JP7628500B2 - Pesticide composition and method for producing same - Google Patents

Description

The present invention relates to a pesticide composition and a granular pesticide formulation having improved dissolution properties of pesticide active ingredients, and to methods for producing the same.

The dissolution of the pesticide active ingredients contained in the pesticide composition needs to be controlled or promoted according to various purposes.

Known means for controlling the release of pesticide active ingredients include, for example, means for processing the pesticide active ingredient itself, such as the microencapsulation described in Patent Document 1, and the sustained-release bulk powder described in Patent Document 2, and means for structurally endowing the pesticide with release control capabilities, such as hydrophobic substance-coated granules described in Patent Document 3, and hydrophobic substance-containing granules described in Patent Document 4. 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 their scope of application is necessarily limited to granular pesticides that do not disintegrate in water.

On the other hand, water-soluble polymers such as polyvinylpyrrolidone are widely known and are used in the agricultural chemical field mainly as physical property adjusting assistants such as binders and disintegrants. In addition, 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 caused by alkylbenzenesulfonic acid, a surfactant contained in aqueous formulations. Patent Document 7, which was also filed by the applicants, discloses that they control the dissolution of fenoxasulfone in water and prevent the occurrence of phytotoxicity due to localized increases in concentration.

However, it has not been previously known that water-soluble polymers such as polyvinylpyrrolidone can promote the dissolution of pesticide active ingredients.

JP 2004-103481 A Japanese Patent Application Publication No. 8-92497 Japanese Patent Application Publication No. 10-25202 JP 2000-26206 A Japanese Patent Application Publication No. 5-320010 JP 2014-196253 A JP 2019-19062 A

Therefore, the objective of the present invention is to provide a technology for promoting the dissolution of pesticide active ingredients using water-soluble polymers.

As a result of intensive research to solve the above problems, the inventors discovered that the dissolution of the pesticide active ingredient can be promoted by reducing the volume median diameter of the pesticide active ingredient combined with a water-soluble polymer, and thus completed the present invention.

That is, the present invention is an agricultural chemical composition characterized by containing crystalline particles of an agricultural chemical active ingredient having a volume median diameter of less than 1 μm and a water-soluble polymer.

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.

The pesticide composition of the present invention promotes the dissolution of the pesticide active ingredient by using a simple technique to reduce the volume median diameter of the crystal particles of the pesticide active ingredient. Therefore, it can be widely used as a herbicide, plant conditioner, insecticide, fungicide, etc.

The method for producing the pesticide composition of the present invention is simple because it does not require any special steps other than the step of reducing the volume median diameter of the crystal particles of the pesticide active ingredient.

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 the diameter at which the larger and smaller sides are equal when a powder is divided into two parts based on the volume of a certain particle diameter. This volume median diameter is obtained, for example, as the median diameter of the volume particle size distribution measured by a laser analysis particle size distribution measuring device.

The pesticide active ingredient used in the composition of the present invention is not particularly limited as long as it can be crystallized. Examples include, but are not limited to, those listed below. These pesticide active ingredients can be used alone or in combination of two or more.

[Insecticidal active ingredient]
Acrinathrin, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, acequinocyl, acetamiprid, acetoprole, acephate ephate), azocyclotin, abamectin, afidopyropene, afoxolaner, amidoflumet, amitraz, alanycarb, aldicarb, aldoxycarb, arethamicarb, Allethrin [including d-cis-trans- and d-trans-isomers], isazophos, isamidophos, isocarbophos, isoxathion, isofenphos-methyl, isoprocarb, ivermectin tin), imicyafos, imidacloprid, imiprothrin, indoxacarb, esfenvalerate, ethiofencarb, ethion, ethiprole, ethylene dibromide, etoxazole, etofenprox, ethoprophos, etrimfos, emamectin benzoate benzoate, endosulfan, empenthrin, oxazosulfyl, oxamyl, oxydemeton-methyl, oxydeprofos, omethoate, cadusafos, kappa-tefluthrin, kappa-bifenthrin, karanjin, cartap, carbaryl, carbosulfan, carbofuran, gamma-B HC (gamma-BHC), xylylcarb, quinalphos, kinoprene, chinomethionate, coumaphos, cryolite, clothianidin, clofentezine, chromafenozide, chlorantraniliprole, chlorethoxyfos, chlordane, chloropicrin, chlorpyrifos, chlorpyrifos-methyl (chlorpyrifos-methyl), chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroprallethrin, cyanophos, diafenthiuron, diamidafos, cyantraniliprole, dienochlor, cyenopyrafen, dioxabenzophos, diofenolan, cyanochlor ... Cyclaniliprole, dicrotophos, diclofenthion, cycloprothrin, dichlorvos, dichloromezotiaz, 1,3-dichloropropene lopropene), dicofol, dicyclanil, disulfoton, dinotefuran, dinobuton, cyhalodiamide, cyhalothrin [including gamma- and lambda-forms], Cyphenothrin [including (1R)-trans-isomer], cyfluthrin [including beta-isomer], diflubenzuron, cyflumetofen, diflovidazin, cyhexatin, cypermethrin (cypermethrin) [including alpha-, beta-, theta-, and zeta-forms], dimethylvinphos, dimefluthrin, dimethoate, silafluofen, cyromazine, spinetoram pinetoram, spinosad, spirodiclofen, spirotetramat, spiromesifen, sulcofuron-sodium, sulfuramide, sulfoxaflor lfoxaflor, sulfotep, diazinon, thiacloprid, thiamethoxam, thioxazafen, thiodicarb, thiocyclam, thiosultap p), thionazine, thiofanox, thiometon, tetrachlorvinphos, tetradifon, tetraniliprole, tetramethylfluthrin, tetramethrin, tebupirimfos, tebufenozide, tebufenpyrad, tefluthrin, teflubenzuron, demeton-S-methyl, teme Temephos, deltamethrin, terbufos, tralomethrin, 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 S-cyclopentenyl, bioresmethrin, bistrifluron, hydramethylnon, bifenazate, bifenthrin, pyflubumid, piperonyl butoxide butoxide, pymetrozine, pyraclofos, pyrafluprole, pyridaphenthion, pyridaben, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, pirimicarb, pyrimidifen, pyriminostrobin, pirimiphos-methyl, pyrethrin hrine), famful, fipronil, fenazaquin, fenamiphos, fenitrothion, fenoxycarb, fenothiocarb, fenothrin [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 fluoroacetate, fluxametamide, flucycloxuron, flucythrinate, flusulfamide, fluvalinate [including tau-form], flupyradifurone, flupyrazofos, flupyrimin, flufiprole, flufenerim
, flufenoxystrobin, flufenoxuron, fluhexafon, flubendiamide, flumethrin, protrifenbut, prothiofos, protrifenbut, flonicamid, propaphos, propargite (propargite), profenofos, broflanilide, profluthrin, propetamphos, propoxur, flometoquin, bromopropylate, hexathiazox, hexaflumuron, Paecilomyces tenuipes tenuipes, Paecilomyces fumosoroseus, heptafluthrin, heptenophos, permethrin, benclothiaz, bensultap, benzoximate, bendiocarb, benfuracarb, Beauveria tenella, Beauveria bassiana, Beauveria brongniartii brongniaartii, phoxim, phosalone, fosthiazate, fosthietan, phosphamidon, phosmet, polynactins, formetanate, phorate, malathion, milbemectin Milbemectin, mecarbam, mesulfenphos, methoprene, methomyl, metaflumizone, methamidophos, metham, methiocarb, methidathion, methyl isothiocyanate isothiocyanate, methyl bromide, methoxychlor, methoxyfenozide, methothrin, metofluthrin, epsilon-metofluthrin, metolcarb, mevinphos, meperfluthrin, Monacrosporium phymatopagum Phymatophagum, monocrotophos, momfluorothrin, epsilon-momfluorothrin, litlure-A, litlure-B, aluminum phosphide, zinc phosphide, hydrogen phosphine, lufenuron, rescale, resmethrin, lepimectin, rotenone, fenbutatin oxide oxide), calcium cyanide, 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 subtilis, Bacillus sphaericus sphaericus, Bacillus thuringiensis subsp. aizawai 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 body, 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).

[Bactericidal active ingredient]
Azaconazole, acibenzolar-S-methyl, azoxystrobin, anilazine, amisulbrom, ametoctradine, aldimorph, isotianil, isopyrazam, isofetamide, isoprothiolane, ipconazole, ipfentrifluconazole, Iprodione, iprovalicarb, iprobenfos, imazalil, iminoctadine-trialbesilate, iminoctadine-triacetate, imibenconazole, edifenphos fenphos, etaconazole, ethaboxam, ethirimol, ethoxyquin, etridiazole, enestroburin, enoxastrobin, epoxyconazole, organic oil oils), oxadixyl, oxazinylazole, oxathiapiproline, oxycarboxin, oxyquinoline copper, oxytetracycline, oxpoconazole fumarate, oxolinic acid, copper octanoate dioctanoate), octhilinone, ofurace, orysastrobin, orthophenylphenol, kasugamycin, captafol, carpropamid, carbendazim, carboxin, carbone, quinoxyfen, quinofumelin, Chinomethionate, Captan, Quinconazole, Quintozene, Guazatine, Cufraneb, Cumoxystrobin, Kresoxim-methyl, Clozylacon , chlozolinate, chlorothalonil, chloroneb, cyazofamid, diethofencarb, diclocymet, dichlofluanid, dichlobenthiazox, diclo Diclomezine, dicloran, dichlorophen, dithianon, diniconazole, diniconazole-M, zineb, dinocap, dipymethitrone, diphenylamine ylamine, difenoconazole, cyflufenamid, diflumetrim, cyproconazole, cyprodinil, simeconazole, dimethylimol, dimethyl disulfide disulfide), dimethomorph, cymoxanil, dimoxystrobin, ziram, silthiofam, streptomycin, spiroxamine, sedaxane, zoxamide, dazomet, tiadinil, thiabendazole, thiuram (thiram), thiophanate, thiophanate-methyl, thifluzamide, tecnazene, tecloftalam, tetraconazole, debacarb, tebuconazole, tebufloquin, terbinafine, dodine, dodemorph odemorph, triadimenol, triadimefon, triazoxide, triclamide, triclopyricarb, tricyclazole, triticonazole, tridemorph, triflumizole, trifloxystrobin, triforin, triforine, tolylfluanid, tolclofos-methyl, tolnifanide, tolprocarb, nabam, natamycin, naftifine, nitrapyrin, nitrothal-isopropyl, nuarimol, copper nonyl phenol sulphonate, Bacillus subtilis (strain: QST) 713), validamycin, valifenalate, picarbutrazox, bixafen, picoxystrobin, pydiflumetofen, bitertanol, binapacryl, biphenyl, piperalin, hymexazol, pyraoxystrobin, pyraclostrobin, Pyraziflumid, 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 acid), fluazinam, fluindapyr, fluoxastrobin, fluopicolide, fluopyram, fluorimide, fluxapyroxad, fluquinconazole, fluconazole, fluconazole-cis, fludioxonil, fluoxonil, Flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, flufenoxystrobin, flumetover, flumorph, proquinazid, prochloraz, procymidone, prothiocarb, prothioconazo prothioconazole, bronopol, propamocarb-hydrochloride, propiconazole, propineb, probenazole, bromuconazole, flometoquin, hexaconazole, benalaxyl, benalaxyl-M, benodanil anil), 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 oil oils), mildiomycin, methasulfocarb, metam, metalaxyl, metalaxyl-M, metiram, metconazole, metominostrobin, metrafenone, mepanipyrim, mefentrifluconazole, Meptyldinocap, mepronil, iodocarb, laminarin, phosphorous acid and salts, basic copper chloride, silver, cuprous oxide, copper hydroxide, potassium bicarbonate, sodium bicarbonate, sulfur, oxyquinoline sulfate, copper sulfate sulfate), (3,4-dichloroisothiazol-5-yl)methyl 4-(tert-butyl)benzoate (chemical name, CAS registration number: 1231214-23-5), BAF-045 (code number), BAG-010 (code number), UK-2A (code number), DBEDC (dodecylbenzenesulfonic acid bis(ethylenediamine) copper complex salt [II]), MIF-1002 (code number), TPTA (triphenyltin acetate), TPTC (triphenyltin chloride), TPTH (triphenyltin hydroxide), nonpathogenic Erwinia carotovora.

[Herbicidal active ingredient]
Ioxynil, aclonifen, acrolein, azafenidine, acifluorfen (including salts with sodium, etc.), azimsulfuron, asulam, acetochlor, atrazine, anilofos, amicarbazone, amidosulfuron, amitrole, aminocyclopyrachlor, ami Nopyralid, amiprofos-methyl, ametryn, alachlor, alloxydim, isouron, isoxachlortole, isoxaflutole, isoxaben, isoproturon, ipfencarbazone, imazaquin, imazapic (including salts with amines, etc.), imazapyr (isopropyl (including salts of amines, etc.), imazamethabenz-methyl, imazamox, imazethapyr, imazosulfuron, indaziflam, indanofan, eglinazine-ethyl, esprocarb, ethametsulfuron-methyl, ethalfluralin, ethidimuron, ethoxysulfuron furon), ethoxyfen-ethyl, ethofumesate, etobenzanide, endothal disodium salt, oxadiazon, oxadiargyl, oxaziclomefone, oxasulfuron, oxyfluorfen, oryzalin, orthosulfamuron, orbencarb, oleic acid acid), cafenstrole, carfentrazone-ethyl, carbutilate, carbetamide, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, quinoclamin, quinclorac, quinmerac ac), cumyluron, clacyfos, glyphosate (including salts such as sodium, potassium, ammonium, amine, propylamine, isopropylamine, dimethylamine, or trimesium), glufosinate (including salts such as amine or sodium), glufosinate-P-sodium, clethodim, clodinafop-propargyl , clopyralid, clomazone, chlormethoxyfen, clomeprop, chloransulam-methyl, chloramben, chloridazon, chlorimuron-ethyl, chlorsulfuron, chlorthal-dimethyl, chlorthiamide amid), chlorphthalim, chlorflurenol-methyl, chlorpropham, chlorbromuron, chloroxuron, chlorotoluron, ketospiradox (including salts such as sodium, calcium or ammonia), saflufenacil, sarmentine, cyanadine, cyanazine, cyanamide, diuron, diethyl-ethyl, dicamba (including amines, diethylamine, isopropylamine, diglycolamine, salts such as sodium or lithium), cycloate, cycloxydim, diclosulam, cyclosulfamuron, cyclopyrimorate, dichlobenil (dichlorobenil), diclofop-P-methyl, diclofop-methyl, dichlorprop, dichlorprop-P, diquat, dithiopyr, siduron, dinitramine, cinidon-ethyl, cinosulfuron, dinoseb, dinoterb dinoterb, cyhalofop-butyl, diphenamide, difenzoquat, diflufenican, diflufenzopyr, simazine, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, simetryn, dimepipere Dimepiperate, dimefuron, cinmethylin, swep, sulcotrione, sulfentrazone, sulfosate, sulfosulfuron, sulfometuron-methyl, sethoxydim, terbacil, daimuron, thaxtomin A A), dalapon, thiazopyr, thiafenacil, thiencarbazone (including sodium salt, methyl ester, etc.), thiocarbazil, thiobencarb, thidiazimin, thifensulfuron-methyl, desmedipham, edipham, desmetryne, thenylchlor, tebutam, tebuthiuron, tepraloxydim, tefuryltrione, tembotrione, terbuthylazine, terbutryn, terbumeton, Pramezone, tralkoxydim, triaziflam, triasulfuron, triafamone, tri-allate, trietazine, triclopyr, triclopyr-butotyl, trifludimoxazine oxazin), tritosulfuron, triflusulfuron-methyl, trifluralin, trifloxysulfuron-sodium salt, tribenuron-methyl, tolpyralate, naptalam (including salts with sodium, etc.) ), naproanilide, napropamide, napropamide-M, nicosulfuron, neburon, norflurazon, vernolate, paraquat, haloxifen-benzyl, haloxifen-methyl en-methyl), haloxyfop, haloxyfop-P, haloxyfop-ethotyl, halosafen, halosulfuron-methyl, picloram, picolinafen, bicyclopyrone, bispyribac-sodium salt spyribac-sodium, pinoxaden, bifenox, piperophos, pyraclonil, pyrasulfotole, pyrazoxyfen, pyrazosulfuron-ethyl, pyrazolinate, bilanafos, pyraflu Pyrafen-ethyl, pyridafol, pyrithiobac-sodium salt, pyridate, pyriftalid, pyributicarb, pyribenzoxim, pyrimisulfan, pyriminobac-methyl
, pyroxasulfone, pyroxsulam, phenisopham, fenuron, fenoxasulfone, fenoxaprop (including methyl, ethyl, isopropyl esters), fenoxaprop-P (including methyl, ethyl, isopropyl esters), fenquinotrione quinotrione, fenthiaprop-ethyl, fentrazamide, phenmedipham, butachlor, butafenacil, butamifos, butyrate, butenachlor, butralin, butroxydim oxydim), flazasulfuron, flamprop (containing methyl, ethyl, isopropyl esters), flamprop-M (containing methyl, ethyl, isopropyl esters), primisulfuron-methyl, fluazifop-butyl, fluazifop-P-butyl , fluazolate, fluometuron, fluoroglycofen-ethyl, flucarbazone-sodium salt, fluchloralin, flucetosulfuron, fluthiacet-methyl, flupyrsulfuron-methyl-sodium salt (flupyrsulfuron-methyl-sodium), flufenacet, flufenpyr-ethyl, flupropanate, flupoxame, flumioxazin, flumiclorac-pentyl, flumetsulam, fluridone , flurtamone, fluroxypyr, flurochloridone, pretilachlor, procarbazone-sodium, prodiamine, prosulfuron, prosulfocarb, propaquizafop, Pachlor, propazine, propanil, propyzamide, propisochlor, propyrisulfuron, propham, profluazol, propoxycarbazone-sodium, profoxydim ydim), bromacil, brompyrazone, prometryn, prometon, bromoxynil (including esters of butyric acid, octanoic acid, heptanoic acid, etc.), bromofenoxim, bromobutide, florasulam, florpyrauxifen , hexazinone, petoxamid, benazolin, penoxsulam, heptamaloxyloglucan, beflubutamid, pebulate, pelargonic acid acid, bencarbazone, pendimethalin, benzfendizone, bensulide, bensulfuron-methyl, benzobicyclon, benzofenap, bentazone, pentanochlor, pentoxazone, benfluralin, benfuresate ), fosamine, fomesafen, foramsulfuron, mecoprop (including salts of sodium, potassium, isopropylamine, triethanolamine, dimethylamine, etc.), mecoprop-P-potassium salt, mesosulfuron-methyl, mesotrione, metazachlor, metazosulfuron, methabenzthiazuron habenzthiazuron, metamitron, metamifop, DSMA (disodium methanarsonate), methiozolin, methyldymuron, metoxuron, metosulam, metsulfuron-methyl, metobromuron, metobenzuron, metolachlor, metribuzin, mef mefenacet, monosulfuron (including methyl, ethyl, isopropyl esters), monolinuron, molinate, iodosulfuron, iodosulfuron-methyl-sodium salt, iofensulfuron, iofensulfuron-sodium salt, 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 salt such as sodium), 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.

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

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. 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), diclobentazox (36.0 ppm), chlorantraniliprole (1.0 ppm), tetraniliprole (1.2 ppm), cyantraniliprole (14.2 ppm), isotianil (0.5 ppm), ferimzone (20.8 ppm), fthalide (46.2 ppm), ethiprole (9.2 ppm), spinetoram (31.9 ppm), oxazosulfil (15.6 ppm), penflufen (10.9 ppm), pencycuron (30.0 ppm), thifluzamide (1.6 ppm), azimsulfuron (48 ppm), ethoxysulfuron (10.5 ppm), oxadiazon (0.57 ppm), oxadiargyl (0.37 ppm), chlorimuron-ethyl (8.6 ppm), cyclosulfamuron (0.34 ppm), dimethicone sulphon (0.79 ppm), triafamone (41 ppm), halosulfuron-methyl (10.2 ppm), pyraclonil (50.1 ppm), pyrazosulfuron-ethyl (9.8 ppm), pyriftalid (1.8 ppm), pyribenzoxim (3.5 ppm), pyrimisulfan (87 ppm), pyriminobac-methyl (E isomer 9.3 ppm), pyroxasulfone (3.5 ppm), fenoxasulfone (0.17 ppm), fenquinotrione (17 ppm), butachlor (16 ppm) , 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).

The pesticide active ingredient may be used as is if its volume median diameter is within the above range, or, if necessary, may be adjusted to the above range by grinding means such as wet grinding or dry grinding.

The water-soluble polymer used in the composition of the present invention is not particularly limited, and examples thereof include polyvinyl alcohol, polyacrylic acid polymers, polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, etc. These water-soluble polymers may 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 the pesticide active ingredient.

It is known that polyvinylpyrrolidone exhibits different viscosities in aqueous solution depending on the degree of polymerization of the vinylpyrrolidone monomers that compose it, and an indicator of this is the K value, expressed by the following formula (I):

（ここで、ｃは溶液１００ｍＬ中のポリビニルピロリドンのグラム数を示し、η_ｒｅｌは水に対する溶液の相対粘度を示す。）
本発明組成物に用いられるポリビニルピロリドンのＫ値は、特に限定されないが、通常１０－１１０、好ましくは２０－１００である。このＫ値はポリビニルピロリドンの１質量％水溶液の粘度を２５℃において毛細管粘度計によって測定したときの値である。

(where c represents the number of grams of polyvinylpyrrolidone in 100 mL of solution, and η _rel represents the relative viscosity of the solution with respect to water.)
The K value of the polyvinylpyrrolidone used in the composition of the present invention is not particularly limited, but is usually 10 to 110, and preferably 20 to 100. This K value is the viscosity of a 1% by mass aqueous solution of polyvinylpyrrolidone measured at 25° C. using a capillary viscometer.

The 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 to the water-soluble polymer is 1:0.05 to 100.0, preferably 0.1 to 20.0.

In addition to the above-mentioned crystalline particles of an agrochemically 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 sulfonates, polyoxyethylene glycol ethers, polyhydric alcohol esters, dialkyl sulfosuccinates, polycarboxylic acids, polyoxyethylene nonylphenyl ether, and sodium lignin sulfonate; starch, alginic acid, glycerin, polyvinylpyrrolidone, polyurethane, polyethylene glycol, polypropylene glycol, polybutene, polyvinyl alcohol, gum arabic, liquid paraffin, ethyl cellulose, polyvinyl acetate, and the like. lubricants such as calcium stearate, talc, silica; colorants such as dyes and pigments; benoxacor, furilazole, dichlormid, dicyclonone, DKA-24 (N1,N2-diallyl-N2-dichloroacetylglycinamide), AD-67 (4-dichloroacetyl-1-ol), 1,8-Naphthalic Anhydride (Naphthalic Anhydride), 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 (Naphthalic Anhydride), Anhydride), mefenpyr-diethyl, mefenpyr, mefenpyr-ethyl, fenchlorazole-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) or other safeners. The amounts and ratios of these components in the composition of the present invention can be appropriately determined by those skilled in the art.

Preferred embodiments of the composition of the present invention include the following.
Pesticide active ingredient (volume median diameter of 0.01 to less than 1.0 μm): 0.1 to 50.0 parts by weight Water-soluble polymer: 0.1 to 20.0 parts by weight Solid carrier: 0 to 30.0 parts by weight Surfactant: 0.1 to 30.0 parts by weight 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 Phytotoxicity safener: 0 to 40.0 parts by weight

The composition of the present invention can be manufactured according to conventional methods, except that it contains the above-mentioned components. The composition of the present invention can also be in the conventional form, such as granules, suspension, powder, or solution, but suspension or powder forms are preferred.

A preferred method for producing the composition of the present invention includes, for example, a process comprising the steps of grinding crystalline particles of the 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 process (hereinafter, this process is referred to as the "method of the present invention").

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

In addition, in the manufacturing method of the present invention, the step of mixing the crystalline particles of the pesticide 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.

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 grinding step as wet grinding. The wet grinding 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.

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

The method and conditions for granulating the above mixture are not particularly limited, and for example, known granulation methods such as extrusion granulation, fluidized bed granulation, and coated granulation can be used, and the conditions are also known.

Furthermore, the granulated pesticide composition may be subjected to a drying process, etc., if necessary.

The composition of the present invention thus obtained has improved dissolution properties of the pesticide active ingredient in water. Here, 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.

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.

In the following examples, the average particle size refers to the median diameter of the volume particle size distribution measured by a laser analysis particle size distribution measuring device. The K value is the value when the viscosity of a 1% by weight aqueous solution of polyvinylpyrrolidone is measured 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 peaks appeared at the peak positions 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.

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, to obtain a chlorantraniliprole-containing slurry.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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, to obtain a chlorantraniliprole-containing slurry.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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, to obtain a chlorantraniliprole-containing slurry.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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, to obtain a chlorantraniliprole-containing slurry.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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, to obtain a chlorantraniliprole-containing slurry.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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, to obtain a chlorantraniliprole-containing slurry.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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 predetermined 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.

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 specified amount of clay were mixed to make a total of 99.8 parts (dry basis). A specified amount of water in which 0.2 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0) had been dissolved was added to this mixture and kneaded, and the mixture was extruded and granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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 predetermined amount of water were mixed to make a total amount of 95 parts. This mixture was wet-pulverized using glass 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.

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 specified amount of clay were mixed to make a total of 99.5 parts (dry basis). A specified amount of water in which 0.5 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0) had been 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.

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 predetermined amount of water were mixed to make a total amount of 95 parts. This mixture was wet-pulverized using glass 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.

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 specified amount of clay were mixed to make a total of 99 parts (dry basis). A specified amount of water in which 1 part of polyvinylpyrrolidone (K value = 27.0 to 33.0) had been dissolved was added to this mixture and kneaded, and the mixture was extruded and granulated using a screen with a 1.2 mm hole size, and then dried to remove the moisture, yielding a granular pesticide composition.

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 predetermined amount of water were mixed to make a total amount of 95 parts. This mixture was wet-pulverized using glass 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.

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 specified amount of clay were mixed to make a total of 98.5 parts (dry basis). A specified amount of water in which 1.5 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0) had been 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.

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 predetermined amount of water were mixed to make a total amount of 95 parts. This mixture was wet-pulverized using glass 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.

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 specified amount of clay were mixed to make a total of 98 parts (dry basis). A specified amount of water in which 2 parts of polyvinylpyrrolidone (K value = 27.0 to 33.0) had been dissolved was added to this mixture and kneaded, and the mixture was extruded and granulated using a screen with a 1.2 mm hole size, and then dried to remove the moisture, obtaining a granular pesticide composition.

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 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, to obtain a chlorantraniliprole-containing slurry.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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 predetermined amount of water were mixed to make a total amount 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.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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 predetermined amount of water were mixed to make a total amount 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.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified 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, to obtain a granular pesticide composition.

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 predetermined amount of water were mixed to make a total amount 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.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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 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 0.77 μm, to obtain a chlorantraniliprole-containing slurry.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

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.

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 specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified amount of water was added to this mixture and kneaded, and the mixture was extrusion granulated using a screen with a 1.2 mm hole diameter, and then dried to remove moisture, to obtain a granular pesticide composition.

Test Example 1
100 mg of the granular pesticide composition of Example 1-11 and Comparative Example 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.

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 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.

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 predetermined 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.

11.21 parts of the slurry, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, and a specified amount of clay were mixed to make a total of 99 parts (dry basis). A specified amount of water in which 1 part of polyvinylpyrrolidone had been 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, to obtain a granular pesticide composition.

Comparative 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 predetermined 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.

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

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 the fenquinotrione concentration in the water after one day were measured by high performance liquid chromatography. The measurement results are shown in Table 2.

Improvements in dissolution concentrations were observed for both pyrimisulfan and fenquinotrione when the average particle size was less than 1 μm and PVP was contained.

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 amount of 100 parts. This mixture was wet-pulverized using glass beads as a grinding medium until the average particle size became 3 μm, to obtain a primary slurry.

In addition, 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.

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

2.5 parts of the secondary slurry, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, and a specified amount of clay were mixed to make a total of 99 parts (dry basis). A specified amount of water in which 1 part of polyvinylpyrrolidone had been 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, to obtain a granular pesticide composition.

Comparative 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 amount of 100 parts. This mixture was wet-pulverized using glass beads as a grinding medium until the average particle size became 3 μm, to obtain a primary slurry.

In addition, 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.

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

2.5 parts of the secondary slurry, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, and a specified amount of clay were mixed to make a total of 100 parts (dry basis). A specified 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.

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 by high performance liquid chromatography. The measurement results are shown in Table 3.

When pyroxasulfone had an average particle size of less than 1 μm and contained PVP, improved elution concentration was observed.

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.

6.67 parts of the secondary slurry, 0.1 parts of polyoxyethylene alkyl ether sulfate, 3 parts of pregelatinized starch, and a specified amount of clay were mixed to make a total of 99 parts (dry basis). A specified amount of water in which 1 part of polyvinylpyrrolidone had been 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, to obtain a granular pesticide composition.

Comparative 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.

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

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

Improved elution concentration was observed when fenoxasulfone had an average particle size of less than 1 μm and contained PVP.

The pesticide composition of the present invention can be used in agriculture in the same manner as ordinary pesticide compositions.

The End

Claims (8)

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. 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 per 100 parts by mass of the pesticide composition. The pesticide composition according to claim 1 or 2, in which the mass ratio of the pesticide active ingredient to the water-soluble polymer is 1:0.05-100. The pesticide composition according to any one of claims 1 to 3, wherein the water solubility of the pesticide active ingredient is 100 ppm or less. 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 . The manufacturing method according to claim 5, in which the pesticide active ingredient and the water-soluble polymer are mixed in a mass ratio of 1:0.05 to 100. The method according to claim 5 or 6, wherein the grinding step is wet grinding and includes a step of obtaining a suspension-type pesticide composition. 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.