BR102018071178B1 - GRANULAR PESTICIDE FORMULATION - Google Patents

Abstract

The granular pesticide formulation of the present invention contains a salt of carboxymethyl cellulose, a formalin condensate of alkyl naphthalene sulfonate and lignin sulfonate therein, while the granules of the granular pesticide formulation are rapidly disintegrated in water when diluted with water in a condition storage after production in high humidity.

Description

FUNDAMENTALS Technical field

[001] The present invention relates to a granular pesticide formulation including pesticide(s) as active ingredient(s). More specifically, it refers to a granular pesticide formulation that maintains good disintegrability in water immediately after production thereof, as well as even in a high temperature and/or high humidity storage condition.

Related technique

[002] In recent years, the use of granular pesticide formulations has tended to increase in the agricultural field. Granular pesticide formulations are more convenient to use compared to powder formulation pesticides for the following advantageous reasons: (1) Granular pesticide formulations are not bulky due to their large bulk density; (2) There is no fear that the worker using the granular pesticide formulations will be exposed to the pesticide by the extremely small spread of fine dust thereof during the preparation of the spray solution; and (3) Granular pesticide formulations are easy for the worker to measure.

[003] Disintegrability in water is generally mentioned as an important physical property of granular pesticide formulations. Water disintegrability is a parameter that represents easy granular disintegration in water. It is necessary for granular pesticide formulations to disintegrate quickly in water when diluted with water to prepare the spray solution.

[004] Known granular pesticide formulations are described in WO 2014/133178, JP 2005-132741 and JP 2008-308447. In WO 2014/133178, water-dispersible granules that have good disintegration and dispersion and that contain pesticides as active ingredients are described. The water-dispersible granules maintain good disintegrability in water after successively stored for 2 weeks at 54°C and the water-dispersible granules include (a) solid pesticide active ingredient(s) at 25°C, ( b) polyoxyalkylene alkyl ether phosphate or a salt thereof, (c) at least one anionic surfactant selected from the group consisting of aryl sulfonate or a formaldehyde condensate thereof, lignin sulfonate, and polycarboxylate and (d) lactose.

[005] The granular pesticide formulation of the present invention contains surfactants: an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate, however, the claims of WO 2014/133178 describe that the water-dispersible granules contain at least one selected anionic surfactant of the group consisting of aryl sulfonate or a formaldehyde condensate thereof, lignin sulfonate and polycarboxylate.

[006] However, in the detailed description of the invention of WO 2014/133178, in paragraph [0041], a formaldehyde condensate of naphthalene sulfonic acid sodium salt is exemplified as a preferred example of constituent (c). However, there is neither description nor suggestion regarding the use of two or more types of anionic surfactants. In Production Example 16, an example of a formulation obtained using an alkyl naphthalene sulfonate formaldehyde condensate is described. In Production Example 17, an example of a formulation obtained using sodium lignin sulfonate is described. In both examples, an anionic type of surfactant is used.

[007] Additionally, the water-dispersible granules of WO 2014/133178 include (d) lactose, however, the granular pesticide formulations of the present invention do not include lactose.

[008] In this way, the granular pesticide formulation of the present invention and the water-dispersible granules of WO 2014/133178 differ in terms of containing two types of surfactants: an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate and not containing lactose.

[009] JP 2005-132741 A describes water-dispersible granules for agriculture and horticulture. Water-dispersible granules for agriculture and horticulture include 2% pesticide(s) as active ingredient(s), an adhesive agent having an aqueous solution viscosity of 10 to 2,000 mlPbs, and a surfactant. Additionally, paragraph [0018] states that specific examples of the adhesive agent include carboxymethyl cellulose or a sodium salt thereof.

[0010] In the case of the granular pesticide formulation of the present invention, the problems to be solved by the invention refer to the improvement of disintegrability in water and the granular pesticide formulation includes a salt of carboxymethyl cellulose and surfactants: an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate. However, in the case of the water-dispersible granules of Jl 2005-132741 A, the problems to be solved by the invention relate to improving rain resistance and the water-dispersible granules include carboxymethyl cellulose or a sodium salt thereof and a surfactant .

[0011] In the detailed description of the invention of Jl 2005-132741 A, paragraph [0019] describes that it is essential to add the surfactant in order to maintain the physical properties of the formulation favorable. Although anionic surfactants including an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate, nonionic surfactants, cationic surfactants and zwitterionic surfactants are only exemplified, the type and number of surfactants to be used are not specifically described. In all Examples 1 to 12, one type of surfactant: sodium lignin sulfonate is used.

[0012] In this way, the granular pesticide formulation of the present invention and the water-dispersible granules of JP 2005-132741 A differ in terms of containing two types of surfactants: an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate and they also differ in the problems to be solved by the invention.

[0013] JP 2008-308447 A describes a water-dispersible particulate agricultural chemical composition that has improved disintegrability and water dispersibility that is produced by a method for producing a water-dispersible particulate composition, including a step of kneading an agricultural chemical active ingredient , a surfactant and water.

[0014] The granular pesticide formulation of the present invention includes surfactants: an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate, however, the water-dispersible particulate agricultural chemical composition of JP 2008-308447 A includes an agricultural chemical active ingredient, a surfactant and water.

[0015] However, in the detailed description of the invention of JP 2008308447 A, paragraph [0022] describes that non-ionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants and the like can be used without limitation. Additionally, paragraphs [0023] to [0025] describe specific examples of nonionic surfactants, anionic surfactants and cationic surfactants. Without a doubt, paragraph [0026] describes that “these surfactants can be used alone, or two or more different types thereof can be used in combination”. When reviewing the specific test examples, in Example 3, an example of a formulation obtained using one type of surfactant: sodium lignin sulfonate is described. In Examples 4 and 6, examples of formulations obtained using one type of surfactant are described: a sodium alkyl naphthalene sulfonate formalin condensate. However, JP 2008-308447 A only describes that one type of surfactant is used to produce any of the example formulations. There is neither description nor suggestion regarding the characteristics of the present invention, in which the formulation contains two types of surfactants: an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate and there is no description regarding a specific example of the formulation .

[0016] In this way, the granular pesticide formulation of the present invention and the water-dispersible granules of JP 2008-308447 A differ in terms of containing two types of surfactants: an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate.

SUMMARY

[0017] The water disintegrability of granular pesticide formulations containing pesticide(s) as active ingredient(s) is poor, whereby a nozzle of a spraying machine is clogged with undisintegrated granules. Known granular pesticide formulations have problems that include a case where the water disintegrability of the granular pesticide formulations is poor immediately after production or a case where the water disintegrability is favorable immediately after production, the water disintegrability of the granular pesticide formulations is poor. deteriorates when granular pesticide formulations are stored in a high humidity condition.

[0018] In the previous literature cited above, neither analysis nor description regarding water disintegrability in each formulation after being stored in a high humidity condition. The water disintegrability of the formulation may be deteriorated depending on the storage conditions of the formulation. Known granular pesticide formulations are not satisfactory.

[0019] Thus, an object of the present invention is to provide a granular pesticide formulation that maintains good disintegrability in water even if the granular pesticide formulations are stored in a high humidity condition.

[0020] In order to resolve the above problems, the present inventors conducted intensive studies. As a result, they found that it is possible to obtain a granular pesticide formulation that maintains good disintegrability in water even if the granular pesticide formulations are stored in a high humidity condition.

[0021] That is, the present invention relates as follows [1] to [11]: [1] a granular pesticide formulation comprising: (1) a pesticide as an active ingredient; (2) a salt of carboxymethyl cellulose; and (3) a formalin condensate of alkyl naphthalene sulfonate and a lignin sulfonate; and which does not comprise (4) lactose; [2] the granular pesticide formulation according to [1], further comprises an amorphous silica in a mixing ratio of 0 to 5% by weight; [3] the granular pesticide formulation according to [1] or [2], wherein the mixing proportion of amorphous silica is 0% by weight; [4] the granular pesticide formulation according to any one of [1] to [3], wherein at least one pesticide contained as the active ingredient is an insecticide having a mechanism of action of a competitive nicotinic acetylcholine receptor modulator (nAChR); [5] the granular pesticide formulation according to any one of [1] to [4], wherein at least one pesticide contained as the active ingredient is a neonicotinoid insecticide; [6] the granular pesticide formulation according to [4] or [5], wherein at least one pesticide contained as the active ingredient is dinotefuran; [7] the granular pesticide formulation according to any one of [1] to [6], wherein the carboxymethyl cellulose salt is sodium carboxymethyl cellulose; [8] the granular pesticide formulation according to any one of [1] to [7], wherein the alkyl naphthalene sulfonate formalin condensate is a sodium alkyl naphthalene sulfonate formalin condensate; [9] the granular pesticide formulation according to any one of [1] to [8], wherein the lignin sulfonate is sodium lignin sulfonate; [10] the granular pesticide formulation according to any one of [1] to [9], comprising: (1) 0.1 to 90% by weight of a pesticide as the active ingredient; (2) 0.1 to 3% by weight of carboxymethyl cellulose salt; (3) 2 to 20% by weight of alkyl naphthalene sulfonate formalin condensate; and 2 to 20% by weight of lignin sulfonate; and [11] the granular pesticide formulation according to any one of [1] to [10], wherein the mixing ratio of the alkyl naphthalene sulfonate formalin condensate to the lignin sulfonate is 1:9 to 9:1 .

[0022] The granular pesticide formulation of the present invention contains a carboxymethyl cellulose salt, an alkyl naphthalene sulfonate formalin condensate and lignin sulfonate in it, while the granules of the granular pesticide formulation are rapidly disintegrated in water when diluted with water even though granular pesticide formulations are stored in a high humidity condition. This allows it to maintain good disintegrability in water.

[0023] Subsequently, various terms used herein will be described.

[0024] A specific example of the “high temperature storage condition” includes a severe test condition in which a formulation is placed in a laminated aluminum foil package and stored in a thermostat set at 54 ° C for 3 days, 14 days or 28 days. It goes without saying that its use in an area with a tropical climate (average annual temperature 18 °C or more) is included.

[0025] A specific example of the “high humidity storage condition” includes a severe test condition in which a formulation is uniformly sprayed onto a Petri dish and stored in a thermohygrostat set at 30°C and 80% RH for 3 days, 7 days or 14 days. Needless to say, its use in tropical forest climates, tropical monsoon climates or the like is included.

[0026] The term “water disintegrability” indicates that the granules of the granular pesticide formulation tend to be disintegrated in water. The method of measuring disintegrability in water is, for example, a method including: placing 500 mg of the granular pesticide formulation into a colorimetric cylinder containing the volume (100 mL) of water having a hardness of 3 degrees defined therein in the inspection method pesticide officer, repeatedly inverting the cylinder at a rate of once per 2 seconds and counting the number of times of cylinder inversion that is required until the granular pesticide formulation no longer maintains the granule form in water.

[0027] The pesticide(s) as active ingredient(s) may be a pesticide that has an effect of preventing harmful organisms and examples thereof include herbicides, insecticides, acaricides, nematicides, fungicides and bactericides. The granular pesticide formulation of the present invention may contain one or two types or more of these pesticides of which the strain is the same or different from the active ingredients. Hereinafter, the pesticide(s) as active ingredient(s) of the present invention will be specifically exemplified, however, the present invention is not limited to them.

[0028] Examples of herbicides include butroxidim, profoxidim, clethodim, tepraloxidim, tralkoxidim, sethoxydim, cycloxidim, propaquizafop, quizalofop, haloxyfop, fluazifop-butyl, fluazifop-P-butyl, ci-halofop-butyl, clodinafop-propafgyl, diclofop-methyl , fenoxaprop-P-ethyl, amidosulfuron, azimsulfuron, trifloxysulfuron, bensulfurone-methyl, cyclosulfamurone, flupyrsulfuron-methyl, foramsulfuron, chlorimuron-ethyl, etametsulfuron, halosulfuron methyl, nicosulfuron, chlorsulfuron, ethoxysulfuron, imazosulfuron, oxasulfuron, pyre zosulfuronacetyl, tritosulfuron, cinosulfuron, flazasulfuron, iodosulfuron-methyl, primisulfuron-methyl, rimsulfuron, thifensulfuron-methyl, mesosulfuron-methyl, methosulfronmethyl, prosulfuron, triasulfuron, triflusulfuron-methyl, sulfosulfuron, tribenuron-methyl, trifloxysulfuron, flucarbazone, propoxycarbazone, bispiribac, pyribenzoxim, pyrithium bac, pyrifthalide, piriminobac-methyl, cloransulam methyl, diclossulam, florassulam, flumetsulam, metosulam, penoxsulam, imazapic, imazapyr, imazametabenz-methyl, imazaquin, imazamox, imazethapyr, desmedifam, phenmedifam, bromacil, lenacil, terbacil, metabenthiazuron, chlorotolurone, fluometurone, isoproturone, isourone , diuron, linurone, tebuthiurone, hexazinone, metamitrone, metribuzin, ametrine, atrazine, dimethamethrin, cyanazine, promethrin, simazine, simethrin, paraquat, diquat, acifluorfen, bifenox, medosafene, lactophen, oxyfluorfen, carfentrazone-ethyl, sulfentrazone, oxadiargyl, oxadiazon , butafenacil, saflufenacil, pyrazolate, pyrazoxifene, benzofenap, topramezone, pyrasulfotol, tolpiralate, mesotrione, sulcotrione, benzobicyclon, tefuryltrione, tembotrione, biciclopyrone, phenquinotrione, lancotrione, glyphosate, glufosinate, bialafos, benfluralin, etalfluralin, pendimethalin, but ralin, oryzalin, trifluralin , acetochlor, butachlor, alachlor, dimetachlor, dimethenamid, propachlor, tenylchlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, pethoxamide, benthiocarb, butyrate, esprocarb, molinate, dimepiperate, orbencarb, prosulfocarb, tri-allate, triclopyr, clopyralid, fluroxypyr , picloram, quinclorac, quinmerac, clomeprop, MCPA, MCPB, 2,4-DB, ioxynil, bromoxynil, diclobenil, amicarbazone, chloridazone, bentazone, cull butyrate, propanil, pyridate, pyraflufen-ethyl, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, picolinafen, aclonifen, fluridone, norflurazon, diflufenican, beflubutamide, flurochloridone, flurtamon, isoxaflutole, clomazone, asulam, dithiopyr, thiazopyr, dicamba, benazolin, diufenzopyr, naptalam, napropamide, tetrapione, pinoxaden, pyroxasulfone, fenoxasulfone, ipfencarbazone, indaziflam, aminocyclopirachlor, halauxifen-methyl, florpyrauxifen-benzyl, thiafenacil, trifludimoxazine and cyclopyrimorate.

[0029] Examples of insecticides, acaricides and nematicides include phosphocarb, alanicarb, butocarboxim, butoxycarboxim, thiodicarb, tiophanox, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, etiofencarb, fenobucarb, formetanate, furatiocarb, isoprocarb, methiocarb, methomyl, oxa thousand , pirimicarb, propoxur, trimetacarb, lorpirifos , chlorpyrifos-ethyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, diclofenthion, dichlorvos, dicrotophos, dimethoate, dimethylvinphos, disulfoton, O-ethyl-O-4-nitrophenylphenylphosphono thioate, ethion, etoprophos, famfur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, isofenphos-methyl, isocarbophos, isoxathione, malathion, mecarbam, methamidophos, methydathione, mevinfos, monocrotophos, naled, omethoate, oxidemeton-methyl, parathione, parathion-methyl, fentoate, phorate, phosalone, phosmet, phosfamidone, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiophos, pyraclophos, pyridafenthion, quinalphos, sulfotep, tebupirimphos, temephos, terbufos, thiometon, triazophos, trichlorfon, vamidothione, chlorthione, brofenvinfors, bromophos, bromophos-ethyl, butathiophos, carbofenothion, c lorfoxim, sulprophos, diamidaphos, tetrachlorvinphos, propaphos, mesulfenphos, dioxabenzophos, etrymphos, oxideprophos, formotiona, fensulfothione, isazophos, imiciaphos, isamidofos, thionazine, fosthiethane, chlordane, endosulfan, linden, dienochlor, etiprol, fipronil, acetoprol, acrinathrin, allethrin [(1 R )- isomer], bifenthrin, bioalethrin, bioalethrin-S-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin , zeta-cypermethrin, cyphenothrin [(1R)-trans-isomer], deltamethrin, empentrin [(EZ)-(1R)-isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucitrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin , methothrin, methofluthrin, epsilon-metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phenothrin [(1R)-trans-isomer], prallethrin, resmethrin, cadetrin, silafluofen, tefluthrin, etramethrin, tetramethrin [(1R)-isomer], tralomethrin , transfluthrin, ZXI8901, bio-permethrin, furamethrin, profluthrin, flubrocitrinate, metofluthrin, DDT, methoxychlor, fenothrin, fluvalinate, acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, nicotine, nicotine sulfate, sulfoxaflor, flupyradifurone, triflume zopirim , spinosad, spinetoram, abamectin, emamectin benzoate, lepimectin, milbemectin, hydroprene, cynoprene, methoprene, fenoxycarb, pyriproxyfen, methyl bromide, chloropicrin, cryolite, sulfuryl fluoride, borax, boric acid, disodium octaborate, sodium metaborate, tartar emetic, dazomet, metam, sodium carbamate, pymetrozine, pyrifluquinazon, clofentezine, diflovidazine, hexithiazox, etoxazole, diafentiurone, azocyclotine, cy-hexatin, fenbutatin oxide, “c- 12.5“ propargite, “c-12.6“ tetradifon, chlorfenapil, DNOC, binapacril, sulfluramide, bensultap, cartap hydrochloride, thiocyclam, monosultap, bistriflurone, chlorfluazurone, diflubenzurone, furcicloxurone, flufenoxurone, hexaflumurone, lufenurone, novalurone, noviflumurone, teflubenzurone, triflumurone, buprofezin, cyromazine, chromafenozide, halofenozide , methoxyfenozide, tebufenozide, amitraz, hydramethylnone, acequinocil, fluacripyrim, bifenazate, fenazaquin, fenpyroximate, pyridabene, pyrimidifen, tebufenpyrate, tolfenpyrate, rotenone, indoxacarb, metaflumizone, spirodiclofen, spiromesiphene, spirotetramat, aluminum phosphite, calcium phosphide, phosphorus hydride, zinc phosphide, sodium cyanide, potassium cyanide, cyenopyrafen, cyflumetofen, piflubumide, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamide, azadirachtin, benzoximate, phenisobromolate, chinomethionat, dicofol, pyridalyl, bromopropylate, triazamate, dicyclanil, dinobutoan, dinocap, hydrogen cyanide, iodide methyl, caranjine, mercury chloride, methyl isothiocyanate, pentachlorophenol, phosphine, piperonyl butoxide, pollinactin, sabadilla, sulcofuron-sodium, tribufos, aldrin, amidithion, amide thioate, aminocarb, amiton, alamite, atidathion, nitrogenate, poly( barium sulfite), benclothiaz, 5-(1,3- benzodioxole-5-yl)-3-hexylcyclohexa-2-enone, 1,1-bis(4-chlorophenyl)-2- ethoxyethanol, butonate, butopyronoxyl, 2- (2-butoxyethoxy)ethyl thiocyanate, camfeclor, chlorbenside, chlordecone, chlordimeform, chlorfenetol, chlorfenson, fluazurone, metaldehyde, bialafos, viverisol hydrochloride, amidoflumet, pyrafluprole, pyriprole, tralopyril, flupyrazophos, diophenolan, chlorbenzylate, flufenzine, benzomate, flufenerimu, albendazole, oxybendazole, fenbendazole, metam-sodium, 1,3-dichloropropene, flometoquin, cyclaniliprole, tetratraniliprole, broflanilide, dichloromezothiaz, ethylene dibromide, acrylonitrile, bis(2-chloroethyl)ether, 1-bromo-2-chloroethane, 3- bromo-1-chloroprop-1-ene, bromocyclene, carbon disulfite, carbon tetrachloride, nemadectin, cymiazole, calcium polysulfite, cytokinin, 2-(octylthio) ethanol, potassium oleate, sodium oleate, machine oil, oil tar, anabasine, morantel tartrate, chrysanthemum cinerariaefolium (pyrethrin), rapeseed oil, soy lecithin, starch, hydroxypropyl starch, fatty acid glyceride, propylene glycol monofat acid ester, diatomaceous earth, afoxolaner, fluazaindolizine, afidopyropene, cyhalodiamide, thioxazaphene, fluexafon, fluralaner, fluxametamide, tetrachlorantraniliprole, sarolaner, lotilaner, cycloxapride, fluensulfone, TPIC, D-D, peroxocarbonate, MB-599, bis(2,3,3,3-tetrachloropropyl)ether, DCIP, ENT-8184, Bayer 22408, Bayer 32394, BAI-1602, BAI-1603, S-1587, chloropralethrin, benzpyrimoxan, acinonapyr, spiropidion, flupirimin and ticlopirazoflor. Examples of the insecticides include insecticides that have a competitive nicotinic acetylcholine receptor (nAChR) modulator mode of action (such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, nicotine, nicotine sulfate, sulfoxaflor, flupyradifurone, triflumezopyrim , dichloromezothiaz and flupirimin); diamide insecticides such as flubendiamide, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, broflanilide, cyhalodiamide and tetrachlorantraniliprole; and insecticides that have a chitin biosynthetic inhibitor mode of action (such as buprofezin). Particularly, dinotefuran, broflanilide and buprofezin are preferred.

[0030] Examples of fungicides and bactericides include benalaxyl, benalaxyl M or kiralaxyl, oxadixyl, furalaxyl, metalaxyl, metalaxyl M or mefenoxam, ofurace, benomyl, carbendazim, fuberidazole, thiabendazole, meptildinocap, dinocap, fluazinam, ametoctradine, cyprodinil, mepanipyrim, pyrimethanil , streptomycin, blasticidin S, casugamycin, oxytetracycline, fenpiclonil, fludioxonil, quinoxifene, proquinazide, clozolinate, dimethaclon, iprodione, procymidone, vincrozoline, edifenfos, iprobenfos, pyrazofos, isoprothiolane, biphenyl, chloroneb, dichloran, quintazene, tecnazen, tolclofos- methyl, ip conazole, metoconazole, myclobutanil , nuarimol, oxpoconazole, oxpoconazole fumarate, pefurazoate, penconazole, prochloraz, propiconazole, prothioconazole, pirifenox, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triazimenol, triflumizole, trifoline, triticonazole, mefentrifluconazole, ipfentrifluconazole, aldimorph, dodemorph , fenpropimorph, tridemorph, fenpropidine, piperaline, spiroxamine, fenhexamide, fenpyrazamine, piributicarb, naftifine, terbinafine, polyoxins, dimethomorph, flumorph, pyrimorph, bentiavalicarb, bentiavalicarb-isopropyl, iprovalicarb, mandipropamide, valifenalate, phthalide, pyroquilone, tricyclazole, carpropamide, diclocimet, fenoxanil, tolprocar be, acibenzolar-S-methyl, probenazole, tiadinil, isotianil, laminarin, mancozeb ormanzeb, maneb, metiram, propineb, thiuram, zineb, ziram, ferbam, capitan, capitafol, folpet, fluorfolpet, guazatine, iminoctadine, iminoctadine albesylate, iminoctadine triacetate, oxychloride basic copper, copper cupric hydroxide, basic copper sulfate, organocopper compound, bis(ethylenediamine)[II] copper dodecylbenzene sulfate complete salt, sulfur, fluoroimide, chlorothalonil, dichlofluanid, tolylfluanide, anilazine, ditianone, quinomethionat, cotyledon extracts from lupine seedlings (BLAD), diclobentiazox, fenpicoxamide, dipimetitron, bupyrimate, dimetirimol, ethirimol, fentin acetate and riphenyltin tchloride, triphenyltin hydroxide, oxolinic acid, himexazol, octylinone, fosetyl, phosphorous acid, sodium salts of phosphorous acid, ammonium salts of phosphorous acid, potassium salts of phosphorous acid, teclophthalam, triazoxide, flusulfamide, diclomedine, siltiofam, diflumetrim, metasulfocarb, ciflufenamide, metrafenone, pyriofenone, dodine, flutianil, ferimzone, oxathiapiproline, tebufloquin, picarbutrazox, validamycins, cymoxanil, quinofumelin, NC-241, NF-180, S-2190, S-2367, inpirfluxam, fluindapir, isoflucipram and aminopyrifen.

[0031] Examples of the combination of pesticide(s) as active ingredient(s) (in the case of insecticides) include a combination of acetamiprid and chlorantraniliprole, a combination of acetamiprid and cyantraniliprole, a combination of clothianidin and chlorantraniliprole , a combination of dinotefuran and chlorantraniliprole, a combination of dinotefuran and cyantraniliprole, a combination of dinotefuran and broflanilide (dinotefuran and buprofezin), a combination of thiamethoxam and flubendiamide, a combination of thiamethoxam and chlorantraniliprole, and a combination of imidacloprid and flubendiamide. Examples of the fungicides include a combination of penthiopyrad and Captan and a combination of penthiopyrad and quinofumelin. In the case of a combination of an insecticide and fungicide, examples thereof include a combination of dinotefuran and hexaconazole, a combination of dinotefuran and azoxystrobin, a combination of dinotefuran and thifluzamide, a combination of dinotefuran and tricyclazole, a combination of dinotefuran and mancozeb, a combination of dinotefuran and quinofumelin, a combination of dinotefuran and picoxystrobin, and a combination of dinotefuran and difenoconazole. Particularly, a combination of dinotefuran and broflanilide, a combination of dinotefuran and buprofezin or the like is preferred.

[0032] The term “carboxymethyl cellulose salt” indicates a salt of a cellulose derivative that has a carboxymethyl group attached to a part of the hydroxyl group of glucopyranose as a structural unit of cellulose. Examples of the carboxymethyl cellulose salt include an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and various amine salts. Among them, alkali metal salt is preferred and sodium salt is particularly preferred.

[0033] Examples of the commercialized product of carboxymethyl cellulose salt include CELLOGEN 701A, CELLOGEN 703A, CELLOGEN 5A, CELLOGEN 6A, CELLOGEN 7A, CELLOGEN PR, CELLOGEN WS-UM, CELLOGEN PL-15, CELLOGEN WS-CN, CELLOGEN WS-C , CELLOGEN WS-D, CELLOGEN BS, CELLOGEN BS-H, CELLOGEN BSH-3, CELLOGEN BSH-4, CELLOGEN BSH-5, CELLOGEN BSH-6, CELLOGEN BSH-10 and CELLOGEN BSH-12 (all manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD); and SUNROSE F10LC, SUNROSE F20LC, SUNROSE F01MC, SUNROSE F10MC, SUNROSE F30MC, SUNROSE F50MC, SUNROSE FT-1, SUNROSE FT-3, SUNROSE 04HC, SUNROSE FT-8, SUNROSE F20HC, SUNROSE APP-84, SUNROSE A02SH, SUNROSE A04SH , SUNROSE A10SH, SUNROSE A20SH, SUNROSE A100SH, SUNROSE PN01L, SUNROSE PN05L, SUNROSE PN20L, SUNROSE SN01L, SUNROSE SN30C, SUNROSE SN60C and SUNROSE SN80C (all manufactured by Nippon Paper Co., Ltd.).

[0034] The “alkyl naphthalene sulfonate formalin condensate” is, for example, a monoalkyl naphthalene sulfonate formalin condensate or di-alkyl naphthalene sulfonate. Specific examples thereof include a formalin condensate of monoalkyl naphthalene sulfonate, such as methyl naphthalene sulfonate, ethyl naphthalene sulfonate, propyl naphthalene sulfonate, isopropyl naphthalene sulfonate, butyl naphthalene sulfonate or isobutyl naphthalene sulfonate; and a dialkyl naphthalene sulfonate formalin condensate, such as dimethyl naphthalene sulfonate, diethyl naphthalene sulfonate, diisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate or diisobutyl naphthalene sulfonate. Particularly, the sodium salt is preferred as alkyl naphthalene sulfonate.

[0035] Examples of the commercialized product of alkyl naphthalene sulfonate formalin condensate include MORWET D-425 POWDER, MORWET D-110 POWDER, MORWET D-450 POWDER and MORWET D500 POWDER (all manufactured by Akzo Nobel Surface Chemistry AB.); Supragil MNS/25 (manufactured by Solvay Nicca, Ltd.); DEMOL N, DEMOL NL, DEMOL RN, DEMOL RN-L, DEMOL T and DEMOL T-45 (all manufactured by Kao Corporation.); LABELIN FC-45, LABELIN FA-N, LABELIN FH-45, LABELIN FH-P, LABELIN A-40 SELFLOW 110P and LABELIN 120 (all manufactured by DAI-ICI KOGYO SEIYAKU Co., Ltd.); and PIONIN A-45-D, PIONIN A-45-PN and NEWKALGEN PS-P (all manufactured by TAKEMOTO OIL & FAT Co., Ltd.).

[0036] The term “lignin sulfonate” indicates a salt of a compound that has a skeleton in which the carbon in the alpha position of the side chain of the lignin hydroxyphenylpropane structure is cleaved and a sulfone group is introduced. Examples of the salt in lignin sulfonate include an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and various amine salts. Among them, alkali metal salt or alkaline earth metal salt is preferred. Particularly, the sodium salt is preferred.

[0037] Examples of the commercialized lignin sulfonate product include NEWKALGEN WG-4, NEWKALGEN RX-B and NEWKALGEN RX-C (all manufactured by TAKEMOTO OIL & FAT Co., Ltd.); Reax80D, Reax81A, Reax83A, Reax85A, Reax88A, Reax88B, Polifon H, Polifon O, Polifon T and Polifon F (all manufactured by MeadWestvaco Corporation); and PEARLLEX CP, PEARLLEX NP, San X P201, San X P200, San X P252, San X M100 and San

[0038] The term “lactose” indicates a-hydrous lactose, a-anhydrous lactose, β-anhydrous lactose or the like.

[0039] The term “granular pesticide formulation” indicates a granular pesticide formulation that has an average particle diameter of about 30 μm to about 10,000 μm. Among them, water-dispersible granules, water-soluble granules, granular formulations and the like are preferred. Particularly, water-dispersible granules or water-soluble granules are preferred.

[0040] The term “amorphous silica” is referred to as “hydric silicic acid”, “wet silica” or “synthetic silicic acid” and indicates an amorphous silica that has a Si-O lattice structure and does not have a regular crystal structure .

[0041] Examples of the commercialized amorphous silica product include CARPLEX #80, CARPLEX #80D, CARPLEX #67, CARPLEX #1120, CARPLEX #XR and Sipernat22S (all manufactured by DSL. Japan Co., Ltd.); FINESEAL A, FINESEAL E-50, FINESEAL ); and Nipsil NS, Nipsil NS-K, Nipsil NS-T, Nipsil NA, Nipgel AZ-200, Nipgel AZ-260 and Nipgel AZ-460 (all manufactured by TOSOH CORPORATION) and ZEOSEAL 1100V (all manufactured by TAKI CHEMICAL CO., LTD.)

[0042] The term “insecticide that has a mechanism of action of a competitive modulator of the nicotinic acetylcholine receptor (nAChR)” indicates a neonicotinoid-based compound (such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid or thiamethoxam) , a butenolide-based compound (such as flupyradifurone), a mesoionic compound (such as triflumezopyrim), nicotine, nicotine sulfate, sulfoxaflor, dichloromezothiaz or flupyrimine. Among them, neonicotinoid compound is preferred. Particularly, dinotefuran is preferred.

[0043] Subsequently, the granular pesticide formulation of the present invention will be described.

[0044] The granular pesticide formulation of the present invention includes: (1) a pesticide as an active ingredient; (2) a salt of carboxymethyl cellulose; and (3) a formalin condensate of alkyl naphthalene sulfonate and a lignin sulfonate; and does not include (4) lactose.

[0045] The “pesticide(s) as active ingredient(s)” in the granular pesticide formulation of the present invention is(are) contained as a main ingredient to prevent harmful organisms in an agricultural field. The mixing ratio in the granular pesticide formulation of the pesticide(s) as active ingredient(s) can be appropriately determined depending on the physical properties of the pesticide(s) as active ingredient(s). and conditions of use. The mixing ratio is preferably 0.1 to 90% by weight, more preferably 1 to 80% by weight and even more preferably 10 to 70% by weight with reference to 100% by weight of the granular pesticide formulation.

[0046] The “carboxymethyl cellulose salt” in the granular pesticide formulation of the present invention is contained as a binder, an adhesive, a dispersant, a disseminator, a thickener, a stabilizer, a water retainer or a colloid protecting agent. The mixing ratio in the granular pesticide formulation of the carboxymethyl cellulose salt can be appropriately determined depending on the physical properties of the carboxymethyl cellulose salt and the conditions of use. From the points of view of hardness, water absorptivity, water disintegrability and dispersion stability of the formulation, the uniformity of effect and production efficiency, the mixing ratio is preferably 0.1 to 3% by weight, more preferably from 0.5 to 2% by weight and even more preferably from 0.5 to 1.5% by weight with reference to 100% by weight of the granular pesticide formulation.

[0047] “Alkyl naphthalene sulfonate formalin condensate and lignin sulfonate” in the granular pesticide formulation of the present invention are contained as dispersants, binders, chelating agents or wetting agents. The mixing ratio of the alkyl naphthalene sulfonate formalin condensate and the lignin sulfonate in the granular pesticide formulation can be appropriately determined depending on the physical properties of the alkyl naphthalene sulfonate formalin condensate and the lignin sulfonate and the conditions of use. From the viewpoint of hardness, water absorptivity, water disintegrability and dispersion stability of the formulation, the uniformity of effect and production efficiency, the mixing ratio is preferably 2 to 20% by weight, more preferably 2 to 15% by weight and even more preferably from 2 to 12% by weight with reference to 100% by weight of the granular pesticide formulation.

[0048] The mixing ratio of the alkyl naphthalene sulfonate formalin condensate and lignin sulfonate of the present invention can be appropriately determined depending on the physical properties of the alkyl naphthalene sulfonate formalin condensate and lignin sulfonate and the conditions of use. From the viewpoint of hardness, water absorptivity, water disintegrability and dispersion stability of the formulation, the uniformity of effect and production efficiency, the mixing ratio is preferably 1 : 9 to 9 : 1, more preferably 2 : 8 to 8 : 2 and even more preferably from 6 : 4 to 4 : 6.

[0049] “Amorphous silica” in the water-dispersible granules of the present invention may be contained as an anti-caking agent, a flow modifier or an extender. The mixing ratio of the amorphous silica in the granular pesticide formulation can be appropriately determined depending on the physical properties of the amorphous silica and the conditions of use. From the viewpoint of hardness, water absorptivity, water disintegrability and dispersion stability of the formulation, the suppression of bubble formation, the uniformity of effect and production efficiency, the mixing ratio is preferably 0 to 5% in weight, more preferably 0 to 3% by weight and even more preferably 0 to 2% by weight and most preferably 0% by weight with reference to 100% by weight of the granular pesticide formulation.

[0050] Note that in the inventions of the related art, amorphous silica (which is referred to as “wet silica, dry silica or the like” in WO 2014/133178), not described in JP 2005-132741 A and is referred to as “carbon white” in JP 2008-308447 A) is described to be used as “a synthetic carrier” in WO 2014/133178 (paragraph [0046]) and is generally described to be added as “an oil absorbing agent or a binder” in JP 2008-308447 A (paragraph [0027]). However, WO 2014/133178, JP 2005-132741 A and JP 2008-308447 A do not specifically describe that the mixing ratio of amorphous silica is specified. JP 2008-308447 A (in Examples 1, 2, 5 and 7) briefly describes 15 or 16 parts by weight of amorphous silica. The amorphous silica in JP 2008-308447 A plays a role as an auxiliary agent used to grind pesticide raw materials. However, the amorphous silica of the present invention plays a role as a flow modifier during mixing, the role and the amount of amorphous silica composition contained in the formulation are substantially different. Therefore, in the present invention, amorphous silica does not need to be used to grind pesticide raw materials. In this way, the mixing ratio of amorphous silica in the granular pesticide formulation may be lower than the normal mixing ratio in the granular pesticide formulation. Consequently, it is possible to increase the proportions of the pesticide(s) as active ingredient(s) in the granular pesticide formulation, as well as other auxiliary agents as ingredients. Additionally, according to the present invention, the mixing ratio of amorphous silica can be adjusted to a certain value or less as described above, while it is possible to prevent the water disintegrability from deteriorating in a high humidity storage condition. Furthermore, it is possible to prevent the water disintegrability from deteriorating in a high temperature storage condition.

[0051] The granular pesticide formulation of the present invention does not contain lactose. In the present invention, the granular pesticide formulation contains an alkyl naphthalene sulfonate formalin condensate surfactant and a lignin sulfonate surfactant, while it is possible to maintain good water disintegrability in a high temperature storage condition despite the fact that lactose to increase solubility is not added. Furthermore, it is possible to maintain good disintegrability in water in immediate condition after production and in high temperature storage condition. Consequently, it is possible to increase the proportions of the pesticide(s) as active ingredient(s) in the granular pesticide formulation, as well as other auxiliary agents as ingredients.

[0052] To the granular pesticide formulation of the present invention, arbitrary components can be added in the range that does not provide the effect. Examples of arbitrary components include clay minerals and fillers, dyes, surfactants, solvents and oils, glycols and saccharides, water-soluble polymers, antiseptics and an antifungal, inorganic salts, ultraviolet shielding agents, latexes and emulsions, defoamers, adjust pH and perfumes.

[0053] Examples of clay minerals and fillers include alumina, zirconia, gairome clay, kaolinite, kaolin, calcium bentonite, chromite sand, quartz sand, quartz sand silica, zirconium silicate, silica stone powder, diatomaceous earth, aluminum nitrite, barium carbonate, saponite, colemanite, calcined diatomaceous earth, shirasu, shirasu balloon, silicon carbide, zirconium sand, zirconium, zirconium powder, aluminum hydroxide, zeolite, glass powder quartz, sodium bentonite, sodium montmorillonite, feldspar powder, ceramic stone, halloysite, borax, magnesia, tree section clay, agalmatolite, perlite, cement, calcium carbonate, mica, kaolin clay, talc, pagodite , soapstone, glass bead, alumina, calcium phosphate, tabular lintel, walastonite, precipitated calcium carbonate, synthetic hydrotalcite, synthetic mica, heavy calcium carbonate, calcined clay, silk powder, slaked lime, selenite, carbonate calcium, ultrafine particulate zinc oxide, precipitated barium sulfate, powdered dolomite, powdered nylon, barium sulfate, particulate aluminum hydroxide, polyethylene wax, organic bentonite, fused silica and agalmatolite.

[0054] Examples of the dye include white zinc, cuprous oxide, lead monoxide, attention red, titanium oxide pigment produced by the chloride method, oil furnace carbon black, chrome yellow, yellow iron oxide , phosphorus oxysulfide, cadmium yellow, cadmium red, ultramarine, fluorescent pigment, graphite, iron oxide black, ultrafine calcium carbonate, cobalt blue, cobalt green, cobalt purple, charcoal, iron blue, thermal black, chromium oxide, oxide titanium (anatase), titanium oxide (rutile), terbium oxide, copper oxide, Disazo yellow, red iron oxide, granular carbon black, brown iron oxide, black channel, ultrafine particulate titanium oxide , black iron, natural graphite powder, natural earthy graphite, blue copper phthalocyanine, green copper phthalocyanine, Permanent Red, phosphorus vanadate, particulate titanium oxide, Fast yellow 10G, rouge and red molybdate.

[0055] Examples of surfactants include anionic surfactants, non-ionic surfactants, cationic surfactants and ampholytic surfactants.

[0056] Examples of anionic surfactants include alkylbenzene sulfonate, alkylsulfonate, polyoxyalkylene alkyl ether sulfate, fatty acid salt, alkanesulfonate, olefin sulfonate, alkylsulfosuccinate, polyoxyalkylene alkyl ether sulfosuccinate, alkylphosphate, polyoxyalkylene alkyl ether phosphate and polyoxyalkylene alkyl ether acetate. Examples of surfactant salts include an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and various amine salts.

[0057] Examples of nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene acyl (which has 6 to 18 carbon atoms) ester, alkyl diethanolamide, polyoxyalkylene triglyceride ether, sorbitan fatty acid ester, sucrose fatty acid ester, ester of polyoxyalkylene sorbitan fatty acid, alkylpolyglucoside and polyoxyethylene polyoxypropylene block polymer.

[0058] Examples of cationic surfactants include a monoalkyl amine salt, a dialkyl amine salt, a trialkyl amine salt, an alkyl trimethyl ammonium salt, a dialkyl dimethyl ammonium salt, an alkyl dimethyl benzyl ammonium salt and an alkyl dimethyl aminopropyl amide. Examples of surfactant salts include halogen salts such as chlorine and bromine.

[0059] Examples of zwitterionic surfactants include an alkyl betaine, a fatty acid amide propyl betaine, a 2-alkyl-N-carboxylmethyl-N-hydroxyethyl imidazolinium betaine, an alkyl diethylene triamine acetic acid, a dialkyl diethylene triamine acetic acid and a alkyl amine oxide.

[0060] Examples of solvents and oils include ethanol, isopropanol, 1-butanol, propylene glycol, polyethylene glycol, polypropylene glycol, acetic acid, acetic anhydride, acetophenone, methyl oleate, coconut oil, rapeseed oil, soybean, castor oil, flax seed oil, paraffin oil, kerosene, higher alcohol, cyclohexanol, benzyl alcohol, ethylene glycol, hexylene glycol, propylene glycol monopropyl ether, propylcellulose, gamma-butyrolactone, fatty acid methyl ester , methyl pyrrolidone, dimethyl sulfoxide, chlorobenzene, chlorotoluene, dichloroaniline, toluene, xylene, alkyl benzene, normal paraffin, butylcellulose, methylcarbitol, ethylcarbitol, butylcarbitol, propylene glycol monobutyl ether, dimethyl phthalate, diet phthalate, dibutyl phthalate, cycle -hexanone, acetonitrile, heating oil, machine oil and aromatic solvent.

[0061] Examples of glycols and saccharides include diol compounds, glycerin and derivatives thereof; pentaerythritol, sorbitol, xylitol, sucrose, grape sugar and fructose (in which lactose is excluded).

[0062] Examples of water-soluble polymers include xanthan gum, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, poly(vinyl alcohol), starch, dextrin and polyvinylpyrrolidone.

[0063] Examples of antiseptics and antifungals include sorbic acid, potassium sorbate, parachloromethaxylenol, sodium dehydroacetate, polyhexamethylene biguanide hydrochloride, 1,2-benzothiazolin-3-one, methyl parahydroxybenzoate, p- ethyl hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, heptyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, p-hydroxybenzonate, orthophenylphenol, sodium orthophenylphenate, glutardialdehyde, quaternary ammonium compounds, tri-(N- chlorohexyldiazeniumdioxy)-aluminum,tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazin-2-thione, 2,5-dimethoxytetrahydrofuran, dimethylolurea, sodium N-methyldithiocarbamate, phenoxyethanol , glyoxal, glutaraldehyde, 1,3,5-tris(2-hydroxyethyl)-1,3,5-hexahydrotriazine, benzalkonium chloride, phenoxypropanol, tetramethylacetylenediurea, povidone-iodine, 2-bromo-2-nitropropane-1,3 -diol and thiazolone.

[0064] Examples of inorganic salts include calcium silicate, magnesium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, ammonium sulfate, sodium sulfate, magnesium sulfate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and potassium chloride.

[0065] Examples of ultraviolet shielding agents include salicylic acid-based ultraviolet shielding agents and benzophenone-based ultraviolet shielding agents.

[0066] Examples of latexes and emulsions include styrene-butadiene copolymers, styreneacrylate copolymers, methyl methacrylate-butadiene copolymers, ethylene-vinyl acetate copolymers, ethylene acrylate copolymers, silicone and acrylate copolymers, and latexes and emulsions, such as polyurethane and polyurea.

[0067] Examples of defoamers include lower alcohol-based defoamers (such as methanol, ethanol, isopropanol, sec-butanol and butanol), amyl alcohol, diisobutyl carbitol, tributyl phosphate, oleic acid, Tall oil, soap metal, sorbitan lauric acid monoester, sorbitan lauric acid triester, polyethylene glycol fatty acid ester, pluronic non-ionic surfactants, organic polar compound-based defoamers (such as acetylene glycol derivatives) and silicone resin-based defoamers (such as silicone resin, products containing silicone resin surfactant and products containing inorganic silicone resin powder).

[0068] Examples of the pH adjusting agent include inorganic acids, such as phosphoric acid; organic acids such as citric acid, phthalic acid and succinic acid; organic metal salts such as sodium citrate and potassium hydrogen phthalate; inorganic metal salts such as disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium carbonate, potassium carbonate and sodium borate; hydroxides, such as sodium hydroxide and potassium hydroxide; and organic amines, such as triethanolamine.

[0069] Examples of the perfumes include lavender oil, jasmine oil, rose oil, lemon oil, orange oil, peppermint oil, thyme oil, iris oil, fennel oil, Cryptomeria japonica oil, Hiba oil , cypress oil, eucalyptus oil, camphor, peppermint oil, peppermint oil, geranium, citrone same, eugenol, limonene, tangerine oil, bitter orange peel and citronellol.

[0070] Subsequently, the method of producing the granular pesticide formulation of the present invention will be explained.

[0071] According to the method of producing the granular pesticide formulation of the present invention, a mixture for the granular pesticide formulation of the present invention can be obtained by adding, for example, pesticide(s) as active ingredient(s), a carboxymethyl cellulose salt, an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonic acid, clay minerals as extenders and a filler; and a surfactant and other arbitrary additives if necessary. The obtained mixture is kneaded by adding water and other arbitrary additives if necessary using a kneading machine and the resulting mixture is formed into a granulated substance using an extrusion granulator. The resulting granular substance is dried and subjected to particle size regulation, at the same time producing the granular pesticide formulation of the present invention. The mixing method and the mixing order of the raw materials used in this production method are not particularly limited, as long as the effect of the present invention is obtained and the method can be carried out appropriately by selecting the mixing conditions, kneading conditions, conditions granulation and drying conditions and particle size regulation.

[0072] Examples of the kneading machine include a kneader, a Nauta mixer, a powerful mixer and a Lodige mixer.

[0073] Examples of the extrusion granulator include a screw-type extrusion granulator, a roller-type extrusion granulator, a disc compaction-type extrusion granulator, a granule mill-type extrusion granulator, a basket-type extrusion granulator, a paddle type extrusion granulator, an oscillatory type extrusion granulator, a gear type extrusion granulator and a ring mold type extrusion granulator.

[0074] In the production method, the pesticide(s) as active ingredient(s) in liquid or solid form may be previously mixed with an extender (or an arbitrary additive, if necessary) and can be crushed, if necessary, before use. The pesticide(s) as active ingredient(s) in liquid or solid form may be bound or attached to clay minerals and water-soluble fillers or polymers, prior to use and can be formed into microcapsules using latexes and emulsions, before use. Additionally, the pesticide(s) as active ingredient(s) in liquid or solid form may be used after being dissolved or suspended in water, a solvent or an oil.

[0075] Subsequently, the method of applying the granular pesticide formulation of the present invention will be described.

[0076] The granular pesticide formulation of the present invention is used to prevent harmful organisms or regulate plant growth depending on the pesticide(s) as active ingredient(s) contained therein. When the pesticide(s) as active ingredient(s) contained in the granular pesticide formulation of the present invention is(are) insecticides, it(s) may be used, for example, as insecticides for vegetables or orchards.

[0077] The granular pesticide formulation of the present invention is used in the following manner. For example, the granular pesticide formulation of the present invention is diluted with water and sprayed onto the crop or soil by means of a sprinkler. Increased dilution of the granular pesticide formulation of the present invention with water can be appropriately selected and determined depending on the type and content of the pesticide(s) as active ingredient(s) in the granular pesticide formulation of the present invention, as well as such as the type of harmful organisms and conditions of use and is typically 10 to 10,000 times.

[Examples]

[0078] Hereinafter, the granular pesticide formulation to be used in the present invention will be specifically described with reference to the Examples and comparative Examples, however, the present invention is not limited to them.

[Example 1]

[0079] 70.0 parts by weight of dinotefuran, 1.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 5A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 4.0 parts by weight of formalin condensate of sodium alkyl naphthalene sulfonate (MORWET D425 POWDER, Akzo Nobel Surface Chemistry AB.), 4.0 parts by weight of sodium lignin sulfonate (PEARLLEX NP, Nippon Paper Co., Ltd.), 1.0 parts by weight of sodium dialkyl sulfosuccinate (AEROLE CT-1, TOHO Chemical Industry Co., Ltd.) and 20.0 parts by weight of a clay (KAOLIN HA, SANYO CLAY Co., Ltd.) were mixed. 11.0 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 70 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of Example 1.

[Example 2]

[0080] 50.0 parts by weight of penthiopyrad, 1.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 7A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 5.0 parts by weight of formalin condensate of sodium alkyl naphthalene sulfonate (DEMOL RN, Kao Corporation.), 4.0 parts by weight magnesium lignin sulfonate (San X SCL, Nippon Paper Co., Ltd.), 1.0 parts by weight magnesium dialkyl sulfosuccinate sodium (AEROLE CT-1L, TOHO Chemical Industry Co., Ltd.) and 39.0 parts by weight of a clay (KAOLIN HA, SANYO CLAY Co., Ltd.) were mixed. 13.0 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 70 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of Example 2.

[Example 3]

[0081] 20.0 parts by weight of dinotefuran, 10.0 parts by weight of broflanilide, 1.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 5A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 3, 0 parts by weight of sodium alkyl naphthalene sulfonate formalin condensate (MORWET D425 POWDER, Akzo Nobel Surface Chemistry AB.), 3.0 parts by weight of sodium lignin sulfonate (PEARLLEX NP, Nippon Paper Co., Ltd. ), 1.0 parts by weight of sodium dialkyl sulfosuccinate (NEWKALGEN EX-70, TAKEMOTO OIL & FAT Co., Ltd.), 60.0 parts by weight of a clay (KAOLIN HA, SANYO CLAY Co., Ltd. ) and 2.0 parts by weight of an amorphous silica (CARPLEX #80D, DSL. Japan Co., Ltd.) were mixed. 16.0 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 80 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of Example 3.

[Example 4]

[0082] 30.0 parts by weight of dinotefuran, 15.0 parts by weight of broflanilide, 1.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 5A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 4, 0 parts by weight of sodium alkyl naphthalene sulfonate formalin condensate (MORWET D425 POWDER, Akzo Nobel Surface Chemistry AB.), 4.0 parts by weight of sodium lignin sulfonate (PEARLLEX NP, Nippon Paper Co., Ltd. ), 1.0 parts by weight of sodium dialkyl sulfosuccinate (NEWKALGEN EX-70, TAKEMOTO OIL & FAT Co., Ltd.), 42.0 parts by weight of a clay (KAOLIN HA, SANYO CLAY Co., Ltd. ) and 3.0 parts by weight of an amorphous silica (Nipsil NS-T, TOSOH CORPORATION) were mixed. 16.5 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 80 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of Example 4.

[Example 5]

[0083] 50.0 parts by weight of dinotefuran, 12.5 parts by weight of broflanilide, 1.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 5A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 4, 0 parts by weight of sodium alkyl naphthalene sulfonate formalin condensate (MORWET D425 POWDER, Akzo Nobel Surface Chemistry AB.), 4.0 parts by weight of calcium lignin sulfonate (PEARLLEX CP, Nippon Paper Co., Ltd. ), 1.0 part by weight of sodium dialkyl sulfosuccinate (NEWKALGEN EX-70, TAKEMOTO OIL & FAT Co., Ltd.), 22.5 parts by weight of a clay (KAOLIN HA, SANYO CLAY Co., Ltd. ) and 5.0 parts by weight of an amorphous silica (TOKUSEAL GU-N, Tokuyama Corporation) were mixed. 14.0 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 80 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of Example 5.

[Example 6]

[0084] 8.0 parts by weight of dinotefuran, 50.0 parts by weight of buprofezin, 1.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 5A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 4, 0 parts by weight of sodium alkyl naphthalene sulfonate formalin condensate (MORWET D425 POWDER, Akzo Nobel Surface Chemistry AB.), 4.0 parts by weight of sodium lignin sulfonate (PEARLLEX NP, Nippon Paper Co., Ltd. ), 1.0 parts by weight of sodium dialkyl sulfosuccinate (NEWKALGEN EX-70, TAKEMOTO OIL & FAT Co., Ltd.) and 32.0 parts by weight of a clay (KAOLIN S-400, LORWATTANA Co., Ltd .) were mixed. 16.0 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 70 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of Example 6.

[Example 7]

[0085] 50.0 parts by weight of dinotefuran, 1.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 7A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 6.0 parts by weight of formalin condensate of sodium alkyl naphthalene sulfonate (MORWET D500 POWDER, Akzo Nobel Surface Chemistry AB.), 6.0 parts by weight of sodium lignin sulfonate (PEARLLEX NP, Nippon Paper Co., Ltd.), 1.5 parts by weight of sodium dialkyl sulfosuccinate (NEWKALGEN EX-70, TAKEMOTO OIL & FAT Co., Ltd.), 29.5 parts by weight of a clay (KAOLIN S-400, LORWATTANA Co., Ltd.) and 6.0 parts by weight of an amorphous silica (TOKUSEAL GU-N, Tokuyama Corporation) were mixed. 16.0 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 70 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of Example 7.

[Comparative example 1]

[0086] 50.0 parts by weight of dinotefuran, 1.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 7A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 4.0 parts by weight of formalin condensate of sodium alkyl naphthalene sulfonate (NEWKALGEN PS-P, TAKEMOTO OIL & FAT Co., Ltd.), 4.0 parts by weight sodium lignin sulfonate (VANILLEX N, Nippon Paper Co., Ltd.), 1.0 part by weight of sodium dialkyl sulfosuccinate (NEWKALGEN EX-70, TAKEMOTO OIL & FAT Co., Ltd.), 35.0 parts by weight of lactose (Meggletose B200, MEGGLE) and 5.0 parts by weight of an amorphous silica (CARPLEX #80D, DSL. Japan Co., Ltd.) were mixed. 15.0 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 70 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of comparative Example 1.

[Comparative example 2]

[0087] 60.0 parts by weight of dinotefuran, 3.0 parts by weight of sodium alkyl naphthalene sulfonate formalin condensate (NEWKALGEN PS-P, TAKEMOTO OIL & FAT Co., Ltd.), 3.0 parts in weight of sodium lignin sulfonate (VANILLEX N, Nippon Paper Co., Ltd.), 1.0 part by weight of sodium dialkyl sulfosuccinate (AEROLE CT- 1L, TOHO Chemical Industry Co., Ltd.), 27.0 parts by weight of a clay (KAOLIN HA, SANYO CLAY Co., Ltd.) and 6.0 parts by weight of an amorphous silica (CARPLEX #80D, DSL. Japan Co., Ltd.) were mixed. 16.0 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 70 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of comparative Example 2.

[Comparative example 3]

[0088] 60.0 parts by weight of dinotefuran, 2.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 5A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 3.0 parts by weight of sodium lignin sulfonate sodium (PEARLLEX CP, Nippon Paper Co., Ltd.), 1.0 parts by weight of sodium dialkyl sulfosuccinate (NEWKALGEN EX-70, TAKEMOTO OIL & FAT Co., Ltd.), 28.0 parts by weight of a clay (KAOLIN HA, SANYO CLAY Co., Ltd.) and 6.0 parts by weight of an amorphous silica (CARPLEX #80D, DSL. Japan Co., Ltd.) were mixed. 16.0 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 70 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of comparative Example 3.

[Comparative example 4]

[0089] 60.0 parts by weight of dinotefuran, 3.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 7A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 4.0 parts by weight of formalin condensate of sodium alkyl naphthalene sulfonate (MORWET D500 POWDER, Akzo Nobel Surface Chemistry AB.), 1.0 part by weight sodium dialkyl sulfosuccinate (NEWKALGEN EX-70, TAKEMOTO OIL & FAT Co., Ltd.), 37.0 parts by weight of a clay (KAOLIN HA, SANYO CLAY Co., Ltd.) and 5.0 parts by weight of an amorphous silica (CARPLEX #1120, DSL. Japan Co., Ltd.) were mixed. 16.0 parts by weight of water with respect to 100.0 parts by weight of the resulting mixture were added to the mixture and the resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extrusion grader which was equipped with a screen having opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 70 °C, the dried granules were selected by shaking through a set of screens composed of sieves in which a 1,180 μm sieve was placed on top of an underlying 500 μm sieve, thus obtaining a granular pesticide formulation of comparative Example 4.

[Test example] (Water disintegrability test)

[0090] In this test, the granular pesticide formulations that were obtained in Examples 1 to 7 and comparative Examples 1 to 4 were used. Each test sample of the granular pesticide formulations was prepared for water disintegrability testing immediately after production, stored for 14 days in a thermostat set at 54°C, and stored for 7 days in a thermohygrostat set at a temperature of 30 °C and an atmosphere of 80% relative humidity.

[0091] 500 mg of each test sample of the granular pesticide formulations were placed in a colorimetric cylinder containing the volume (100 mL) of water that has a hardness of 3 degrees defined in the official pesticide inspection method. Then, the cylinder was repeatedly inverted at a rate of once per 2 seconds. The number of times of cylinder inversion that was required until each test sample of the granular pesticide formulations was completely disintegrated and did not maintain the granule shape in water was counted. If the inversion count is small, the sample of granular pesticide formulations was disintegrated quickly in water and had good disintegrability in water. In this test, the test sample having the inversion times count less than or equal to 20 was evaluated as having good disintegrability in water.

[0092] The results are shown in Table 1. [Table 1] Water disintegrability of the granular agricultural formulation

[0093] As shown in the test results of Examples 1 to 7, due to the inversion times count less than or equal to 20, the granular pesticide formulation of the present invention including: (1) a pesticide as an active ingredient; (2) a salt of carboxymethyl cellulose; and (3) a formalin condensate of alkyl naphthalene sulfonate and a lignin sulfonate; and not including (4) lactose can maintain good water disintegrability in a high humidity storage condition. Furthermore, the granular pesticide formulation of the present invention can maintain good disintegrability in water in immediate condition after production thereof and in a high temperature storage condition. Additionally, as in Examples 1, 2 and 6, in the case of the granular pesticide formulation having an amorphous silica mixing ratio of 0% by weight, it is possible to prevent the water disintegrability from deteriorating in a high temperature storage condition. and/or high humidity. However, as in comparative Examples 1 to 4, it was observed that the granular pesticide formulation which contains none of (2) a carboxymethyl cellulose salt and (3) an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate or the formulation Granular pesticide containing (4) lactose had the inversion times count greater than 20 in a high humidity storage condition. Furthermore, the granular pesticide formulation of comparative Examples 1 and 3 had the inversion times count greater than 20 in immediate condition after production thereof and in a high temperature storage condition. The granular pesticide formulation of comparative Examples 1 to 4 resulted in significant deterioration of water disintegrability.

[0094] According to the present invention, it is possible to obtain a granular pesticide formulation that maintains good disintegrability in water in a successive high humidity condition. Furthermore, it is possible to obtain a granular pesticide formulation that maintains good disintegrability in water immediately after its production and in a successive condition at high temperature. The granular pesticide formulation is useful as a pesticide formulation that is suitable for use on various crops without being restricted by the climatic conditions of the area where the pesticide formulation is used, for example, in a high temperature and/or high humidity condition.

Claims (11)

1. Granular pesticide formulation, characterized by the fact that it comprises: (1) a pesticide as an active ingredient; (2) a salt of carboxymethyl cellulose; and (3) a formalin condensate of alkyl naphthalene sulfonate and a lignin sulfonate; and which does not comprise (4) lactose. 2. Granular pesticide formulation according to claim 1, characterized in that it additionally comprises an amorphous silica in a mixing ratio of 0 to 5% by weight. 3. Granular pesticide formulation according to claim 1 or 2, characterized in that the mixing proportion of amorphous silica is 0% by weight. 4. Granular pesticide formulation according to any one of claims 1 to 3, characterized by the fact that at least one pesticide contained as the active ingredient is an insecticide that has a competitive modulator of the nicotinic acetylcholine receptor (nAChR) ). 5. Granular pesticide formulation according to any one of claims 1 to 4, characterized in that at least one pesticide contained as the active ingredient is a neonicotinoid insecticide. 6. Granular pesticide formulation according to claim 4 or 5, characterized in that at least one pesticide contained as the active ingredient is dinotefuran. 7. Granular pesticide formulation according to any one of claims 1 to 6, characterized in that the carboxymethyl cellulose salt is sodium carboxymethyl cellulose. 8. Granular pesticide formulation according to any one of claims 1 to 7, characterized in that the alkyl naphthalene sulfonate formalin condensate is a sodium alkyl naphthalene sulfonate formalin condensate. 9. Granular pesticide formulation according to any one of claims 1 to 8, characterized in that the lignin sulfonate is sodium lignin sulfonate. 10. Granular pesticide formulation according to any one of claims 1 to 9, characterized in that it comprises: (1) 0.1 to 90% by weight of a pesticide as the active ingredient; (2) 0.1 to 3% by weight of carboxymethyl cellulose salt; (3) 2 to 20% by weight of alkyl naphthalene sulfonate formalin condensate; and 2 to 20% by weight of lignin sulfonate. 11. Granular pesticide formulation according to any one of claims 1 to 10, characterized in that the mixing ratio of alkyl naphthalene sulfonate formalin condensate to lignin sulfonate is 1: 9 to 9: 1.