Coated pesticide composition

Abstract

To provide a coated agrochemical composition which suppresses initial elution of an agrichemical active component and is excellent in elution after a predetermined period has elapsed, and accordingly can control an elution amount of the agrichemical active component at a desired timing and reduces occurrence of chemical injury due to the agrichemical active component and is excellent in effect development of the agrichemical active component.SOLUTION: A coated agrochemical composition includes a solid granular composition containing an agrichemical active component (a), and a coating layer which coats the surface of the solid granular composition and contains a resin (i) and a polyvalent metal compound (ii), wherein the polyvalent metal compound (ii) is at least one selected from an aluminum compound, a titanium compound, a zinc compound and a zirconium compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a coated solid pesticide composition. [Background technology]

[0002] In recent years, the agricultural field has been in need of the development of pesticide formulations aimed at reducing costs and labor. To achieve cost reduction, there is a demand for highly productive production of formulations with excellent performance. To achieve labor savings, there is also a demand for formulations that reduce the amount and frequency of pesticide application. Under these circumstances, the seedling box application method, in which pesticides are applied to seedling boxes prior to planting, has become increasingly popular for paddy rice pesticides. This application method allows pesticide active ingredients that previously were not effectively absorbed by plants due to runoff into the environment, etc., to be efficiently absorbed by plants, enabling long-term plant concentrations to be maintained with a small amount of active ingredient, leading to reduced costs and environmental impact. Furthermore, this application method is labor-saving and ideal, as it eliminates the need for workers to enter paddy fields and carry heavy sprayers to spray pesticides, as was previously done.

[0003] However, in such application methods, formulations that release the pesticidal active ingredient over a short period of time can cause problems such as a shortened duration of efficacy, phytotoxicity, etc. Generally, pests in paddy fields occur over a long period of time after rice planting, so it is necessary to control the release of the pesticidal active ingredient from the pesticide formulation over the long term. For this reason, various attempts have been made to date with regard to formulations or methods for producing such formulations for sustained release, in which the pesticidal active ingredient is gradually released, but the sustained release of the pesticidal active ingredient has not always been satisfactory.

[0004] To solve this problem, a time-controlled release coated pesticide composition has been proposed in which pesticide granules with a swelling capacity of 1 to 30 mL / 2 g upon water absorption are coated with a coating material containing a thermoplastic resin as an active ingredient (Patent Document 1). However, after the coated pesticide composition is sprayed on paddy fields or the like, the pesticide granules may suddenly swell, causing the coating to break down, resulting in insufficient initial release control and resulting in phytotoxicity or insufficient efficacy. Another example of a method for producing such a coated pesticide composition is to coat the surface of a pesticide granule consisting of a pesticidal active ingredient and a water-swellable substance with a coating primarily composed of a thermoplastic resin. However, because volatile organic compounds are used, these compounds can cause health hazards such as pollution if released into the environment. Therefore, production equipment is required to recover the solvent when the solvent is removed from the surface of the pesticide granules and then dried, which is not desirable for pesticide manufacturers.

[0005] Another example of a method that does not use volatile organic compounds as plasticizers is a sustained-release pesticide granule (Patent Document 2), in which a core granule containing an active ingredient in a pesticide is coated with a coating material made of a thermoplastic resin and iron or copper powder. According to this technology, dissolution is suppressed for approximately five days after treatment, and the presence of water molecules accelerates oxidation of the iron or copper powder, causing it to increase in volume, which then destroys the coating, initiating dissolution. However, rust on the surface of the iron or copper powder forms a film that prevents oxidation from progressing, preventing the volume from increasing enough to destroy the film. On the other hand, if the coating is thickened to extend the period during which dissolution is suppressed, the dissolution rate after the start of dissolution becomes very slow, and dissolution may not be completed within the growth period, making it difficult to control dissolution. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 11-322503 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-363004 Summary of the Invention [Problem to be solved by the invention]

[0007] As described above, the techniques described in these patent documents do not adequately control the release of the pesticide active ingredient, and have had problems with the occurrence of phytotoxicity caused by the pesticide active ingredient and the manifestation of the effect of the pesticide active ingredient. [Means for solving the problem]

[0008] In order to solve these problems, the present inventors have conducted extensive research and found that the above problems can be solved by adding a specific component to the coating layer of a solid granular composition (agricultural chemical granules).

[0009] That is, the present invention is as follows. [1] A solid granular composition containing an agrochemically active ingredient (a); a coating layer containing a resin (i) and a polyvalent metal compound (ii) that coats the surface of the solid granular composition; Equipped with The coated pesticide composition, wherein the polyvalent metal compound (ii) is at least one selected from aluminum compounds, titanium compounds, zinc compounds, and zirconium compounds. [2] The coated pesticide composition according to [1], wherein the polyvalent metal compound (ii) is a zirconium compound. [3] The coated pesticide composition according to [1] or [2], wherein the solid granular composition further contains a swelling agent (b). [4] The coated pesticide composition according to [3], wherein the swelling agent (b) is at least one selected from the group consisting of bentonite, starch, and cellulose derivatives. [5] The coated pesticide composition according to any one of [1] to [4], wherein the resin (i) is a copolymer of one or more monomers selected from acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters. [Effects of the Invention]

[0010] The coated pesticide composition of the present invention suppresses the initial elution of the pesticidal active ingredient and exhibits excellent elution after a predetermined period of time, making it possible to control the elution amount of the pesticidal active ingredient at a desired timing, thereby reducing the occurrence of phytotoxicity caused by the pesticidal active ingredient and exhibiting excellent effects of the pesticidal active ingredient. Furthermore, the coated pesticide composition of this embodiment has excellent stability over time, with little change in the elution start timing or elution rate even after aging, resulting in excellent product quality stability. DETAILED DESCRIPTION OF THE INVENTION

[0011] The coated pesticide composition of the present invention will be described below based on embodiments. Note that "to" indicates "more than" to "less than" unless otherwise specified.

[0012] The coated pesticide composition of the present embodiment is A solid granular composition containing an agrochemically active ingredient (a); and a coating layer covering the surface of the solid granular composition, the coating layer containing a resin (i) and a polyvalent metal compound (ii), wherein the polyvalent metal compound (ii) is at least one selected from aluminum compounds, titanium compounds, zinc compounds, and zirconium compounds.

[0013] The coated pesticide composition of this embodiment has controlled elution, suppressing the initial elution of the pesticidal active ingredient, and after a predetermined period of time has passed, the elution of the pesticidal active ingredient is excellent and the elution rate is fast (timed-release type), so it is possible to control the elution amount of the pesticidal active ingredient at the desired timing. This reduces the occurrence of phytotoxicity caused by the pesticidal active ingredient and provides excellent efficacy of the pesticidal active ingredient. Furthermore, the coated pesticide composition of this embodiment has excellent stability over time, with little change in the elution start timing or elution rate even after aging, resulting in excellent product quality stability.

[0014] [Solid granular composition] In this embodiment, the solid granular composition contains an agriculturally active ingredient (a). The agriculturally active ingredient (a) may be of any type as long as it is effective against pests. The proportion of the pesticidal active ingredient (a) is not particularly limited, but the amount of pesticide treatment required to exert its effect increases. Therefore, the proportion is usually 0.1 to 80% by weight, more preferably 0.5 to 70% by weight, relative to 100% by weight of the solid granular composition.

[0015] For example, herbicides, insecticides, miticides, nematicides, fungicides, bactericides, etc. may be blended, and there are no particular limitations on the physical properties of the compounds themselves. The composition of this embodiment may contain one of these pesticide active ingredients or two or more pesticide active ingredients exceeding the types of pesticide active ingredients. Specific examples of pesticide active ingredients are given below, but the present invention is not limited to these.

[0016] Examples of the herbicides include butroxydim, profoxydim, clethodim, tepraloxydim, tralkoxydim, sethoxydim, cycloxydim, propaquizafop, quizalofop, haloxyfop, fluazifop-butyl, fluazifop-P-butyl, cyhalofop-butyl, clodinafop-propargyl, diclofop-methyl, fenoxaprop-P-ethyl, amidosulfuron, azimsulfuron, trifloxysulfuron, bensulfuron-methyl, cyclosulfamuron, flupyrsulfuron-methyl, formasulfuron, and chlorifop-methyl. Muron ethyl, ethametsulfuron methyl, halosulfuron methyl, nicosulfuron, chlorsulfuron, ethoxysulfuron, imazosulfuron, oxasulfuron, pyrazosulfuron ethyl, tritosulfuron, cinosulfuron, flazasulfuron, iodosulfuron methyl, primisulfuron methyl, rimsulfuron, thifensulfuron methyl, mesosulfuron methyl, metsulfuron methyl, prosulfuron, triasulfuron, triflusulfuron methyl, sulfosulfuron, tribenuron methyl, trifloxysulfuron, flucarbazone, Propoxycarbazone, bispyribac, pyribenzoxim, pyrithiobac, pyriftalid, pyriminobac-methyl, cloransulam-methyl, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, imazapic, imazapyr, imazamethabenz-methyl, imazaquin, imazamox, imazethapyr, desmedipham, phenmedipham, bromacil, lenacil, terbacil, metabentiazuron, chlorotoluron, fluometuron, isoproturon, isouron, diuron, linuron, tebuthiuron, hexazinone, meta Mitron, metribuzin, ametryn, atrazine, dimethamethryn, cyanazine, prometryn, simazine, simetryn, paraquat, diquat, acifluofen, bifenox, fomesafen, lactofen, oxyfluorfen, carfentrazone ethyl, sulfentrazone, oxadiargyl, oxadiazon, butafenacil, saflufenacil, pyrazolate, pyrazoxyfen, benzofenap, topramezone, pyrasulfotol, tolpyralate, mesotrione, sulcotrione, benzobicyclon, tefuryltrione,Tembotrione, bicyclopyrone, fenquinotrione, lancotrione, glyphosate, glufosinate, bialaphos, benfluralin, ethalfluralin, pendimethalin, butralin, oryzalin, trifluralin, acetochlor, butachlor, alachlor, dimethachlor, dimethenamid, propachlor, thenylchlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, petoxamide, benthiocarb, butyrate, esprocarb, molinate, dimepiperate, orbencarb, prosulfocarb, triallate, triclopyr, clopyralid, fluroxypyr, picloram, quinclorac, quinmerac, clomeprop, MCPA, MCPB, 2,4-D, ioxynil, bromoxynil, dichlobenil, Examples of such antibacterial agents include amicarbazone, chloridazon, bentazone, carbutilate, propanil, pyridate, pyraflufenethyl, cinidonethyl, flumiclorac pentyl, flumioxazin, picolinafen, aclonifen, fluridone, norflurazon, diflufenican, beflubutamide, flurochloridone, flurtamone, isoxaflutole, clomazone, asulam, dithiopyr, thiazopyr, dicamba, benazolin, diflufenzopyr, naptalam, napropamide, tetrapion, pinoxaden, pyroxasulfone, fenoxasulfone, ipfencarbazone, indaziflam, aminocyclopyrachlor, halaxifenmethyl, florpyrauxifenbenzyl, thiafenacil, trifludimoxazine, and cyclopyrimorate.

[0017] Examples of the insecticides, acaricides and nematicides include phosphocarb, alanycarb, butocarboxim, butoxycarboxim, thiodicarb, thiofanox, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, trimethacarb, XMC, alixicarb, aldoxycarb, and bufencarb. , butacarb, carbanolate, metolcarb, xylylcarb, fenothiocarb, xylylcarb, bendiocarb, acephate, azamethiphos, azinphos-methyl, azinphos-ethyl, ethephon, cadusafos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, diclofenthion, dichlorvos, dicrotophos, dimethoate, dimethylvinphos, disulfoton, O-ethyl O-4-nitrophenyl Phenylphosphonothioate, Ethion, Ethoprophos, Famfur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Isofenphos-methyl, Isocarbophos, Isoxathion, Malathion, Mecarbam, Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimiphos-methyl, Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyridaf Enthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, thiometon, triazophos, trichlorfon, vamidothion, chlorthion, bromfenvinphos, bromophos, bromophos-ethyl, butathiophos, carbophenothion, chlorphoxim, sulprofos, diamidaphos, tetrachlorvinphos, propafos, mesulfenphos, dioxabenzophos, etrimphos, oxydeprofos, formothion, fensulfothion, isazophos, imicyaphos, isamidophos, thionazine, fosthietane, chlordane, endosulfan, lindane,Dienochlor, Ethiprole, Fipronil, Acetoprole, Allethrin [(1R)-isomer], Bioallethrin, Bioallethrin S-cyclopentenyl isomer, Bioresmethrin, Beta-cyfluthrin, Gamma-cyhalothrin, Lambda-cyhalothrin, Alpha-cypermethrin, Beta-cypermethrin, Ceta-cypermethrin, Zeda-cypermethrin, Cyphenothrin [(1R)-trans-isomer], Deltamethrin, Empenthrin [(EZ)-(1R)-isomer], Esfenvalerate, Flumethrin, Tau-fluvalinate, Halfenprox, Imiprothrin, Metothrin, Metofluthrin, Epsilon-metofluthrin, Mo Fluorothrin, epsilon-monfluorothrin, fenothrin [(1R)-trans-isomer], prallethrin, resmethrin, kadethrin, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer], transfluthrin, etofenprox, ZXI8901, biopermethrin, furamethrin, profluthrin, flubrocythrinate, dimefluthrin, DDT, methoxychlor, fenothrin, clothianidin, imidacloprid, thiacloprid, dinotefuran, nicotinamide nicotine, nicotine sulfate, sulfoxaflor, flupyradifurone, triflumezopyrim, spinosad, spinetoram, abamectin, emamectin benzoate, lepimectin, milbemectin, hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen, methyl bromide, chloropicrin, cryolite, sulfuryl fluoride, borax, boric acid, disodium octaborate, sodium metaborate, tartar emetic, dazomet, metam, carbam sodium, pymetrozine, pyrifluquinazone, cloric acid, methyl bromide, methyl benzoate ... Fentezine, diflobidazine, hexythiazox, etoxazole, diafenthiuron, azocyclotine, cyhexatin, fenbutatin oxide, "c-12.5" propargite, "c-12.6" tetradifon, chlorfenapyr, DNOC, binapacryl, sulfuramide, bensultap, cartap hydrochloride, thiocyclam, monosultap, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,Noviflumuron, teflubenzuron, triflumuron, buprofezin, cyromazine, chromafenozide, halofenozide, methoxyfenozide, tebufenozide, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, bifenazate, fenazaquin, fenpyroximate, pyridaben, pyrimidifen, tebufenpyrad, tolfenpyrad, rotenone, indoxacarb, metaflumizone, spirodiclofen, spiromesifen, spirotetramat, aluminum phosphide, calcium phosphide, hydrogen phosphide, sulfur phosphide Lead, calcium cyanide, sodium cyanide, potassium cyanide, cyenopyrafen, cyflumetofen, piflubumid, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirachtin, benzoximate, phenisobromorate, chinomethionate, dicofol, pyridalyl, bromopropylate, triazamate, dicyclanil, dinobuton, dinocap, hydrogen cyanide, methyl iodide, karanjin, mercury chloride, methyl isothiocyanate, pentachlorophenol, phosphine, piperonyl Butoxide, Polynactin Complex, Sabadilla, Sulcofuron Salt (Sulcofuron-Sodium), Tribufos, Aldrin, Amidithione, Amidothioate, Aminocarb, Amiton, Aramite, Atidathion, Azotoate, Polysulfide Barium, Benclothiaz, 5-(1,3-Benzodioxol-5-yl)-3-hexylcyclohex-2-enone, 1,1-Bis(4-chlorophenyl)-2-ethoxyethanol, Butonate, Butopyronoxyl, 2-(2-Butoxyethoxy)ethyl Thiocyanate, camphechlor, chlorbeneside, chlordecone, chlordimeform, chlorphenetole, chlorfenson, fluazuron, metaldehyde, bialaphos, levamisole hydrochloride, amidoflumet, pyrafluprole, pyriprole, tralopyril, flupyrazophos, diofenolan, chlorbenzilate, flufenzin, benzomate, flufenerim, albendazole, oxibendazole, fenbendazole, metam sodium, 1,3-dichloropropene, flometoquin, cyclaniliprole, tetratraniliprole, brofuranilide, dichloromezothiazol, ethylene dibromide,Acrylonitrile, bis(2-chloroethyl) ether, 1-bromo-2-chloroethane, 3-bromo-1-chloroprop-1-ene, bromocyclen, carbon disulfide, carbon tetrachloride, nemadectin, cymiazole, calcium Polysulfides, cytokinin, 2-(octylthio)ethanol, potassium oleate, sodium oleate, machine oil, tar oil, anabasine, morantel tartrate, pyrethrin, rapeseed oil, soybean lecithin, starch, hydroxypropyl starch, fatty acid glycerides, propylene glycol mono-fatty acid esters, diatomaceous earth, afoxolaner, fluazaindolizine, afidopiropen, cyhalodiamide, thioxazafen, fluhexafon, fluralaner, fluxamethamide, tetrachlorantraniliprole, 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, oxazosulfil, chloroprallethrin, benzpyrimoxane, acinonapyr, spiropyridione, flupirimine, cyclopyrazoflurane, etc.

[0018] Examples of the fungicides and bactericides include benalaxyl, benalaxyl M or chiralaxyl, oxadixyl, furalaxyl, metalaxyl, metalaxyl M or mefenoxam, ofurase, benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate, thiophanate methyl, diethofencarb, zoxamide, ethaboxam, pencycuron, fluopicolide, fenamacryl, benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluphenoxam ... Xapyroxad, furametpyr, isofetamide, isopyrazam, mepronil, oxycarboxin, penthiopyrad, penflufen, pydiflumetofen, sedaxane, thifluzamide, pyraziflumide, azoxystrobin, cumoxystrobin, dimoxystrobin, enoxastrobin, famoxadone, fenamidone, phenaminestrobin, flufenoxystrobin, fluoxastrobin, kresoximmethyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pirametostrobin Vin, pyraoxystrobin, pyribencarb, triclopiricarb, trifloxystrobin, cyazofamid, amisulbrom, binapacryl, meptyldinocap, dinocap, fluazinam, ametoctrazine, cyprodinil, mepanipyrim, pyrimethanil, streptomycin, blasticidin S, kasugamycin, oxytetracycline, fenpiclonil, fludioxonil, quinoxyfen, proquinazide, chlozolinate, dimethaclon, iprodione, procymidone, vinclozolin, edifenphos, iprobenfos, pyra Zophos, isoprothiolane, biphenyl, chloroneb, dicloran, quintozene, tecnazene, tolclofos-methyl, etridiazole, iodocarb, propamocarb, prothiocarb, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole M, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fluquinconazole, quinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole,Metconazole, myclobutanil, nuarimol, oxpoconazole, oxpoconazole fumarate, pefurazoate, penconazole, prochloraz, propiconazole, prothioconazole, pyrifenox, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triforine, triticonazole, mefentrifluconazole, ipfentrifluconazole, aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, piperaline, Spiroxamine, fenhexamid, fenpyrazamine, pyributicarb, naftifine, terbinafine, polyoxins, dimethomorph, flumorph, pyrimorph, benthiavalicarb, benthiavalicarb isopropyl, iprovalicarb, mandipropamid, valifenalate, fthalide, pyroquilon, tricyclazole, carpropamid, diclocymet, fenoxanil, tolprocarb, acibenzolar-S-methyl, probenazole, tiadinil, isotianil, laminarin, mancozeb or mancozeb, maneb, metiram, propineb , thiuram, zineb, ziram, ferbam, captan, captafol, folpet, fluorofolpet, guazatine, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, basic copper chloride, cupric hydroxide, basic copper sulfate, organic copper compounds, dodecylbenzenesulfonic acid bisethylenediamine copper complex salt [II], sulfur, fluorimide, chlorothalonil, dichlofluanid, tolylfluanid, anilazine, dithianon, chinomethionate, extract from cotyledons of lupin seedlings (BLAD), dichlobenthiazox, fenpicox Samid, dipimethitron, bupirimate, dimethirimol, ethirimol, triphenyltin acetate, triphenyltin chloride, triphenyltin hydroxide, oxolinic acid, hymexazole, octhilinone, fosetyl, phosphorous acid, sodium salt of phosphorous acid, ammonium salt of phosphorous acid, potassium salt of phosphorous acid, tecloftalam, triazoxide, flusulfamide, diclomedine, silthiofam, diflumetrim, metasulfocarb, cyflufenamid, metrafenone, pyriophenone, dodine, fluthianil, ferimzone, oxathiapiproline,Examples include tebufloquine, picarbutrazox, validamycins, cymoxanil, quinofumelin, NC-241, NF-180, S-2190, S-2367, impilfluxam, fluindapyr, isoflucipram, and aminopyrifen.

[0019] The solid granular composition of this embodiment may further contain a swelling agent (b). By adjusting the type and amount of swelling agent (b), the dissolution rate of the active ingredient after the start of dissolution can be adjusted.

[0020] The swelling agent (b) may be any agent that increases in volume when it absorbs water, such as bentonite, starch and derivatives, cellulose and derivatives, hyaluronic acid, agarose, collagen, and other proteins, and synthetic polymers such as polyvinyl alcohol polymers, acrylic polymers, other maleic anhydride polymers, vinylpyrrolidone polymers, polyether polymers, and condensation polymers. Of these, bentonite, starch and derivatives, and cellulose and derivatives are preferred from the standpoint of cost.

[0021] The solid granular composition of the present embodiment may contain optional components within the range that does not impair the effects of the composition, such as surfactants, colorants, solvents, oils, sugars, water-soluble polymers, inorganic salts, UV filters, and fragrances.

[0022] The surfactant may be one or more selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants that are commonly used in agricultural chemicals, and may be used in combination.

[0023] Examples of nonionic surfactants include ether type, ester type, ester ether type, and nitrogen-containing type. Examples of ether type nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polystyrylphenyl ether, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene allylphenyl ether. Examples of ester type nonionic surfactants include glycerin fatty acid partial ester, sorbitan fatty acid ester, pentaerythritol fatty acid ester, propylene glycol monofatty acid ester, and sucrose fatty acid ester.

[0024] Examples of ester ether type nonionic surfactants include polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, and polyoxyethylated castor oil.

[0025] Examples of nitrogen-containing nonionic surfactants include fatty acid diethanolamides, N,N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, and trialkylamine oxides.

[0026] Anionic surfactants include carboxylates, sulfonates, sulfates, phosphates, polymerized polymers, polycondensation polymers, etc. Examples of carboxylate anionic surfactants include aliphatic monocarboxylates, N-acyloyl sarcosinates, N-acyloyl-β-alanines, N-acyloyl glutamates, and abietic acid salts.

[0027] Examples of sulfonate-type anionic surfactants include dialkyl sulfosuccinates, alkane sulfonates, hydroxyalkane sulfonates, linear alkylbenzene sulfonates, alkyl (branched) benzene sulfonates, alkyl naphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkylphenol sulfonates, naphthalene sulfonate-formaldehyde condensates, sodium N-methyl-N-oleyl taurate, N-alkyl sulfosuccinate monoamide disodium salt, and petroleum sulfonates.

[0028] Examples of sulfate salt-type anionic surfactants include sulfated castor oil, sulfated oxfoot oil, sulfate salts of fatty acid alkyl esters, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, fatty acid monoglyceride sulfate salts, polyoxyethylene alkyloylamide sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, polyoxyethylene styrylphenyl ether sulfate salts, and polyoxyethylene allylphenyl ether sulfate salts.

[0029] Examples of phosphate salt-type anionic surfactants include alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkylphenyl ether phosphate salts, etc. Examples of polymerized high-molecular-weight and polycondensation high-molecular-weight anionic surfactants include partially saponified styrene-maleic anhydride copolymers, partially saponified olefin-maleic anhydride copolymers, and naphthalenesulfonate-formalin condensates.

[0030] Cationic surfactants include amine salt types, quaternary ammonium salt types, polyethylene polyamine derivative types, etc. Amine salt type cationic surfactants include, for example, alkylamine salts and dialkylamine salts.

[0031] Examples of quaternary ammonium salt cationic surfactants include tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridinium salts, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium salts, and N,N-dialkylmorpholinium salts.

[0032] Examples of polyethylene polyamine derivative cationic surfactants include polyethylene polyamine fatty acid amide salts, salts of polyethylene polyamine fatty acid amide urea condensates, and quaternary ammonium salts of polyethylene polyamine fatty acid amide urea condensates.

[0033] Examples of amphoteric surfactants include carboxybetaine, aminocarboxylic acid, sulfobetaine, aminosulfate, and imidazoline types. Examples of carboxybetaine amphoteric surfactants include N,N-dimethyl-N-alkyl-N-carboxyalkyleneammonium betaine. Examples of aminocarboxylic acid amphoteric surfactants include N,N-dialkylaminoalkylenecarboxylate salts. Examples of aminocarboxylic acid amphoteric surfactants include N,N,N-trialkyl-N-sulfoalkyleneammonium betaine.

[0034] Examples of sulfobetaine-type amphoteric surfactants include N-alkyl-N,N-bispolyoxyethylene sulfate ester salts, etc. Examples of imidazoline-type amphoteric surfactants include 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium salts, etc.

[0035] Examples of the solvents and oils include ethanol, isopropanol, 1-butanol, acetic acid, acetic anhydride, acetophenone, methyl oleate, coconut oil, rapeseed oil, soybean oil, castor oil, linseed oil, paraffin oil, kerosene, higher alcohols, cyclohexanol, γ-butyrolactone, fatty acid methyl esters, methylpyrrolidone, dimethyl sulfoxide, chlorobenzene, chlorotoluene, dichloroaniline, normal paraffin, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, cyclohexanone, acetonitrile, kerosene, and machine oil.

[0036] Examples of the sugars include α-hydrated lactose, α-anhydrous lactose, β-anhydrous lactose, diol compounds, glycerin and its derivatives, pentaerythritol, sorbitol, xylitol, sucrose, glucose, and fructose.

[0037] Examples of the 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.

[0038] Examples of the fragrances include lavender oil, jasmine oil, rose oil, lemon oil, orange oil, peppermint oil, thyme oil, calamus oil, fennel oil, cedar oil, hiba oil, cypress oil, eucalyptus oil, camphor, peppermint oil, spearmint oil, geraniol, citronellal, eugenol, limonene, mandarin orange oil, spruce, and citronellol.

[0039] The solid granular composition of this embodiment can be obtained by a conventionally known method, for example, it can be produced using a conventional granulation method. According to this production method, for example, a mixture for producing the granular pesticide composition of the present invention can be obtained by adding an agrochemical active ingredient, a mineral fine powder, and, if necessary, a surfactant and other optional additives. The obtained mixture can be made into a kneaded product by adding water and, if necessary, other optional additives.

[0040] The resulting mixture or kneaded product can be kneaded using a kneader and then extruded into granules using an extrusion granulator. The resulting extruded granules can be dried and sized to obtain the granular pesticide composition of the present invention. The mixing method and mixing order of the raw materials used in this production method are not particularly limited as long as the effects of the present invention are obtained, and mixing conditions, kneading conditions, granulation conditions, and drying / sizing conditions can be appropriately selected. As typical conditions for the production method of the granular pesticide composition of the present invention, the mixing, kneading, and granulation steps are usually carried out at room temperature, or cooled as necessary. The drying step can usually be carried out at a temperature of 50°C to 90°C. Examples of equipment used in each step include the following.

[0041] Examples of the kneading machine include a double-arm kneader, a Nauta mixer, a universal mixer, and a Loedige mixer.

[0042] Examples of extrusion granulators include screw-type extrusion granulators, roll-type extrusion granulators, disc pelleter-type extrusion granulators, pellet mill-type extrusion granulators, basket-type extrusion granulators, blade-type extrusion granulators, oscillating-type extrusion granulators, gear-type extrusion granulators, and ring die-type extrusion granulators.

[0043] In the above-mentioned production method, the liquid or solid pesticide active ingredient may be mixed in advance with a bulking agent and, if necessary, any additives, and then pulverized if necessary before use, or the liquid or solid pesticide active ingredient may be adsorbed or encapsulated in clay minerals, fillers, water-soluble polymers, etc., or may be microencapsulated using latexes, emulsions, etc. Furthermore, the liquid or solid pesticide active ingredient may be dissolved or suspended and dispersed in water, solvents, or oils before use.

[0044] [Coating layer] The coated pesticide composition of this embodiment has a coating layer containing a resin (i) and a polyvalent metal compound (ii) on the surface of the above-mentioned solid granular composition. The thickness of the coating layer varies depending on the specific surface area of ​​the solid granular composition, but is about 10 μm to 200 μm. The coating layer may cover at least a portion of the surface of the solid granular composition as long as it can achieve the effects of the present invention, but it is preferable that it covers the entire surface from the viewpoint of suppressing the initial elution of the pesticide active ingredient and achieving excellent elution after a predetermined period of time has passed. Furthermore, the coated pesticide composition of this embodiment has excellent stability over time, and the coated pesticide composition after aging shows almost no change in the timing at which dissolution starts or the dissolution rate compared to before aging.

[0045] Resin (i) may be either a thermoplastic resin or a thermosetting resin, but it is desirable to use an inexpensive resin that does not require the addition of a volatile solvent. Examples include latexes and emulsions of styrene-butadiene copolymer, styrene-acrylic copolymer, methyl methacrylate-butadiene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic copolymer, silicone-acrylic copolymer, polyurethane, polyurea, etc. Among these, copolymers of one or more monomers selected from acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters are preferred from the standpoint of cost.

[0046] Trade names of such resins (i) include the Movinyl series (Japan Coating Resins Co., Ltd.), the Saivinol series (Saiden Chemical Co., Ltd.), the Acryset series (Nippon Shokubai Co., Ltd.), the Boncoat series (DIC Corporation), and the Almatex series (Mitsui Chemicals, Inc.), and their compositions and glass transition temperatures can be found in catalogs, SDSs, etc. Regarding the glass transition temperature, a low temperature makes the granule surface sticky, making the granules more likely to stick together during production, thereby reducing the yield of the coated pesticide composition. On the other hand, a high glass transition temperature requires maintaining a high product temperature to prevent cracking during coating, which ultimately requires a high hot air drying temperature, prolongs the coating time, increases costs, and reduces the productivity of the coated pesticide composition. Therefore, from these perspectives, the glass transition temperature of resin (i) is preferably 0 to 50°C, more preferably 10 to 40°C.

[0047] The polyvalent metal compound (ii) is at least one selected from aluminum compounds, titanium compounds, zinc compounds, and zirconium compounds. From the viewpoint of uniformity during blending, the compound is preferably one that dissolves or disperses uniformly in water. Examples include aluminum alkoxides, aluminates, titanium lactates and salts, titanium triethanolamine, zinc oxide, ammonium zirconium carbonate, potassium zirconium carbonate, zirconium acetate, and zirconium nitrate, with ammonium zirconium carbonate being preferred.

[0048] From the viewpoint of the effects of the present invention, the amount of the polyvalent metal compound (ii) is usually 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the solid granular composition. From the viewpoint of the effects of the present invention, the weight ratio (i / ii) of the resin (i) to the polyvalent metal compound (ii) is usually 1-1,000, more preferably 3-500, and most preferably 5-100.

[0049] The coated pesticide composition of this embodiment can adjust the amount and timing of elution according to the water solubility of the pesticidal active ingredient (a) contained in the solid granular composition, the type and growth stage of the target crop, and the period for suppressing initial elution and the elution rate after the start of elution can be adjusted. Specifically, the amount and timing of elution of the pesticidal active ingredient (a) can be further adjusted by adjusting the type and water solubility of the pesticidal active ingredient (a) by adjusting the type and amount of the resin (i) and polyvalent metal compound (ii) contained in the coating layer, the size of the solid granular composition, the thickness of the coating layer, the amount of the swelling agent (b) contained in the solid granular composition, etc.

[0050] The coated pesticide composition of this embodiment is a time-release pesticide formulation in which the initial dissolution of the pesticidal active ingredient (a) is suppressed, and after a predetermined period of time has passed, the pesticidal active ingredient (a) is excellently dissolves and has a fast dissolution rate. The dissolution profile of the coated pesticide composition of this embodiment varies depending on conditions such as the type of pesticidal active ingredient (a) and the target crop, but as an example, the period during which dissolution is suppressed (for example, the period during which the dissolution rate reaches 1%) can be arbitrarily adjusted within a range of 7 days or more, the period from the start of dissolution to the achievement of a predetermined dissolution rate (for example, the period during which the dissolution rate reaches 50%) can be arbitrarily adjusted within a range of 60 days or less, and further the period from the dissolution rate reaching 1% to the achievement of 50% can be arbitrarily adjusted within a range of 30 days or less.

[0051] [Method of manufacturing coated pesticide composition] The coated pesticide composition of this embodiment can be obtained by coating the surface of the solid granular composition obtained by the above-mentioned method with a coating layer. The coating method can be carried out by a conventionally known method, namely, the resin (i) and the polyvalent metal compound (ii) are mixed in a mixer or the like, and then diluted with water as needed to adjust the viscosity to obtain a coating liquid. Next, the solid granular composition is placed in a sugar pan, concrete mixer, aerated drum coater, fluidized bed coater, etc., and dried by ventilation while adding a coating liquid, to obtain the coated pesticide composition of the present invention.

[0052] The coated pesticide composition of this embodiment does not use a volatile organic compound during coating, and therefore the coating layer does not have the pores that would be generated if a volatile organic compound were to suddenly evaporate, and elution is controlled, so that elution of the active ingredient can be suppressed for a desired period of time, reducing phytotoxicity and the like, and the elution rate after elution begins is fast, allowing the effect of the active ingredient to be effectively exerted.

[0053] [Method of using coated pesticide composition] The coated pesticide composition of this embodiment can be used in accordance with the method for applying a normal coated pesticide composition (agricultural chemical granules). Such methods include a method for applying the coated pesticide granules simultaneously with the seeds in rice seedling box application or paddy field application, a method for previously mixing the coated pesticide composition into the seedling soil, a method for applying the pesticide granules to the water surface simultaneously with rice planting in paddy field application, and a method for applying the pesticide granules to the water surface after rice planting in paddy field application.

[0054] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted as long as they do not impair the effects of the present invention. [Example]

[0055] The present invention will be explained in more detail below with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to these. All blending ratios shown here are in parts by weight.

[0056] [Example 1] 11.2% tolprocarb, 0.3% Newcalgen TG-100 (polyoxyethylene alkyl ether phosphate, Takemoto Oil & Fat), 1% Cellogen 5A (sodium carboxymethylcellulose, Daiichi Kogyo Seiyaku), 30.0% Hodaka Bentonite (Hojun), and 57.5% NS#100 (calcium carbonate, Nitto Funka Kogyo) were mixed in a bag, water was added, and the mixture was kneaded using a kneader. The resulting mixture was granulated using a basket-type extrusion granulator (model BR-150, Dalton) with a 1.2 mm mesh screen. The resulting granules were dried at 70 °C using a fluidized bed dryer, then crushed and sieved (sieve mesh size 1000-1700 μm) using a New Speed ​​Mill to obtain a solid granular composition. Next, 30% of an acrylic copolymer emulsion (solid content 50%, glass transition temperature 25°C), 0.2% of Olfin EXP4001 (acetylene-based surfactant, manufactured by Nissin Chemical Industry Co., Ltd.), 2% of ethylene glycol monophenyl ether, 1.5% of Zircosol AC-7 (30% solution of ammonium zirconium carbonate, manufactured by Daiichi Kigenso Chemical Industry Co., Ltd.), and 66.3% of water were mixed to obtain a coating liquid. The solid granular composition was placed in a ventilation drum coating machine (model number PRC-GTXmini, manufactured by Powrex), coated with a coating liquid, and then dried to obtain the composition of Example 1. The coating ratio was 133 parts of the coating liquid to 80 parts of the solid granular composition.

[0057] [Example 2] 11.2% tolprocarb, 0.3% Newcalgen TG-100, 6% Cellogen BSH-6 (sodium carboxymethylcellulose, Daiichi Kogyo Seiyaku), 28.7% Talc GTA (talc, Seiko Industries), and 53.8% Wando Clay (clay, Showa KDE) were mixed in a bag, water was added, and the mixture was kneaded using a kneader. The resulting mixture was granulated using a basket-type extrusion granulator (model BR-150, Dalton) with a 1.2 mm mesh screen. The resulting granules were dried at 70°C using a fluidized bed dryer, then crushed and sieved (sieve mesh size 1000-1700 μm) using a New Speed ​​Mill to obtain a solid granular composition. Next, 30% of an acrylic copolymer emulsion (solid content 50%, glass transition temperature 25°C), 0.2% of Olfine EXP4001, 2% of ethylene glycol monophenyl ether, 1% of Baycoat 20 (a 50% solution of ammonium zirconium carbonate, manufactured by Nippon Light Metal Co., Ltd.), and 66.8% of water were mixed to obtain a coating liquid. The solid granular composition was placed in a ventilation drum coating machine (model number PRC-GTXmini, manufactured by Powrex), coated with a coating liquid, and then dried to obtain the composition of Example 2. The coating ratio was 133 parts of the coating liquid to 80 parts of the solid granular composition.

[0058] [Example 3] Tolprocarb 11.2%, Newkalgen TG-100 0.3%, Cellogen HE-1500F (carboxymethylcellulose sodium, Daiichi Kogyo Seiyaku) 6%, Talc GTA 18.7%, and Wando Clay 63.8% were mixed in a bag, water was added, and the mixture was kneaded using a kneader. The resulting mixture was granulated using a basket-type extrusion granulator (model BR-150, Dalton) with a 1.2 mm mesh screen. The resulting granules were dried at 70 °C using a fluidized bed dryer, then crushed and sieved (sieve mesh 1000-1700 μm) using a New Speed ​​Mill to obtain a solid granular composition. Next, 30% of an acrylic copolymer emulsion (solid content 50%, glass transition temperature 30°C), 0.2% of Olfine EXP4001, 2% of ethylene glycol monophenyl ether, 1% of AZ Coat 5800MT (45% solution of ammonium zirconium carbonate, manufactured by San Nopco), and 66.8% of water were mixed to obtain a coating liquid. The solid granular composition was placed in a ventilation drum coating machine (model number PRC-GTXmini, manufactured by Powrex), coated with a coating liquid, and then dried to obtain the composition of Example 3. The coating ratio was 133 parts of the coating liquid to 80 parts of the solid granular composition.

[0059] [Comparative Example 1] In Example 1, except that all of the Zircosol AC-7 was replaced with water, a solid granular composition and coating liquid were prepared using the composition and method described in Example 1, and after coating in the same manner, they were dried to obtain the composition of Comparative Example 1.

[0060] Comparative Example 2 In Example 3, except that the entire amount of AZ Coat 5800MT was replaced with water, a solid granular composition and coating liquid were prepared using the composition and method described in Example 3, and after coating in the same manner, they were dried to obtain the composition of Comparative Example 2.

[0061] [Test Example 1 (In-container elution test)] 85 mg of the compositions described in Examples 1 to 3 and Comparative Examples 1 and 2 were placed in a glass bottle filled with 1 L of ion-exchanged water and allowed to stand in an incubator at 25°C. The supernatant was then sampled at predetermined intervals and filtered to obtain a sample solution. The sample solution was injected into a high-performance liquid chromatograph, and the concentration of the active ingredient in the solution was determined from the peak area of ​​the active ingredient. The dissolution rate in water was calculated using the following formula:

[0062] TIFF0007794661000001.tif15153

[0063] The results are shown in Table 1. As shown in Table 1, in the Example, no dissolution occurred for the first 14 days, then dissolution began, and by the 42nd day, the amount of dissolution had reached 50%, showing a rapid increase in the amount of dissolution. In contrast, in the Comparative Example, no dissolution occurred for the first 14 days, as in the Example, but the dissolution rate thereafter was slow.

[0064] [Table 1]

[0065] [Test Example 2 (Dissolution test after accelerated aging)] The compositions of Example 1 and Comparative Example 1 were stored in a thermostat at 40°C for 90 days (accelerated aging treatment), taken out and returned to room temperature, and then subjected to an in-container dissolution test in the same manner as in Test Example 1. The results are shown in Table 2. It can be seen that the composition of Example 1 showed only a slight change in the amount of elution before and after the accelerated aging treatment, whereas the composition of Comparative Example 1 showed a large change in the amount of elution before and after the accelerated aging treatment.

[0066] [Table 2] [Industrial Applicability]

[0067] The coated pesticide composition of the present invention is prevented from dissolving for a certain period of time after being put into water, which makes it possible to avoid phytotoxicity caused by the pesticide active ingredient, and it is presumed that the effect is quickly manifested due to the excellent dissolution after the period has elapsed. Furthermore, since there is little change in dissolution between immediately after production and after several days have passed, there is an advantage that there is substantially no change in the quality of the product during storage in a warehouse or during distribution.

Claims

1. a solid granular composition comprising an agrochemically active ingredient (a) and a swelling agent (b); a coating layer containing a resin (i) and a polyvalent metal compound (ii) that coats the surface of the solid granular composition; Equipped with Resin (i) is a copolymer of one or more monomers selected from acrylic acid, an acrylic acid ester, methacrylic acid, and a methacrylic acid ester; The coated pesticide composition, wherein the polyvalent metal compound (ii) is a zirconium compound.

2. 2. The coated pesticide composition according to claim 1, wherein the swelling agent (b) is at least one selected from the group consisting of bentonite, starch, and cellulose derivatives.

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