BR102018071178A2 - GRANULAR PESTICIDAL FORMULATION - Google Patents

Abstract

The granular pesticide formulation of the present invention contains a carboxymethyl cellulose salt, an alkyl naphthalene sulfonate formalin condensate and lignin sulfonate therein, while 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

GRANULAR PESTICIDE FORMULATION FUNDAMENTALS

Technical field [001] The present invention relates to a granular pesticide formulation including pesticide (s) as an active ingredient (s). More specifically, it refers to a granular pesticide formulation that maintains good disintegrability in water in an immediate condition after its production, 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 pesticidal formulations are more convenient to use compared to powdered formulation pesticides as the following advantageous reasons: (1) Granular pesticidal formulations are not bulky due to their high bulk density; (2) There is no fear that the worker using the granular pesticide formulations will be exposed to the pesticides by the extremely small spread of fine powder during the preparation of the spray solution; and (3) Granular pesticide formulations are easy to measure by the worker.

[003] Water disintegrability is generally mentioned as an important physical property of granular pesticide formulations. Disintegrability in water is a parameter that represents the easy granular disintegration in water. Granular pesticidal formulations must be rapidly disintegrated in water when diluted with water to prepare the spray solution.

[004] The known granular pesticidal 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

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2/38 dispersion and containing pesticides as active ingredients are described. Water-dispersible granules maintain good water disintegrability after successively stored for 2 weeks at 54 ° C and water-dispersible granules include (a) active 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 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 WO invention

2014/133178, in paragraph [0041], a condensate of sodium salt formaldehyde of naphthalene sulfonic acid 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, a type of anionic surfactant is used.

[007] Additionally, WO water-dispersible granules

2014/133178 include (d) lactose, however, the granular pesticidal formulations of the present invention do not include lactose.

[008] In this way, the granular pesticidal formulation of the present invention and the water-dispersible granules of WO 2014/133178 differ

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3/38 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 that has an aqueous solution viscosity of 10 to 2,000 mPa-s and a surfactant. In addition, paragraph [0018] that specific examples of the adhesive include carboxymethyl cellulose or a sodium salt thereof.

[0010] In the case of the granular pesticidal formulation of the present invention, the problems to be solved by the invention refer to the improvement of disintegrability in water and the granular pesticidal formulation includes a salt of carboxymethyl cellulose and surfactants: a condensate of alkyl naphthalene sulfonate formalin and a lignin sulfonate. However, in the case of water-dispersible granules of JP 2005-132741 A, the problems to be solved by the invention refer to the improvement of resistance to rain 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 JP 2005-132741 A, paragraph [0019] describes that it is essential to add the surfactant in order to maintain the physical properties of the favorable formulation. 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, a type of surfactant: sodium lignin sulfonate is used.

[0012] Thus, the granular pesticide formulation of this

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4/38 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 for the invention.

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

[0014] The granular pesticidal 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 nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants and the like can be used without limitation. In addition, paragraphs [0023] to [0025] describe specific examples of non-ionic surfactants, anionic surfactants and cationic surfactants. Undoubtedly, paragraph [0026] describes that "these surfactants can be used alone, or two or more different types of them can be used in combination". When reviewing the specific test examples, in Example 3, an example of a formulation obtained using a type of surfactant is described: sodium lignin sulfonate. In Examples 4 and 6, examples of formulations obtained using a type of surfactant are described: a sodium formalin condensate of alkyl naphthalene sulfonate. However, JP 2008-308447 A describes only that one type of surfactant is used to produce any of the formulation examples. There is neither description nor suggestion regarding the

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5/38 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 with respect to a specific example of the formulation.

[0016] In this way, the granular pesticidal 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 an active ingredient (s) is weak, whereby a nozzle of a sprinkler is clogged with unintegrated granules. The known granular pesticidal formulations have problems that include a case where the water disintegrability of the granular pesticidal formulations is weak immediately after production or a case where the water disintegrability is favorable immediately after production, the water disintegrability of the granular pesticidal formulations becomes deteriorates when granular pesticide formulations are stored in a high humidity condition.

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

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

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6/38 [0020] In order to solve the previous 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 refers as follows [1] to [11]:

[1] a granular pesticidal formulation comprising: (1) a pesticide as an active ingredient; (2) a carboxymethyl cellulose salt; and (3) an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate; and which does not comprise (4) lactose;

[2] the granular pesticidal formulation according to [1], further comprises an amorphous silica in a mixture ratio of 0 to 5% by weight;

[3] the granular pesticidal formulation according to [1] or [2], wherein the mixing ratio of the amorphous silica is 0% by weight;

[4] the granular pesticidal formulation according to any one of [1] to [3], wherein at least one pesticide contained as the active ingredient is an insecticide that has a mechanism of action for a competitive nicotinic acetylcholine receptor modulator (nAChR);

[5] the granular pesticidal 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 pesticidal 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

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7/38 one of [1] to [7], wherein the alkyl naphthalene sulfonate formalin condensate is an alkyl naphthalene sulfonate formalin condensate;

[9] the granular pesticidal formulation according to any one of [1] to [8], wherein the lignin sulfonate is sodium lignin sulfonate;

[10] the granular pesticidal 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 the carboxymethyl cellulose salt; (3) 2 to 20% by weight of the alkyl naphthalene sulfonate formalin condensate; and 2 to 20% by weight of lignin sulfonate; and [11] the granular pesticidal 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 from 1: 9 to 9: 1 .

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

[0023] Subsequently, several 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. Needless to say, its use in a tropical climate area (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

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8/38 uniformly sprayed on a Petri dish and stored in a thermo-hygrostat set at 30 ° C and 80% RH for 3 days, 7 days or 14 days. It goes without saying that the use of the same in a tropical forest climate, tropical monsoon climate or the like is included.

[0026] The term "water disintegrability" indicates that granules in 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 in a colorimetric cylinder containing the volume (100 mL) of water that has a hardness of 3 degrees defined in it in the inspection method pesticide officer, repeatedly inverting the cylinder at a rate of once for 2 seconds and counting the number of times the cylinder inversion is required until the granular pesticide formulation does not maintain the granule form in water.

[0027] The pesticide (s) as an active ingredient (s) may be a pesticide that has an effect on preventing harmful organisms and examples of which include herbicides, insecticides, acaricides, nematicides, fungicides and bactericides. The granular pesticidal formulation of the present invention can contain one or two or more types of these pesticides of which the lineage is the same or different from the active ingredients. Hereinafter, the pesticide (s) as the 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, cletodim, tepraloxidim, tralcoxidim, setoxidim, cycloxidim, propaquizafop, quizalofop, haloxifop, fluazifop-butyl, fluazifop-P-butyl, ci-halofop-butyl, propyl-dopyl-butyl , phenoxaprop-P-ethyl, amidosulfurone, azimsulfurone, trifloxysulfurone, bensulfurone-methyl, cyclosulfamurone, fhipirsulfurone-methyl, foramsulfurone, chlorimuron-ethyl, etametsulfurone, methyl halosulfurone, nicosulfurone, clorsulfurone

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9/38 imazosulfurone, oxasulfurone, pyrazosulfuronacetyl, tritosulfuron, kinasulfurone, flazassulfurone, iodosulfurone-methyl, primissuifurone-methyl, rimsulfurone, tifensuifurone-methyl, mesosulfonone, methionone, trosulfone, methionone , flucarbazone, propoxycarbazone, bispiribac, pyribenzoxim, pyrithiobac, pyriftalide, pyriminobac-methyl, chloransulam methyl, diclossulam, florassulam, flumetsulam, metossulam, penoxsulam, imazapic, imazapir, imazametam, imazametam, imazametamzam, imazametamzam, lenacil, terbacil, metabentiazurone, chlorotolurone, fluometurone, isoproturone, isourone, diurone, linurone, tebutiurone, hexazinone, metamitrone, metribuzin, ametrine, atrazine, dimetamethrin, cyanazine, promethine, simazine, simazine, simazine, simazine, simazine, simazine, syzazine lactofen, oxyfluorfen, carfentrazone-ethyl, sulfentrazone, oxadiargyl , oxadiazon, butafenacil, saflufenacil, pyrazolate, pyrazoxifene, benzofenap, topramezone, pirasulfotol, tolpyralate, mesotrione, sulcotrione, benzobicyclon, tefuriltrione, tembotrione, bicyclopyrone, phenquinotrione, lancotrin, bifalin, glifal, bifalan , trifluralin, acetochlor, butachlor, alachlor, dimetachlor, dimethenamide, propachlor, tenilchlor, methachlor, metolachlor, S-metolachlor, pretilachlor, pethoxamide, benthiocarb, butyrate, sporocarb, molinate, dimepiperate, fliroxyride, orbencirpyride, tricarpyride , picloram, quinclorac, quinmerac, clomeprop, MCPA, MCPB, 2,4-DB, ioxynil, bromoxynil, diclobenyl, amicarbazone, chloridazone, bentazone, cull butyrate, propanyl, pyridate, piraflufen-ethyl, cinidon-ethyl, pentidor-ethyl, flumiclor flumioxazin, picolinafen, aclonifene, fluridone, norflurazon, diflufenican, beflubutamide, flurochloridone, flurtamone, isoxaflutol, clomazone, asulam, dithiop ir, tiazopir, dicamba, benazoline, diufenzopir, naptalam, napropamide, tetrapione, pinoxadene, pyroxasulfone, phenoxasulfone, ipfencarbazone, indaziflam,

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10/38 aminocyclopyrachlor, halauxifen-methyl, florpirauxifen-benzyl, thiafenacil, trifludimoxazine and cyclopyrimorate.

[0029] Examples of insecticides, acaricides and nematicides include phosfocarb, alanicarb, butocarboxy, butoxycarboxy, thiodicarb, thiofanox, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, etiofencarb, methoxycarbam, carbamethyl, carbamethyl, carbamide, methoxycarbam, carbamide, , pirimicarb, propoxur, trimetacarb, XMC, alloxicarb, aldoxicarb, bufencarb, butacarb, carbanolate, metolcarb, phenothiocarb, xylilcarb, bendiocarb, acephate, azametiphos, azinfos-methyl, azinfos-chloros, chlorosphosphos, chloros, , chlorpyrifos-ethyl, coumafos, cyanofos, demeton-S-methyl, diazinon, diclofentiona, dichlorvos, dicrotofos, dimetoate, dimethilvinfos, disulfoton, Oetil-O-4-nitrophenylphenylphosphono thioate, etione, feneto, feneto, feneto, feneto, feneto fostiazate, heptenophos, isofenfos-methyl, isocarbofos, isoxathione, malationa, mecarbam, metamidophos, metidathione, mevinfos, monocrotofos, naled, ometoate, oxidemeton -methyl, parathione, paration-methyl, fentoate, phorate, fosalone, fosmet, phosphamidone, phoxim, pirimiphos-methyl, profenofos, propetamfos, protiofos, piraclofos, pyridafentiona, quinalfos, sulfotep, tebupirimofos, trefos, trefos, trefos, trefos, trefos, trefos, trefos, trefos, trefos, trefos, trefos, trifos , vamidothione, chlortiona, brofenvinfors, bromophos, bromophos-ethyl, butathiophes, carbophenothione, chlorfoxin, sulprofos, diamidafos, tetrachlorvinphos, propafos, mesulfenfos, dioxabenzofos, etrimfos, oxideprofos, isoformos, isoformes, isothione , endosulfan, linden, dienochlor, etiprol, fipronil, acetoprol, acrinatrin, alethrin [(1R) isomer], bifentrin, bioalethrin, bioallethrin-S-cyclopentenyl isomer, biormethrin, cycloprotrine, cyflothrin, gamma-cyhalothin , lambda-cy-halothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, cyphenothrin [(lR) -trans-isomer], deltamethrin, empentrine [(EZ) - (lR) -isomer], sphenolvalerate , etofenprox,

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11/38 fenpropatrin, fenvalerato, flucitrinaato, flumetrina, tau-fluvalinato, halfenprox, imiprotrina, methotrina, metoflutrina, epsilon-metoflutrina, momfluorotrina, epsilon-momfluorotrina, permethrin, prethromine, pretrine, preterm; silafluofen, teflutrin, etramethrin, tetramethrin [(lR) -isomer], tralometrine, transflutrin, ZXI8901, bio-permethrin, furamethrin, proflutrin, flubrocitrinaate, metoflutrin, DDT, methoxychloride, phenotyrene, acetaminophen, fluvalin, fluvalin , thiacloprid, thiamethoxam, nicotine, nicotine sulfate, sulfoxaflor, flupiradifurone, triflumezopyrim, spinosad, spinetoram, abamectin, emamectin benzoate, lepimectin, milbemectin, hydroprene, cinoprene, metoprene, chloroxyphenol, pyroxyphenol, pyroxyphenol, pyroxyphenol sulfuryl, borax, boric acid, disodium octaborate, sodium metaborate, emetic tartar, dazomet, metam, sodium carbamate, pimetrozine, pyrifluquinazon, clofentezine, diflovidazine, hexitiazox, ethoxazole, diafentiurone, azocyclotine, cyhexatin, fenbutatin oxide, “c12.5“ propargite, “c-12.6“ tetradifon, chlorfenapil, DNOC, sulflpharide, DNOC, cartap, thiocyclam, monossultap, bistriflurona, clorfluazurona, diflubenzuron, furcicloxurona, flufenoxuron, hexaflumuron, lufenuron, novalurona, noviflumurona, teflubenzurona, triflumuron, buprofezin, cyromazine, chromafenozida, halofenozide, methoxyfenozide, tebufenozide, amitraz, hydramethylnon, acequinocyl, fluacripirim, bifenazate, fenazaquin, fenpyroximate, pyridabene, pyrimidifene, tebufenpirate, tolfenpirate, rotenone, indoxacarb, metaflumizone, spirodiclofen, spiromesifene, spirotetramat, aluminum phosphite, calcium phosphide, phosphorus hydride, zinc phosphide, sodium cyanate, potassium cyanate, sodium cyene kyflumetophen, piflubumide, chlorantraniliprol, cyantraniliprol, flubendiamide, flo nicamide, azadiractin, benzoxide, phenisobromolate, chinometionat, dicofol, pyridalyl, bromopropylate, triazamate, dicyclanil, dinobutoan, dinocap, hydrogen cyanide, iodide

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12/38 methyl, caranjine, mercury chloride, methyl isothiocyanate, pentachlorophenol, phosphine, piperonyl butoxide, polynactin, sabadilla, sulcofuron-sodium, tribufos, aldrina, amiditiona, amide thioate, aminocarb, amiton, alamite, amidate, amidate, amidate , poly (barium sulfite), benclothiaz, 5- (1,3benzodioxole-5-yl) -3-hexylcyclohexa-2-enone, 1,1-bis (4-chlorophenyl) -2ethoxyethanol, butonate, butopyronoxyl, 2- ( 2-butoxyethoxy) ethyl thiocyanate, camfeclor, clorbenside, chlordecone, chlordimeform, chlorphenethol, chlorfenson, fluazurone, metaldehyde, bialaphos, levamisole hydrochloride, amidoflumet, pirafluprole, pyriprole, tralopyril, flirofol, fluorol, fluorol, fluorazole , oxybendazole, fenbendazole, metam-sodium, 1,3-dichloropropene, flometoquin, cyclaniliprol, tetratraniliprole, broflanilide, dichloromezothiaz, ethylene dibromide, acrylonitrile, bis (2-chloroethyl) ether, l-bromo-2-chloro-3-chloro-3 -chloroprop-l-ene, bromocyclene, car disulfite bono, carbon tetrachloride, nemadectin, cyimiazole, calcium polysulfite, cytokinin, 2- (octyllium) ethanol, potassium oleate, sodium oleate, machine oil, tar oil, anabasine, morantel tartrate, cinerariaefolium chrysanthemum (pyrethrin) , rapeseed oil, soy lecithin, starch, hydroxypropyl starch, fatty acid glyceride, mono-propylene glycol ester, diatomaceous earth, afoxolaner, fluazaindolizine, aphidopyropene, cy-halodiamide, tioxazafene, fluexafon, fluexafon, fluralamide, flural tetrachlorantraniliprol, sarolaner, lotilaner, cycloxapride, fluensulfone, TPIC, DD, 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 ticlopyrazoflor. Examples of insecticides include insecticides that have a mode of action of the competitive modulator of the nicotinic acetylcholine receptor (nAChR) (such as acetamipride, clothianidin, dinotefuran, imidacloprid, nitenpiram, thiaclopride, thiamethoxam, nicotine, nicotine sulfate, sulfoxaflor,

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13/38 flupiradifurone, triflumezopyrim, dichloromezothiaz and flupirimin); diamide insecticides, such as flubendiamide, chlorantraniliprol, cyantraniliprol, cyclaniliprol, tetraniliprol, broflanilide, cyhalodiamide and tetrachloranthraniliprol; and insecticides that have a mode of action of the chitin biosynthetic inhibitor (such as buprofezin). In particular, dinotefuran, broflanilide and buprofezin are preferred.

[0030] Examples of the fungicides and bactericides include benalaxyl, benalaxyl M or kiralaxil, oxadixil, furalaxil, metalaxyl, metalaxyl M or mefenoxam, ofurace, benomil, carbendazim, fuberidazole, thiabendazole, thiophanate, thiophanoxam, zinc, tofanoxamide, zinc , fluopicolide, fenamacril, benodanil, benzovindiflupir, bixafen, boscalide, carboxin, fenfuram, fluopiram, flutolanil, fluxapiroxad, furametpir, isofetamide, isopirazam, mepronil, oxycarboxin, pentiopirifen, pyrofoxamine, pyrofoxamine, pyrofluoxamine, pyrofluidone , enoxastrobina, famoxadone, fenamidone, fenaminstrobina, flufenoxistrobina, fluoxastrobin, kresoxim-methyl, mandestrobina, metominostrobin, orysastrobin, pirametostrobina, trifloxystrobin, picoxystrobin, piribencarbe, cyazofamid, amisulbrom, binapacryl, piraoxistrobina, pyraclostrobin, triclopiricarbe, meptyldinocap, dinocap, fluazinam, ametoctradina , ciprodinil, mepanipirim, pirimetanil, streptomycin, blasticidin S, casugamycin, oxytetracycline, fenpiclonil, fludioxonil, quinoxyphene, proquinazide, clozolinate, dimethaclone, iprodione, procymidone, vincrozoline, edifenphos, iprobenphos, pyrazofos, isoprothiol, chlorohexan, chloride , propamocarb, protiocarb, azaconazole, bitertanol, bromoconazole, cyproconazole, diphenoconazole, diniconazole, diniconazole M, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fluquinconazole, quinconazole, flusilazon, methanol, hexagonal, flacil

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14/38 oxpoconazole, oxpoconazole fumarate, pefurazoate, penconazole, prochloraz, propiconazole, protioconazole, pirifenox, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triazimenol, triflumizon, triflumone, triflazole, triflazole, triflone phenpropidine, piperalin, spiroxamine, fenhexamide, fenpyrazamine, pyributicarb, naphthifine, terbinafine, polyoxins, dimetomorph, flumorfo, pyrimorph, bentiavalicarb, bentiavalicarb-isopropyl, iprovalicarbe, mandipropamide, valiphenyl, trifilicyanide, trifilicyanide, trifenylate acibenzolar-S-methyl, probenazole, thiadinyl, isothianil, laminarine, mancozeb ormanzeb, maneb, metiram, propineb, thiuram, zineb, ziram, ferbam, captan, captafol, folpet, fluorfolpet, guazatin, iminoctadine, iminoctadine, iminoctadine, trin, albin basic copper, copper cupric hydroxide, basic copper sulfate, compound d and organocopper, salt of copper dodecylbenzene sulfate bis (ethylenediamino) [II], sulfur, fluoroimide, chlorothalonil, diclofluanide, tolylfluanide, anilazine, dithianone, quinometionat, cotyledonous extracts of lupine seedlings (BLAD), diclobentha dipimethitrone, bupyrime, dimethyrimol, ethirimol, fentin acetate and rifeniltin chloride, triphenyltin hydroxide, oxolinic acid, himexazole, octylin, phosethyl, phosphoric acid, phosphoric acid sodium salts, phosphoric acid ammonium salts, phosphoric acid ammonium salts phosphorous acid, keyboardophthalam, triazoxide, flusulfamide, diclomedine, siltiofam, diflumetorim, metasulfocarb, cyflufenamide, metrafenone, pyriophenone, dodine, flutianil, ferimzone, oxathiaproline, tebufloquin, Nicaragua, picarbutrazox, 180 -2190, S-2367, inpirfluxam, fluindapyr, isoflucipram and aminopyrifene.

[0031] Examples of the combination of the pesticide (s) as active ingredient (s) (in the case of insecticides) include a combination of acetamipride and chloranthranilprol, a combination of acetamipride and

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15/38 cyantraniliprol, a combination of clothianidin and chlorantraniliprol, a combination of dinotefuran and chlorantraniliprol, a combination of dinotefuran and cyantraniliprol, a combination of dinotefuran and broflanilide (dinotefuran and buprofezin), a combination of thiamethoxy and thiamethoxy and thiamethoxy and thiamethoxy chlorantraniliprol and a combination of imidacloprid and flubendiamide. Examples of the fungicides include a combination of pentiopirad and captan and a combination of pentiopirad and quinofumelin. In the case of a combination of an insecticide and fungicide, examples of it include a combination of dinotefuran and hexaconazole, a combination of dinotefuran and azoxystrobin, a combination of dinotefuran and tifluzamide, 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 diphenoconazole. In particular, 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 glucopyranose hydroxyl group as a structural cellulose unit. 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, the alkali metal salt is preferred and the sodium salt is particularly preferred.

[0033] Examples of the commercialized product of the 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,

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CELLOGEN BSH-10 and CELLOGEN BSH-12 (all manufactured by DAIICHI 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, SUNROSE4, SUNROSE0 , 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 dialkyl naphthalene sulfonate formalin. Specific examples thereof include a monoalkyl naphthalene sulfonate formalin condensate, 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. In particular, the sodium salt is preferred as the alkyl naphthalene sulfonate.

[0035] Examples of the marketed 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.);

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17/38 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 at 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 the lignin sulfonate include an alkali metal salt, an alkaline earth metal salt, an ammonium salt and various amine salts. Among them, the alkali metal salt or the alkaline earth metal salt is preferred. In particular, 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 X SCL (all manufactured by Nippon Paper Co., Ltd.). [0038] The term "lactose" indicates a-hydrous lactose, a-anhydrous lactose, β-anhydrous lactose or the like.

[0039] The term "granular pesticidal formulation" indicates a granular pesticidal formulation that has an average particle diameter of about 30 pm to about 10,000 pm. Among them, water-dispersible granules, water-soluble granules, granular formulations and the like are preferred. In particular, water-dispersible granules or water-soluble granules are preferred.

[0040] The term "amorphous silica" is referred to as "silicic acid", "wet silica" or "synthetic silicic acid" and indicates an amorphous silica that has a Si-0 lattice structure and does not have a regular crystal structure .

[0041] Examples of the commercialized amorphous silica product include

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CARPLEX # 80, CARPLEX # 80D, CARPLEX # 67, CARPLEX # 1120, CARPLEX #XR and Sipemat22S (all manufactured by DSL. Japan Co., Ltd.); FINESEAL A, FINESEAL E-50, FINESEAL X-37, FINESEAL K-41, FINESEAL P-8, TOKUSEAL U, TOKUSEAL CU-N, TOKUSEAL P, TOKUSEAL NP, TOKUSEAL NR and TOKUSEAL GU-N (all manufactured by Tokuyama Corporation ); 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 for a competitive modulator of the nicotinic acetylcholine receptor (nAChR)” indicates a neonicotinoid-based compound (such as acetamipride, clothianidin, dinotefuran, imidacloprid, nitenpiram, thiaclopride or thiamethoxam), a butenolide-based compound (such as flupiradifurone), a mesoionic compound (such as triflumezopyrim), nicotine, nicotine sulfate, sulfoxaflor, dichloromezothiaz or flupirimine. Among them, the neonicotinoid compound is preferred. Particularly, dinotefuran is preferred.

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

[0044] The granular pesticidal formulation of the present invention includes:

(1) a pesticide as an active ingredient; (2) a carboxymethyl cellulose salt; and (3) an alkyl naphthalene sulfonate formalin condensate 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 (s) 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 an active ingredient (s) can be appropriately determined depending on the physical properties of the pesticide (s) as

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19/38 active ingredient (s) and conditions of use. The mixing ratio is preferably from 0.1 to 90% by weight, more preferably from 1 to 80% by weight and even more preferably from 10 to 70% by weight with reference to 100% by weight of the granular pesticidal formulation.

[0046] The "carboxymethyl cellulose salt" in the granular pesticidal formulation of the present invention is contained as a binder, an adhesive, a dispersant, a spreader, a thickener, a stabilizer, a water retainer or a colloid protection agent. The mixing ratio in the granular pesticidal 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 point of view of hardness, water absorptivity, disintegrability in water and dispersion stability of the formulation, 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 pesticidal formulation.

[0047] "The alkyl naphthalene sulfonate formalin condensate and lignin sulfonate" in the granular pesticidal 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 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 point of view of hardness, water absorptivity, disintegrability in water and dispersion stability of the formulation, 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

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100% by weight of the granular pesticide formulation.

[0048] The mixing ratio of the alkyl naphthalene sulfonate formalin condensate and the lignin sulfonate of the present invention 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 point of view of hardness, water absorption, disintegrability in water and dispersion stability of the formulation, 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 can be contained as an anti-caking agent, a flow modifier or an extender. The mixing ratio of the amorphous silica in the granular pesticidal formulation can be appropriately determined depending on the physical properties of the amorphous silica and the conditions of use. From the point of view of hardness, water absorption, disintegrability in water and stability of the dispersion of the formulation, the suppression of the formation of bubbles, the uniformity of the effect and the efficiency of production, 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 pesticidal formulation.

[0050] Note that in inventions of the related technique, 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 “white carbon” 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

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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. Amorphous silica in JP 2008-308447 A plays a role as an auxiliary agent used to crush pesticide raw materials. However, the amorphous silica of the present invention plays a role as a flow modifier during mixing, the paper and the amount of amorphous silica composition contained in the formulation are substantially different. Thus, in the present invention, amorphous silica does not need to be used to crush the raw materials for pesticides. In this way, the mixing ratio of amorphous silica in the granular pesticidal formulation can be less than the normal mixing ratio in the granular pesticidal formulation. Consequently, it is possible to increase the proportions of the pesticide (s) as an active ingredient (s) in the granular pesticide formulation, as well as other auxiliary agents as ingredients. In addition, according to the present invention, the mixing ratio of the amorphous silica can be adjusted to a certain value or less as previously described, while it is possible to prevent the disintegrability in water from deteriorating in a high humidity storage condition. Furthermore, it is possible to prevent deterioration in water from deteriorating in a high temperature storage condition.

[0051] The granular pesticidal formulation of the present invention does not contain lactose. In the present invention, the granular pesticidal formulation contains a surfactant of the alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate surfactant, while it is possible to maintain good disintegrability in water 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 a

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22/38 high temperature storage condition. Consequently, it is possible to increase the proportions of the pesticide (s) as an active ingredient (s) in the granular pesticide formulation, as well as other auxiliary agents as ingredients.

[0052] To the granular pesticidal formulation of the present invention, arbitrary components can be added in the range that does not confer 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, agents that adjust the 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 flask, silicon carbide, zirconium sand, zirconium, zirconium powder, aluminum hydroxide, zeolite, glass powder quartz, sodium bentonite, sodium montmorillonite, feldspar powder, ceramic stone, haloisite, borax, magnesia, tree section clay, agalmatolite, perlite, cement, calcium carbonate, mica, kaolin clay, talc, pagodite , soapstone, glass bead, alumina, calcium phosphate, tabular wicker, walastonite, precipitated calcium carbonate, synthetic hydrotalcite, synthetic mica, heavy calcium carbonate, calcined clay, silk powder, slaked lime, s elenite, calcium carbonate, ultrafine particulate zinc oxide, precipitated barium sulfate, powdered dolomite, nylon powder, 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

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23/38 produced by the chloride method, oil-fired carbon black, yellowish chrome, yellow iron oxide, phosphorus oxide, yellow cadmium, red cadmium, oversea, fluorescent pigment, graphite, black iron oxide, carbonate ultrafine calcium, cobalt blue, cobalt green, cobalt purple, coal, iron blue, thermal black, chromium oxide, titanium oxide (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 powder graphite, natural earth 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, alkyl phosphate, polyoxyalkylene ethoxyl alkylene. Examples of the salts of surfactants 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, alkyl polyglycoside 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 salt

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24/38 dimethyl benzyl ammonium and an alkyl dimethyl aminopropyl amide. Examples of the salts of surfactants include halogen, such as chlorine and bromine.

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

[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 oil, castor oil, flax seed oil, oil paraffin, 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, cyclohexanone, 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 (where 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 antifungal include sorbic acid, potassium sorbate, parachloromethaxylenol, sodium dehydroacetate, polyhexamethylene biguanide hydrochloride, methyl 1,2-benzothiazolin-3-one, methyl hydroxybenzoate, p-hydroxy ethyl, p-hydroxybenzoate

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25/38 propyl, butyl p-hydroxybenzoate, heptyl p-hydroxybenzoate, benzyl phydroxybenzoate, p-hydroxybenzonate, orthophenylphenol, sodium orthophenylphenate, glutardialdehyde, quaternary ammonium compounds, tri- (N-chlorohexylalysium) tetrahydro-3,5-dimethyl-2H-1, 3,5 thiadiazin-2-thione, 2,5-dimethoxytetrahydrofuran, dimethylolurea, sodium N-methyldithiocarbamate, phenoxyethanol, glyoxal, glutaraldehyde, l, 3,5- tris (2hydroxyethyl) -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, diamonium 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, styrene-acrylate copolymers, methyl-butadiene methacrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, acrylates and copolymers such as silicones and acrylates and such polymers and silicones. polyurethane and polyurea.

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

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26/38 silicone (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 perfumes include lavender oil, jasmine oil, rose oil, lemon oil, orange oil, mint oil, thyme oil, iris oil, fennel oil, Cryptomeria japonica oil, Hiba oil , cypress oil, eucalyptus oil, camphor, mint oil, mint oil, geranium, same citrone, eugenol, limonene, tangerine oil, bitter orange peel and citronellol.

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

[0071] According to the method of producing the granular pesticidal formulation of the present invention, a mixture for the granular pesticidal 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 granulated substance

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The resulting 27/38 is dried and subjected to particle size regulation, while producing the granular pesticidal formulation of the present invention. The mixing method and the order of mixing 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 disk compaction-type extrusion granulator, a granule-type extrusion granulator, a basket-type extrusion granulator, a granulator extrusion granulator, oscillatory extrusion granulator, gear extrusion granulator and ring mold extrusion granulator.

[0074] In the production method, the pesticide (s) as active ingredient (s) in liquid or solid form can be mixed in advance 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 can be bonded or attached to the clay minerals and water-soluble fillers or polymers before use and can be formed in microcapsules using latexes and emulsions, before use. Additionally, the pesticide (s) as active ingredient (s) in liquid or solid form can be used after being dissolved or suspended in water, a solvent or an oil.

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

[0076] The granular pesticidal formulation of the present invention is used

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28/38 to prevent harmful organisms or regulate plant growth depending on the pesticide (s) as active ingredient (s) contained therein. When the pesticide (s) as an active ingredient (s) contained in the granular pesticidal formulation of the present invention is (are) insecticides, it can be used, for example, as insecticides for vegetables or orchards.

[0077] The granular pesticidal formulation of the present invention is used as follows. For example, the granular pesticidal formulation of the present invention is diluted with water and sprayed on the crop or soil by means of a sprinkler. The increase in dilution of the granular pesticidal 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 pesticidal formulation of the present invention, as well as as the type of harmful organisms and the conditions of use and is usually 10 to 10,000 times.

[Examples] [0078] Hereinafter, the granular pesticidal formulation for use in the present invention will be specifically described with reference to the Comparative Examples and 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 sodium 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 (AEROLE CT-1, TOHO Chemical Industry Co., Ltd.) and 20.0 parts by weight of a clay (KAOLIN HA, SANYO CLAY Co.,

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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 extruder that was equipped with a screen that has 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 pm sieve was placed on top of an underlying 500 pm sieve, thus obtaining a granular pesticide formulation of Example 1.

[Example 2] [0080] 50.0 parts by weight of pentiopirad, 1.0 parts by weight of sodium carboxymethyl cellulose (CELLOGEN 7A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 5.0 parts by weight of sodium naphthalene sulphonate formalin condensate (DEMOL RN, Kao Corporation.), 4.0 parts by weight of magnesium lignin sulfonate (San X SCL, Nippon Paper Co., Ltd.), 1.0 parts by weight of sodium dialkyl sulfosuccinate (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 extruder that was equipped with a screen that has 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 pm sieve was placed on top of an underlying 500 pm 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

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30/38 broflanilide, 1.0 part by weight of sodium carboxymethyl cellulose (CELLOGEN 5A, DAI-ICI KOGYO SEIYAKU Co., Ltd.), 3.0 parts by weight of sodium naphthalene sulphonate alkyl 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 extruder that was equipped with a screen that has opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 80 ° C, the dried granules were selected by stirring through a set of screens composed of sieves in which a sieve of

1,180 pm was placed on top of an underlying 500 pm sieve, thereby obtaining a granular pesticidal formulation from 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 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 part 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

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31/38 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 extruder that was equipped with a screen that has opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 80 ° C, the dried granules were selected by stirring through a set of screens composed of sieves in which a sieve of

1,180 μτη was placed on top of an underlying 500 μπι sieve, thus obtaining a granular pesticidal formulation from 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 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 extruder that was equipped with a screen that has 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 pm sieve was placed on top of an underlying 500 pm sieve, thus obtaining a granular pesticide formulation of Example 5.

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32/38 [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 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 part 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 extruder that was equipped with a screen that has opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 70 ° C, the dried granules were selected by stirring through a set of screens composed of sieves in which a sieve of

1,180 pm was placed on top of an underlying 500 pm sieve, thereby obtaining a granular pesticidal formulation from 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 Sodium alkyl naphthalene formalin condensate (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 part by weight of sodium dialkyl sulfosuccinate (NEWKALGEN EX-70, TAKEMOTO OIL & FAT Co., Ltd.), 29.5 parts by weight of a clay (KAOLIN S400, LORWATTANA Co., Ltd.) and 6.0 parts by weight of amorphous silica

Petition 870190024549, of 03/14/2019, p. 8/8

33/38 (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 extruder that was equipped with a screen that has 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 pm sieve was placed on top of an underlying 500 pm 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 sodium naphthalene sulfonate formalin condensate (NEWKALGEN PS-P, TAKEMOTO OIL & FAT Co., Ltd.), 4.0 parts by weight of sodium lignin sulfonate (VANILLEX N, Nippon Paper Co., Ltd. ), 1.0 parts by weight of sodium dialkyl sulfosuccinate (NEWKALGEN EX-70, TAKEMOTO OIL & FAT Co., Ltd.), 35.0 parts by weight of lactose (Meggletosis 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 extruder that was equipped with a screen that has 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 pm sieve was placed on top of an underlying 500 pm sieve, thus obtaining a granular pesticide formulation of Example

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Comparative 34/38 1.

[Comparative example 2] [0087] 60.0 parts by weight of dinotefuran, 3.0 parts by weight of sodium naphthalene sulfonate formalin condensate (NEWKALGEN PS-P, TAKEMOTO OIL & FAT Co., Ltd.), 3.0 parts by weight of sodium lignin sulfonate (VANILLEX N, Nippon Paper Co., Ltd.), 1.0 parts by weight of sodium dialkyl sulfosuccinate (AEROLE CT1L, 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 extruder that was equipped with a screen that has 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 prn sieve was placed on top of an underlying 500 μτη 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 sodium 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.), 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

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35/38 resulting mixture was kneaded. The kneaded product thus obtained was granulated by means of a screw-type extruder that was equipped with a screen that has 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 pm sieve was placed on top of an underlying 500 pm 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 sodium naphthalene sulfonate formalin condensate (MORWET D500 POWDER, Akzo Nobel Surface Chemistry AB.), 1.0 part by weight of 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 extruder that was equipped with a screen that has opening holes of 0.8 mm in diameter. The granules thus obtained were dried at 70 ° C, the dried granules were selected by stirring through a set of screens composed of sieves in which a sieve of

1,180 pm was placed on top of an underlying 500 pm sieve, thereby obtaining a granular pesticidal formulation from Comparative Example 4.

[Test example] (Water disintegration test) [0090] In this test, the granular pesticidal formulations that were obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were used.

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36/38

Each test sample of the granular pesticidal formulations was prepared to perform the disintegrability test in water immediately after production, stored for 14 days in a thermostat set at 54 ° C and stored for 7 days in a thermo-hygrostat 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 therein in the official pesticide inspection method. Then, the cylinder was repeatedly inverted at a rate of once for 2 seconds. The number of times the cylinder was inverted, which was necessary until each test sample of the granular pesticide formulations was completely disintegrated and did not maintain the shape of the granules in water, was counted. If the inversion count is small, the sample of granular pesticidal formulations was rapidly disintegrated in water and had good disintegrability in water. In this test, the test sample that has the inversion count less than or equal to 20 times 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

Granular pesticide formulation under investigation Immediately after production After being stored at 54 ° C for 14 days After being stored at 30 ° C and 80% RH for 7 days Example 1 12 12 12 Example 2 14 15 15 Example 3 13 16 17 Example 4 13 17 17 Example 5 13 16 17 Example 6 13 13 13 Example 7 14 15 15 Comparative example 1 28 > 50 45 Comparative example 2 14 17 21 Comparative example 3 22 29 29 Comparative example 4 15 17 21

[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

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37/38 granular pesticidal formulation of the present invention including: (1) a pesticide as an active ingredient; (2) a carboxymethyl cellulose salt; and (3) an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate; and not including (4) lactose can maintain good disintegrability in water in a high humidity storage condition. Furthermore, the granular pesticidal formulation of the present invention can maintain good disintegrability in water in an immediate condition after production and in a high temperature storage condition. In addition, as in Examples 1, 2 and 6, in the case of the granular pesticidal formulation which has an amorphous silica mixture ratio of 0% by weight, it is possible to prevent the disintegrability in water 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 pesticidal formulation that contains none of (2) a carboxymethyl cellulose salt and (3) an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate or formulation granular pesticide containing (4) lactose had an inversion times count greater than 20 in a high humidity storage condition. In addition, the granular pesticidal formulation of Comparative Examples 1 and 3 had an inversion times count greater than 20 in immediate condition after production and in a high temperature storage condition. The granular pesticidal 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 pesticidal formulation that maintains good disintegrability in water in a successive condition in high humidity. Furthermore, it is possible to obtain a granular pesticide formulation that maintains good disintegrability in water in an immediate condition after its production and in a successive condition at high temperature. The granular pesticide formulation is useful as

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38/38 a pesticide formulation that is suitable for use in various crops without being restricted by the climatic conditions of the area where the pesticide formulation is used, for example, in a condition of high temperature and / or high humidity.

Claims (11)

1. Granular pesticide formulation, characterized by the fact that it comprises: (1) a pesticide as an active ingredient; (2) a carboxymethyl cellulose salt; and (3) an alkyl naphthalene sulfonate formalin condensate and a lignin sulfonate; and which does not comprise (4) lactose. Granular pesticidal formulation according to claim 1, characterized in that it further comprises an amorphous silica in a mixture ratio of 0 to 5% by weight. Granular pesticidal formulation according to claim 1 or 2, characterized in that the mixing ratio of the amorphous silica is 0% by weight. Granular pesticidal 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 mechanism of action for a competitive modulator of the nicotinic acetylcholine receptor (nAChR) ). Granular pesticidal formulation according to any one of claims 1 to 4, characterized by the fact that at least one pesticide contained as the active ingredient is a neonicotinoid insecticide. Granular pesticidal formulation according to claim 4 or 5, characterized by the fact that at least one pesticide contained as the active ingredient is dinotefuran. Granular pesticidal formulation according to any one of claims 1 to 6, characterized in that the carboxymethyl cellulose salt is sodium carboxymethyl cellulose. Granular pesticidal formulation according to any one of claims 1 to 7, characterized in that the alkyl naphthalene sulfonate formalin condensate is an alkyl naphthalene sulfonate formalin condensate. Petition 870180141018, of 10/15/2018, p. 45/47 2/2 Granular pesticidal formulation according to any one of claims 1 to 8, characterized in that the lignin sulfonate is sodium lignin sulfonate. Granular pesticidal 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 the carboxymethyl cellulose salt; (3) 2 to 20% by weight of the alkyl naphthalene sulfonate formalin condensate; and 2 to 20% by weight of lignin sulfonate. Granular pesticidal formulation according to any one of claims 1 to 10, characterized in that the mixing ratio of the alkyl naphthalene sulfonate formalin condensate to the lignin sulfonate is from 1: 9 to 9: 1.