepare a diluted solution with a total volume of 100 parts.

[0084] 76.99 parts of the primary slurry and 23.01 parts of the diluent were mixed, and this mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.66 μm, to obtain a secondary slurry containing pyroxasulfone.

[0085] 2.5 parts of the secondary slurry, 0.1 part of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, and a predetermined amount of clay were mixed to make a total amount of 99 parts (dry basis). A predetermined amount of water in which 1 part of polyvinylpyrrolidone was dissolved was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole size, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0086] Comparison example 8 47.62 parts of pyroxasulfone, 1.97 parts of formalin condensate of naphthalenesulfonate, 0.69 parts of dialkyl sulfosuccinate, 0.98 parts of polyoxyethylene tristyrylphenyl ether, 11.87 parts of propylene glycol, 0.06 parts of xanthan gum, 0.03 parts of a mixture of CMIT, MIT and bronopol, 0.24 parts of dimethylpolysiloxane and a predetermined amount of water were mixed to a total of 100 parts. This mixture was wet-milled using glass beads as a milling medium until the average particle size became 3 μm, to obtain a primary slurry.

[0087] Also, 4.09 parts of propylene glycol, 0.35 parts of xanthan gum, 0.09 parts of dimethylpolysiloxane, 0.04 parts of a mixture of CMIT, MIT and bronopol, 0.35 parts of bentonite and a specified amount of water were mixed to prepare a diluted solution with a total volume of 100 parts.

[0088] 76.99 parts of the primary slurry and 23.01 parts of the diluent were mixed, and this mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.66 μm, to obtain a secondary slurry containing pyroxasulfone.

[0089] 2.5 parts of the secondary slurry, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a hole diameter of 1.2 mm, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0090] Test Example 3 100 mg of the granular pesticide compositions of Example 13 and Comparative Example 8 were put into 700 mL of 3 degree hard water, and the pyroxasulfone concentration in the water after one day was measured using high performance liquid chromatography. The measurement results are shown in Table 3.

[0091] [Table 3]

[0092] The elution concentration of pyroxasulfone was improved when the average particle size was less than 1 μm and PVP was included.

[0093] Example 14 30 parts of fenoxasulfone, 12 parts of formalin condensate of naphthalenesulfonate, 1 part of dialkyl sulfosuccinate, 1.4 parts of polyoxyethylene styrylphenyl ether sulfate, 0.4 parts of polyoxyethylene alkyl ether, 6.2 parts of propylene glycol, 0.05 parts of xanthan gum, 0.1 parts of a mixture of CMIT, MIT and bronopol, 0.02 parts of dimethylpolysiloxane and a predetermined amount of water were mixed to a total of 100 parts. This mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.16 μm, to obtain a slurry containing fenoxasulfone.

[0094] 6.67 parts of the secondary slurry, 0.1 part of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, and a predetermined amount of clay were mixed to make a total amount of 99 parts (dry basis). A predetermined amount of water in which 1 part of polyvinylpyrrolidone was dissolved was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole size, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0095] Comparison example 9 30 parts of fenoxasulfone, 12 parts of formalin condensate of naphthalenesulfonate, 1 part of dialkyl sulfosuccinate, 1.4 parts of polyoxyethylene styrylphenyl ether sulfate, 0.4 parts of polyoxyethylene alkyl ether, 6.2 parts of propylene glycol, 0.05 parts of xanthan gum, 0.1 parts of a mixture of CMIT, MIT and bronopol, 0.02 parts of dimethylpolysiloxane and a predetermined amount of water were mixed to a total of 100 parts. This mixture was wet-pulverized using zirconia beads as a grinding medium until the average particle size became 0.16 μm, to obtain a slurry containing fenoxasulfone.

[0096] 6.67 parts of the secondary slurry, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, and a predetermined amount of clay were mixed to make a total amount of 100 parts (dry basis). A predetermined amount of water was added to this mixture, which was then kneaded, extrusion granulated using a screen with a 1.2 mm hole size, and then dried to remove moisture, thereby obtaining a granular pesticide composition.

[0097] Test Example 4 100 mg of the granular pesticide composition of Example 14 and Comparative Example 9 was put into 700 mL of 3 degree hard water, and the fenoxasulfone concentration in the water after 3 days was measured using high performance liquid chromatography. The measurement results are shown in Table 4.

[0098] [Table 4]

[0099] When fenoxasulfone had an average particle size of less than 1 μm and contained PVP, the elution concentration was improved. [Industrial Applicability]

[0100] The pesticide composition of the present invention can be used in agriculture in the same manner as ordinary pesticide compositions. That's all

Claims

1. A pesticide composition comprising crystalline particles of a pesticide active ingredient having a volume median diameter of less than 1 μm and a water-soluble polymer, wherein the pesticide active ingredient is one or more selected from the group consisting of chlorantraniliprole, pyrimisulfan, fenquinotrione, pyroxasulfone and fenoxasulfone, the water-soluble polymer is polyvinylpyrrolidone, and the pesticide composition is in a granular form, and further comprising, relative to 100 parts by mass of the pesticide composition, 0.1 to 30.0 parts by mass of a surfactant, 0.1 to 99.6 parts by mass of an excipient and 0.1 to 10.0 parts by mass of a binder.

2. 2. The pesticide composition according to claim 1, wherein the pesticide active ingredient is 0.1 to 50.0 parts by mass and the water-soluble polymer is 0.1 to 20.0 parts by mass, based on 100 parts by mass of the pesticide composition.

3. 3. The pesticide composition according to claim 1, wherein the mass ratio of the pesticide active ingredient to the water-soluble polymer is 1:0.05-100.

4. 4. The pesticide composition according to claim 1, wherein the water solubility of the pesticide active ingredient is 100 ppm or less.

5. 5. A method for producing an agrochemical composition comprising the steps of: grinding crystalline particles of an agrochemically active ingredient until the volume median diameter is less than 1 μm; and mixing the crystalline particles of the agrochemically active ingredient with a water-soluble polymer before or after the grinding step, wherein the water-soluble polymer is polyvinylpyrrolidone, and the agrochemically active ingredient is one or more selected from the group consisting of chlorantraniliprole, pyrimisulfan, fenquinotrione, pyroxasulfone, and fenoxasulfone.

6. The method according to claim 5, wherein the pesticide active ingredient and the water-soluble polymer are mixed in a mass ratio of 1:0.05 to 100.

7. The method according to claim 5 or 6, wherein the grinding step is wet grinding to obtain a suspension-type pesticide composition.

8. A method for producing an agrochemical composition, comprising the steps of mixing the suspension-form agrochemical composition obtained by the method according to claim 7 with a powder containing a solid carrier to obtain a mixture, and granulating the mixture to obtain a granular agrochemical composition.

Images