JP5935976B2 - Stabilized agricultural chemical solid formulation - Google Patents

Description

  The present invention relates to a stabilized agricultural chemical solid preparation that suppresses decomposition of a sulfonylurea herbicidal active ingredient under acidic conditions and is stabilized.

  Although the sulfonylurea herbicidal active ingredient itself is hardly decomposed and is stable, when it is formulated into a normal agricultural chemical solid preparation such as a powder, wettable powder, granule, etc., it is decomposed during storage of the preparation. There is a case. In particular, when the preparation pH is acidic, the decomposition of the sulfonylurea herbicidal active ingredient is remarkably accelerated. Therefore, there is a demand for a technique that suppresses and stabilizes the decomposition of the sulfonylurea herbicidal active ingredient under acidic conditions.

  Conventionally, as a method for suppressing and stabilizing the decomposition of the sulfonylurea herbicidal active ingredient, a method of adding zinc oxide (Patent Document 1) or a sodium polyacrylate having an average molecular weight of 2000 to 50000 and basic white carbon are added. A method (Patent Document 2) is known. However, these prior arts do not describe the use of sugar under acidic conditions.

JP-A-8-225416 JP 11-269016 A

  An object of the present invention is to provide a technique for stabilizing a sulfonylurea herbicidal active ingredient in an acidic region.

  In view of such a demand, the present inventor diligently studied novel stabilization of the sulfonylurea herbicidal active ingredient in the acidic region, and by adding sugar, each active component is significantly stabilized even in the acidic region. I found.

  That is, the present invention relates to an agricultural chemical solid preparation (hereinafter referred to as the present preparation) described in [1] to [8] below.

  [1] A solid agricultural chemical formulation comprising a sulfonylurea herbicidal active ingredient, an acid and a sugar.

  [2] The agrochemical solid preparation according to the above [1], wherein the acid is an inorganic acid or an organic acid.

  [3] The agrochemical solid preparation according to the above [1], wherein the acid is a carboxylic acid or a lactone.

  [4] The agrochemical solid preparation according to the above [1], wherein the acid is a carboxylic acid.

  [5] The agrochemical solid preparation according to the above [1], wherein the acid is citric acid.

  [6] The agrochemical solid preparation according to any one of [1] to [5], wherein the sugar is glucose or dextrin.

  [7] The agrochemical solid preparation according to any one of [1] to [6], wherein the sugar content is 5 to 20% by weight based on the solid preparation.

  [8] The agrochemical solid preparation according to any one of [1] to [7], wherein the solid preparation is a granule.

  In agricultural chemical solid preparations, decomposition of the sulfonylurea-based active ingredient in the acidic region can be suppressed and stabilized.

  Examples of the acid used in the agricultural chemical formulation of the present invention include organic acids and inorganic acids, and are not particularly limited. Preferable examples of the organic acid include lactones such as ascorbic acid and erythorbic acid, and carboxylic acids such as citric acid, tartaric acid and malic acid, and citric acid is particularly preferable. Further, preferred examples of the inorganic acid include sulfuric acid, sulfurous acid, and bisulfite, and bisulfite is particularly preferred.

  Examples of the sugar used in the present invention include monosaccharides, disaccharides, trisaccharides, tetrasaccharides and polysaccharides. Monosaccharides include tricarbon sugars such as glyceraldehyde and dioxyacetone, tetracarbon sugars such as threose and erythrulose, pentose sugars such as ribose, lyxose, and xylulose, glucose, mannose, galactose, fructose, sorbose, tagatose, etc. Hexose sugars, mannose heptose, heptose sugars such as sedoheptose, derivatized monosaccharides such as sorbitol, mannitol, glucuronic acid. Examples of oligosaccharides include disaccharides such as maltose, cellobiose, trehalose, lactose and sucrose, trisaccharides such as maltotriose, and tetrasaccharides such as maltotetraose. Moreover, dextrin etc. are mentioned as a polysaccharide.

  Examples of the dosage form of the solid agricultural chemical preparation of the present invention include granules, jumbo agents and powders that can be directly sprayed onto paddy fields, wettable powders and granular wettable powders that are diluted in water when used. Of these, granules are particularly preferred.

  The preparation of the present invention can be produced according to the usual production method for each dosage form. There is no restriction | limiting in particular in the addition method of the acid of this invention, or saccharide | sugar, It may mix with an agrochemical active ingredient and may add separately. For example, in the case of kneaded granules, agrochemical active ingredients, acids, sugars and other adjuvants are mixed, mixed with appropriate water, kneaded, molded by extrusion granulation, etc., dried and sized Is mentioned.

  In the pesticidal solid preparation of the present invention, the content of the sulfonylurea herbicidal active ingredient is 0.05 to 10 parts by weight with respect to 100 parts by weight of the pesticidal solid preparation.

  In the pesticidal solid preparation of the present invention, the acid content is 0.05 to 10 parts by weight with respect to 100 parts by weight of the pesticidal solid preparation.

In the pesticidal solid preparation of the present invention, the sugar content is preferably 5 to 20 parts by weight, more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the pesticidal solid preparation.
The sulfonylurea herbicidal active ingredient used in the present invention is not particularly limited as long as it is a compound having a sulfonylurea structure, and specific examples thereof include the following.

Sulphonylurea herbicidal active ingredients: pyrazosulfuron ethyl, metazosulfuron, halosulfuron methyl, bensulfuron methyl, imazosulfuron, azimsulfuron, inosulfuron, innosulfuron ), Cyclosulfamuron, ethoxysulfuron, orthosulfamrun, flucetosulfuron, monosulfuron, monosulfuron-methyl
Moreover, the agrochemical solid preparation of the present invention may contain an agrochemical active ingredient other than the sulfonylurea herbicidal active ingredient. Examples of the pesticidal active ingredient other than the sulfonylurea herbicidal active ingredient that can be contained in the preparation of the present invention include the following.

  Herbicides: quinoclamin, pyraclonil, aminocyclopyrachlor, tefuryltirone, pyrimisulfan, penoxsulam, aminopyralid, bencarbazone, bencarbazone Pinoxaden, propoxycarbazone sodium salt (propoxycarbazone-sodium), pyrasulfotole (pyrasulfotole), pyroxasulfone (pyroxasulfone), pyroxsulam, tembotrione, thiencarbazone-methyl, Topramezon, metamitron, esprocarb, benthiocarb, molinate, dimepiperate, pyributicarb, mefena Set (mefenacet), butachlor, pretilachlor, tenylchlor, thenylchlor, bromobutide, etobenzanid, dimron, cumyluron, bentazone, piriphthalide, pyrifrid (Bispyribac), bentazone salt, 2,4-D, 2,4-D salt, 2,4-D ester, MCP, MCP salt, MCP ester, MCPB, MCPB salt, MCPB ester, Phenothiol (MCPA-thioethyl), Chromeprop, naproanilide, oxadiazon, pyrazolate, pyrazoloxy, benzofenap, oxadiargyl, dimethametryn, dimethametryn Shime Trimetry, piperophos, anilofos, butamifos, bensulide, dithiopyr, pyriminobac methyl, CNP, chlormethoxynil, cyhalohop butyl (Cyhalofop butyl), bifenox, caffenstrole, pentoxazone, indanofan, oxaziclomefone, fentolazamide, butenachlor, ACN, benzobicyclon, benzobicyclon (Benfuresate), cymmethylin, simazine, dichlobenil, diuron, chloro IPC (chlorpropham), atrazine, alachlor, i Isouron, chlorphtalim, cyanazin, trifluralin, butamifos, quinclorac, propyzamide, promethrin, pendimethalin, metolachlor (Metolachlor), metribuzin, linuron, lenacil, propanil, MCPA, ioxynil octanoate, ashram, quizalofop-ethyl, propoxahop (Propaquizafop), quizalofop-tefuryl, sethoxydim, thifensulfuron-methyl, fenoxaprop-ethyl, phenmedipham, fluazihop Butyl (flua zifop-butyl), bentazone, SAP (bensulide), TCTP (chlorthal-dimethyl, tetorachlorothiophene), amiprophosmethyl, amethrin, isoxaben, orbencarb, carbylate ), Dithiopyr, siduron, thiazafluron, napropamide, prodiamine, bethrodine, methyl dymron, 2,4-PA, MCPPA, Frazas Luflon (flazasulfuron), metsulfuron-methyl, imazaquin, imazapyr, tetrapion (flupropanate), tebuthiuron, bromacil, hexazinone, glyphosate ammonium salt osate-ammonium), glyphosate-iso-propylammonium, glyphosate-trimesium, glyphosate-sodium, glyphosate-potassium, bialaphos, Glufosinate-ammonium, OK-701 (test name), HOK-201 (test name), TH-547 (test name), MCC.

  Bactericides: amisulbrom, acibenzolar, ampropyfos, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, Benomyl, benzamacril, binapacryl, biphenyl, bitertanol, bethoxazine, bordeaux mixture, blasticidin-S, bromoconazole (Bromoconazole), bupirimate, buthiobate, calcium polysulfide, captafol, captan, copper oxychloride, carpropamid, calpropamid Carbendazim, carboxin, chinomethionat, clobenthiazone, chlorfenazol, chloroneb, chlorothalonil, chlorothalonil, chlozolinate, cufraneb, cufraneb Simoxanil, cyproconazol, cyprodinil, cyprofuram, debacarb, dichlorophen, dichlorophenrazol, diclofrazol, dicloine , Dicloran, diethofencarb, diclocymet, difenoconazole, diflumetorim, dimethirimol, dimethomol methomorph, dinicoazole, diniconazole-M, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine ), Drazoxolon, edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole, famoxadone, fenarimol, buconazole , Fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin, ferbam, ferimzone, fluazina Fluazinam, fludioxonil, fluoroimide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet Fosetyl-aluminium, fuberidazole, fluralaxyl, fenamidone, fenhexamid, guazatine, hexachlorobenzene, hexaconazole, Hymexazol, imazalil, imibenconazole, iminoctadine, ipconazole, iprobenfos, iprodione, isopro Isoprothiolane, iprovalicarb, kasugamycin, kresoxim-methyl, mancopper, mancozeb, maneb, mepanipyrim, mepronil, mepronil Metalaxyl, metconazole, metiram, mettominostrobin, microbutanil, nabam, nickel bis (dimethyldithiocarbamate), nitrotar-isopropyl (Nitrothal-isopropyl), nuarimol, octhilinone, offurace, oxadixyl, oxycarboxin, oxpoconazole fumarate, pef Pefurzoate, penconazole, penencycuron, phthalide, piperalin, polyoxins, probenazole, prochloraz, procymidone, propamocarbcarb (propamocarb) hydrochloride, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen, quintozene, sulfur ), Spiroxamine, tebuconazole, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl (th iophanate-methyl, thiram, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph (tridemorph) , Triflumizole, triforine, triticonazole, validamycin, vinclozolin, zineb, ziram, oxine-copper.

  Bactericides: streptomycin, oxyterracycline, oxolinic acid.

  Nematicides: aldoxycarb, fosthiazate, fosthietan, oxamyl, fenamiphos.

  Acaricides: cyenopyrafen, acrylonitrile compounds such as cyfulmetofen, spiromesifen, spirodiclofen, pyridaben, amitraz, bromopropylate, Chinomethionat, chlorobezilate, clofentezine, cyhexatine, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide oxide, fenpropathrin, fenproximate, halfenprox, hexythiazox, milbemectin, propargite ( propargite), pyrimidifen, tebufenpyrad.

  Insecticides: abamectin, acephate, acetamipirid, azinphos-methyl, bendiocarb, benfuracarb, bensultap, bifenthrin, prof ), Butocarboxim, carbaryl, carbfuran, carbofuran, carbosulfan, cartap, chlorfenapyr, chlorpyrifos, chlorfenvinphos, chlor Flufluron (chlorfluazuron), clothianidin (clothianidin), chromafenozide (chromafenozide), chlorpyrifos-methyl (chlorpyrifos-methyl), cyfluthrin (cyfluthrin), beta-cyfluthrin (beta-cyfluthrin), cype Methperin (cypermethrin), cyromazine, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diacloden, diflubenzuron ), Dimethylvinphos, diofenolan, disulfoton, dimethoate, EPN, esfenvalerate, ethiofencarb, ethiprole, etofenprox, Etrimfos, fenitrothion, fenobucarb, phenoxy curve, fenpropathrin, fenvalerate, fiproni (Fipronil), flucythrinate, flufenoxuron, flufenprox, tau-fluvalinate, fonophos, formetanate, formothion ), Furathiocarb, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, isofenphos, indoxacarb, isoprocarb, isoxathione isoxathion, lufenuron, malathion, metaldehyde, metamidophos, methidathion, methacrifos, metalcarb, methomyl yl), metoprene, methoxychlor, methoxyfenozide, monocrotophos, muscalure, nitenpyram, omethoate, oxydemeton-methyl, oxdemeton-methyl (Oxamyl), parathion, parathion-methyl, permethrin, phenthoate, phoxim, phorate, phosalone, phosmet, phosphamidone ( phosphamidon, pirimicarb, pirimiphos-methyl, profenofos, pymetrozine, pyraclofos, pyriproxyfen, rotenone, sulprofo (Sulprofos), silafluofen, spinosad, sulfotep, sulfotep, tebfenozide, teflubenzuron, teflubenzuron, tebuthorin, terbufos, tetrachlorovinphos (tetrachlorvinphos) ), Thiamethoxam, thiofanox, thiometon, tolfenpyrad, tralomethrin, trichlorfon, triazuron, triflumuron, bamidion, etc. can give.

  Agrochemical active ingredients other than these sulfonylurea herbicidal active ingredients can be used alone or in admixture of two or more, and the ratio in the case of mixing can also be freely selected. The content of the pesticidal active ingredient other than the sulfonylurea herbicidal active ingredient in the preparation of the present invention can be appropriately selected, but is preferably in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the preparation of the present invention.

  The preparation of the present invention can further contain various adjuvants. Adjuvants that can be used include surfactants, binders, solid carriers, solvents, and the like.

  Examples of the surfactant include the following (A), (B), (C), (D), and (E).

(A) Nonionic surfactant:
(A-1) Polyethylene glycol type surfactant: For example, polyoxyethylene alkyl (C _8-18 ) ether, ethylene oxide adduct of alkyl naphthol, polyoxyethylene (mono or di) alkyl (C _8-12 ) phenyl Ether, formalin condensate of polyoxyethylene (mono or di) alkyl ( _C8-12 ) phenyl ether, polyoxyethylene (mono, di or tri) phenyl phenyl ether, polyoxyethylene (mono, di or tri) benzyl phenyl Ether, polyoxypropylene (mono, di or tri) benzyl phenyl ether, polyoxyethylene (mono, di or tri) styryl phenyl ether, polyoxypropylene (mono, di or tri) styryl phenyl ether, polyoxyethylene (Mono-, di- or tri-) styryl phenyl ether polymer, alkyl (C _{8 to 18)} polyoxyethylene polyoxypropylene block polymer ethers, alkyl (C _{8 to 12)} polyoxyethylene polyoxypropylene block polymer ether, polyoxy Ethylene bisphenyl ether, polyoxyethylene resin acid ester, polyoxyethylene fatty acid (C _8-18 ) monoester, polyoxyethylene fatty acid (C _8-18 ) diester, polyoxyethylene sorbitan fatty acid (C _8-18 ) ester, glycerol fatty acid ester ethylene oxide adduct, castor oil ethylene oxide adduct, hydrogenated castor oil ethylene oxide adduct, alkyl (C _{8 to 18)} amine ethylene oxide adduct and lipid Acid _{(C 8 to 18)} amide ethylene oxide adducts.

(A-2) Polyhydric alcohol type surfactant: For example, glycerol fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid (C _8-18 ) ester, sorbitan fatty acid (C _8-18 ) ester, Examples thereof include sugar fatty acid esters, polyhydric alcohol alkyl ethers, and fatty acid alkanolamides.

  (A-3) Acetylene-based surfactant: Examples thereof include acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, ethylene oxide adduct of acetylene alcohol, and the like.

  (A-4) Other surfactants: Examples include alkyl glycosides.

(B) Anionic surfactant:
(B-1) Carboxylic acid type surfactant: For example, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, maleic acid or maleic anhydride and olefin (for example, isobutylene and diisobutylene) Polymer, Copolymer of acrylic acid and itaconic acid, Copolymer of methacrylic acid and itaconic acid, Copolymer of maleic acid or maleic anhydride and styrene, Copolymer of acrylic acid and methacrylic acid, Acrylic acid Copolymer of acrylic acid and methyl ester of acrylic acid, copolymer of acrylic acid and vinyl acetate, copolymer of acrylic acid and maleic acid or maleic anhydride, N-methyl-fatty acid ( _C8-18 ) sarcosinate, resin _Examples thereof include carboxylic acids such as acids and fatty acids (C _8-18 ), and salts of these carboxylic acids.

(B-2) sulfate surfactants: for example, alkyl _{(C 8 to 18)} sulfates, polyoxyethylene alkyl _{(C 8 to 18)} ether sulfuric acid ester, polyoxyethylene (mono or di) alkyl _{(C 8 -12} ) phenyl ether sulfate, polyoxyethylene (mono or di) alkyl ( _C8-12 ) phenyl ether polymer sulfate, polyoxyethylene (mono, di or tri) phenyl phenyl ether sulfate, polyoxyethylene (Mono, di or tri) benzyl phenyl ether sulfate, polyoxyethylene (mono, di or tri) styryl phenyl ether sulfate, polyoxyethylene (mono, di or tri) styryl phenyl ether polymer sulfate, polyoxyethylene Down sulfate ester polyoxypropylene block polymers, sulfated oils, fatty acid ester sulfuric, sulfate ester such as sulfated fatty acid and sulfated olefin, and salts of these sulfuric esters.

(B-3) Sulfonic acid type surfactant: For example, paraffin ( _C8-22 ) sulfonic acid, alkyl ( _C8-12 ) benzenesulfonic acid, alkyl ( _C8-12 ) benzenesulfonic acid formalin condensate, Formalin condensate of cresol sulfonic acid, α-olefin (C _8-16 ) sulfonic acid, dialkyl (C _8-12 ) sulfosuccinic acid, polyoxyethylene (mono or di) alkyl (C _8-12 ) phenyl ether sulfonic acid, Polyoxyethylene alkyl (C _8-18 ) ether sulfosuccinic acid half ester, naphthalene sulfonic acid, (mono or di) alkyl (C _1-6 ) naphthalene sulfonic acid, formalin condensate of naphthalene sulfonic acid, (mono or di) alkyl _{(C 1 to 6)} formalin condensates of naphthalenesulfonic acid, Formalin condensate of Reosoto oil sulfonic acid, alkyl (C _{8 to 12)} ether disulfonic acid, Igepon T (trade name), polystyrene sulfonic acid and styrene sulfonic acid and methacrylic acid copolymer of acrylic acid, and their sulfone Examples include acid salts.

(B-4) Phosphate ester type surfactants: For example, alkyl (C _8-12 ) phosphate ester, polyoxyethylene alkyl (C _8-18 ) ether phosphate ester, polyoxyethylene (mono or di) alkyl (C _{8 -12} ) phenyl ether phosphate ester, polyoxyethylene (mono, di or tri) alkyl ( _C8-12 ) phenyl ether polymer phosphate ester, polyoxyethylene (mono, di or tri) phenyl phenyl ether phosphate ester, poly Oxyethylene (mono, di or tri) benzyl phenyl ether phosphate ester, polyoxyethylene (mono, di or tri) styryl phenyl ether phosphate ester, polyoxyethylene (mono, di or tri) styryl phenyl ether polymer phosphate ester, Polyoxye Examples thereof include phosphate esters of a tylene polyoxypropylene block polymer, phosphate esters such as phosphatidylcholine, phosphatidylethanolimine and condensed phosphoric acid (for example, tripolyphosphoric acid), and salts of these phosphate esters.

  Examples of the salt in the above (B-1) to (B-4) include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.), ammonium and various amines (for example, alkylamine, cyclohexane). Alkylamine and alkanolamine).

(C) Cationic surfactant:
Examples thereof include alkylamines, alkyl quaternary ammonium salts, alkylamine ethylene oxide adducts, and alkyl quaternary ammonium salt ethylene oxide adducts.

(D) Amphoteric surfactant:
Examples thereof include betaine type surfactants and amino acid type surfactants.

(E) Other surfactants:
For example, silicone surfactants and fluorine surfactants can be used.

  These surfactants can be used alone or in admixture of two or more, and the ratio in the case of mixing can be freely selected. The content of the surfactant in the preparation of the present invention can be appropriately selected, but is preferably in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the preparation of the present invention.

  Examples of the binder include dextrin (roasted dextrin and enzyme-modified dextrin, etc.), acid-decomposed starch, oxidized starch, pregelatinized starch, etherified starch (carboxymethyl starch, hydroxyalkyl starch, cationic starch, etc.), esterified starch ( Processed starch such as starch acetate and phosphate starch), cross-linked starch and grafted starch, natural substances such as sodium alginate, gum arabic, gelatin, tragacanth gum, locust bean gum and casein such as carboxymethylcellulose sodium salt, hydroxyethylcellulose, Cellulose derivatives such as hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, ethylcellulose and acetylcellulose; Polyethylene glycol, polypropylene glycol, polyethylene polypropylene block copolymer, polyvinyl alcohol, partially saponified vinyl acetate and vinyl ether copolymer, polyvinyl pyrrolidone, polyvinyl pyrrolidone and vinyl acetate copolymer, and other polymers such as polyacrylamide Is mentioned.

  Examples of the solid carrier include quartz, calcite, gypsum, dolomite, chalk, kaolinite, pyrophyllite, sericite, halosite, metahalosite, kibushi clay, glazed clay, porcelain stone, siegrite, and allophane. Natural minerals such as shirasu, kira, talc, bentonite, activated clay, acid clay, pumice, attapulgite, zeolite and diatomaceous earth, for example, calcined clay, perlite, shirasu balloon, vermiculite, attapulgus clay and calcined diatomaceous earth Baked products such as magnesium carbonate, calcium carbonate, sodium carbonate, sodium bicarbonate, ammonium sulfate, sodium sulfate, magnesium sulfate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and potassium chloride, such as glucose, fructose , And Saccharides such as sugar and lactose, polysaccharides such as starch, powdered cellulose and dextrin, organic substances such as urea, urea derivatives, benzoic acid and benzoic acid salts, such as wood flour, corn cob, walnut shell and tobacco stem Plant, fly ash, white carbon, and fertilizer.

  Specific examples of bentonite include, for example, Kunigel VA (trade name / Kunimine Industry Co., Ltd.), Kunigel V2 (trade name / Kunimine Industry Co., Ltd.), Hotaka Bentonite (trade name / Toyojun Yoko Co., Ltd.) , Myogi bentonite (trade name / manufactured by Toyoshiro Yoko Co., Ltd.), Haruna bentonite (brand name / manufactured by Toyoshun Yoko Co., Ltd.), bentonite super clay (brand name / manufactured by Toyoshun Yoko Co., Ltd.) and granular bentonite ( Examples thereof include sodium bentonite such as trade name / Toyojun Yoko Co., Ltd. and calcium bentonite such as Kunibond (trade name / Kunimine Industries Co., Ltd.).

  Specific examples of natural minerals other than bentonite include H fine powder (trade name / manufactured by Asada Flour Milling Co., Ltd.), Neocarrier K (trade name / manufactured by Asada Flour Milling Co., Ltd.), Fusami K clay (trade name / fubashimi clay ( Co., Ltd.) and Tokuyuki F clay (trade name / manufactured by Showa Mining Co., Ltd.).

  Specific examples of calcium carbonate include Microcal 250 (trade name / Aokura Lime Industry Co., Ltd.), Microcal 100 (trade name / Aokura Industry Co., Ltd.), NS # 100 (trade name / Nitto Flour Industry ( NS # 200 (trade name / manufactured by Nitto Flour Chemical Co., Ltd.), NS # 3000 (trade name / manufactured by Nitto Flour Chemical Co., Ltd.) and Super SS (trade name / Maruo Calcium Co., Ltd.) Manufactured) and the like.

  Specific examples of white carbon include Carplex # 80D (trade name / DSL. Japan), Carplex # 67 (trade name / DSL. Japan), Carplex # 1120 (trade name / DSL). Japan Co., Ltd.), Carplex #XR (trade name / DSL Japan Co., Ltd.), Fine Seal A (trade name / Tokuyama Soda Co., Ltd.), Fine Seal E-50 (trade name / Tokuyama Soda Co., Ltd.) )), Fine Seal X-37 (trade name / Tokuyama Soda Co., Ltd.), Fine Seal K-41 (trade name / Tokuyama Soda Co., Ltd.), Fine Seal P-8 (trade name / Tokuyama Soda Co., Ltd.) , Toxeal U (trade name / Tokuyama Soda Co., Ltd.), Toxeal CU-N (trade name / Tokuyama Soda Co., Ltd.), Toxeal P (trade name / Tokuyama Soda Co., Ltd.), Toxeal NR (Product name / Tokuyama Sato) Nip Seal NS (trade name / Nippon Silica Industry Co., Ltd.), Nip Seal NSK (trade name / Nippon Silica Industry Co., Ltd.), Nip Seal NA (trade name / Nippon Silica Industry Co., Ltd.), Syloid 244 (Trade name / Fuji Devison Chemical), Cyloid 65 (trade name / Fuji Devison Chemical), Cyloid 308 (trade name / Fuji Devison Chemical), Mizukacil P-705 (trade name / Mizusawa Chemical Co., Ltd.), Mizukasil P-802 Hydrous silica such as (trade name / Mizusawa Chemical Co., Ltd.), Mizukasil P-78 (trade name / Mizusawa Chemical Co., Ltd.) and Mizukasil P-832 (trade name / Mizusawa Chemical Co., Ltd.), such as Carplex CS- 5 (trade name / DSL. Japan), Carplex CS-7 (trade name / DSL. Japan) and Carplex CS-70 Baked products of hydrous silica such as (trade name / DSL. Japan), such as Aerosil 130 (trade name / Japan Aerosil), Aerosil 200 (trade name / Japan Aerosil), Aerosil 380 (product) Name / Nippon Aerosil Co., Ltd.) and Aerosil MOX80 (Product Name / Nippon Aerosil Co., Ltd.), etc. Hydrous calcium silicates such as Toyohero TH (trade name / Toyo Denka Kogyo Co., Ltd.), Zonolite (trade name / Onoda Chemical) and Microcell E (trade name / Johns Manville), for example, SIPERNAT D17 ( Product name / Nippon Aerosil Co., Ltd.), NipSeal SS-10 (Product name / Nippon Silica Co., Ltd.), Nippi Surface-treated silica made from hydrous silica such as RuSS-20 (trade name / Nippon Silica Co., Ltd.) and Nipsil SS-30P (trade name / Nippon Silica Co., Ltd.), such as Aerosil R972 (trade name / Nippon Aerosil) Surface-treated silica made from anhydrous silica such as Aerosil R202 (trade name / Nippon Aerosil Co., Ltd.) and Aerosil R812 (trade name / Nippon Aerosil Co., Ltd.).

Examples of the solvent include aromatic hydrocarbons such as xylene, alkyl (C ₉ or C ₁₀ etc.) benzene, phenyl xylyl ethane and alkyl (C ₁ or C ₃ etc.) naphthalene, machine oil, normal paraffin, isoparaffin and naphthene. Aliphatic hydrocarbons such as kerosene, a mixture of aromatic and aliphatic hydrocarbons such as kerosene, alcohols such as ethanol, isopropanol, cyclohexanol, phenoxyethanol and benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, hexylene glycol, Polyhydric alcohols such as polyethylene glycol and polypropylene glycol, propyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene Ethers such as ethylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and propylene glycol monophenyl ether, ketones such as acetophenone, cyclohexanone and γ-butyrolactone, fatty acid methyl esters, succinic acid dialkyl esters, glutamic acid dialkyl esters, Esters such as adipic acid dialkyl ester and phthalic acid dialkyl ester, acid amides such as N-alkyl (C ₁ , C ₈ or C ₁₂ ) pyrrolidone, soybean oil, linseed oil, rapeseed oil, coconut oil, cottonseed oil and castor oil Oils and fats, dimethyl sulfoxide and water.

EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these. In the following, “part” means part by weight.
[Example 1] Preparation of metazosulfuron paraffin premix 22.3 parts of metazosulfuron (generic name, sulfonylurea herbicidal active ingredient) finely ground to about 5 microns, crystalline-quartz (trade name: H fine powder, Keiwa) 46.9 parts of furnace material (trade name), calcium silicate (trade name: Florite R, manufactured by Tokuyama Co., Ltd.) 0.75% and petroleum paraffin wax (melting point 69 ° C. to 72 ° C.) 30 parts, The mixture was melted and kneaded using a kneader at 100 ° C. Then, it cooled to about 75 degreeC, extruded and granulated with the screen which has a hole with a diameter of 1.2 mm, and this was grind | pulverized with the pin mill, and the metazosulfuron paraffin premix was obtained.

[Example 2]
4 parts of metazosulfuron paraffin premix, 10 parts of glucose, 1 part of anhydrous citric acid, 1 part of sodium tripolyphosphate, 30 parts of bentonite mineral powder (trade name: Kunigel V2, manufactured by Kunimine Co., Ltd.) , 52.73 parts of clay mineral fine powder (trade name: Neocarrier K, manufactured by Asada Flour Milling Co., Ltd.). To this, 1.5 parts of dialkylsulfosuccinic acid sodium salt (trade name: Aerol CT-1L, manufactured by Toho Chemical Co., Ltd.) and water were added and mixed. Next, the mixture was granulated using an extrusion granulator equipped with a screen having a 1.0 mm diameter and then dried at 50 ° C. to obtain an agrochemical granule having a moisture content of 2.69%.

Example 3
4 parts of metazosulfuron paraffin premix, 10 parts of dextrin (trade name: Paindex Y, manufactured by Matsutani Chemical Co., Ltd.), 1 part of anhydrous citric acid, 1 part of sodium tripolyphosphate, 30 parts of Kunigel V2 52.73 parts of Neocarrier K were mixed. Here, 1.5 parts of air roll CT-1L and water were added and mixed. Next, the mixture was granulated using an extrusion granulator equipped with a screen having a 1.0 mm diameter, and dried at 50 ° C. to obtain an agrochemical granule having a moisture content of 2.88%.

[Example 4] Production of pyrazosulfuron ethyl paraffin premix 4.3 parts of pyrazosulfuron ethyl (generic name, sulfonylurea herbicidal active ingredient) finely ground to about 5 microns, 65.7 parts of H fine powder, petroleum 30 parts of paraffin wax (melting point: 69 ° C. to 72 ° C.) was melted and kneaded using a kneader at about 100 ° C. Then, it cooled to about 75 degreeC, extruded and granulated with the screen which has a hole with a diameter of 1.2 mm, and this was grind | pulverized with the pin mill, and the metazosulfuron paraffin premix was obtained.

Example 5
5 parts of pyrazosulfuron ethyl paraffin premix, 10 parts of glucose, 1 part of anhydrous citric acid, 1 part of sodium tripolyphosphate, 30 parts of Kunigel V2 and 51.73 parts of Neocarrier K were mixed. Here, 1.5 parts of Air Roll CT-1L and water were added and mixed. Next, after granulating using an extrusion granulator equipped with a screen having a 1.0 mm diameter, the granules were dried at 50 ° C. to obtain agricultural chemical granules having a moisture content in the grains of 3.09%.

Example 6
5 parts of a pyrazosulfuron ethyl paraffin premix, 10 parts of Paindex Y, 1 part of anhydrous citric acid, 1 part of sodium tripolyphosphate, 30 parts of Kunigel V2 and 51.73 parts of Neocarrier K were mixed. Here, 1.5 parts of Air Roll CT-1L and water were added and mixed. Next, after granulating using an extrusion granulator equipped with a screen having a 1.0 mm diameter, the granules were dried at 50 ° C. to obtain agricultural chemical granules having a moisture content of 3.27%.

Example 7
0.91 part of halosulfuron methyl (generic name, sulfonylurea herbicidal active ingredient) ground to about 5 μm, 10 parts of glucose, 1 part of anhydrous citric acid, 1 part of sodium tripolyphosphate, 30 parts of Kunigel V2, neocarrier 55.82 parts of K were mixed. Here, 1.5 parts of Air Roll CT-1L and water were added and mixed. Subsequently, after granulating using an extrusion type granulator equipped with a screen having a 1.0 mm diameter, it was dried at 50 ° C. to obtain an agrochemical granule having a moisture content of 2.98%.

Example 8
0.91 part of halosulfuron methyl ground to about 5 μm, 10 parts of Paindex Y, 1 part of anhydrous citric acid, 1 part of sodium tripolyphosphate, 30 parts of Kunigel V2 and 55.82 parts of Neocarrier K were mixed. . Here, 1.5 parts of Air Roll CT-1L and water were added and mixed. Subsequently, after granulating using an extrusion type granulator equipped with a screen having a 1.0 mm diameter, it was dried at 50 ° C. to obtain an agrochemical granule having a moisture content of 3.10%.

[Comparative Example 1]
In Example 2, except for glucose, the same treatment as in Example 2 was performed except that neocarrier K was increased by that amount to obtain an agrochemical granule having a moisture content of 2.17%.

[Comparative Example 2]
In Example 5, except for glucose, the same treatment as in Example 5 was performed except that neocarrier K was increased by that amount to obtain an agrochemical granule having a moisture content of 2.68%.

[Comparative Example 3]
In Example 7, except for glucose, except that the neocarrier K was increased correspondingly, the same treatment as in Example 7 was performed to obtain an agrochemical granule having a moisture content in the grain of 2.75%.

  Next, a severe test was performed using each of the above-mentioned granules, and the effect of stabilizing the solid agricultural chemical formulation of the present invention was examined.

[Test Example 1] Measurement of moisture in grains The moisture in grains is the weight (%) of moisture contained in a predetermined granular material, and was determined by a method for measuring loss on drying.

Model name: Infrared moisture meter FD-240 manufactured by Kett Co., Ltd.
Drying temperature: 105 ° C
Stabilization time ^* : 2 minutes * Measure the loss on drying when the time at which no weight change is observed reaches this time.

[Test Example 2] Severe test (1)
Each solid granule obtained in Examples 2 and 3 and Comparative Example 1 was used as a sample for this test. The sample was put in an aluminum bag with a chuck, placed in a 54 ° C. thermostat, stored for 14 days, and subjected to a severe test. Table 1 shows the results of measuring the time-dependent change rate (decomposition rate) by measuring the content of metazosulfuron in the sample before and after the test. The content of metazosulfuron was quantified by an internal standard method using liquid chromatography.

Rate of change over time (decomposition rate)% = (R−S) / R × 100
R: Content of metazosulfuron in the sample before the severe test S: Content of metazosulfuron in the sample after the severe test Table 1 ――――――――――――――――――――― ――――――――――――――――
Water content in sugar particles (%) Decomposition rate of metazosulfuron (%)
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Example 2 Glucose 2.69 3.6
Example 3 Dextrin 2.88 2.6
Comparative Example 1 None 2.17 14.2
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As is apparent from the results in Table 1, the degradation rate of metazosulfuron is significantly suppressed in the agrochemical solid preparation of the present invention to which sugars such as glucose and dextrin are added as compared with the preparation of Comparative Example in which no sugar is added.

[Test Example 3] Severe test (2)
Each solid granule obtained in Examples 5 and 6 and Comparative Example 2 was used as a sample for this test. The sample was put in an aluminum bag with a chuck, placed in a 54 ° C. thermostat, stored for 14 days, and subjected to a severe test. Table 2 shows the results of calculating the rate of change with time (decomposition rate) by measuring the content of pyrazosulfuron ethyl in the samples before and after the test. The content of pyrazosulfuron ethyl was quantified by an internal standard method by liquid chromatography.

Rate of change over time (decomposition rate)% = (R−S) / R × 100
R: Content of pyrazosulfuron ethyl in the sample before the severe test S: Content of pyrazosulfuron ethyl in the sample after the severe test Table 2 -------- ――――――――――――――――――――――
Sugar content (%) Decomposition rate of pyrazosulfuron ethyl (%)
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Example 5 Glucose 3.09 10.2
Example 6 Dextrin 3.27 8.6
Comparative Example 2 None 2.68 25.9
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As is apparent from the results in Table 2, the decomposition rate of pyrazosulfuron ethyl is significantly suppressed in the solid agricultural chemical preparation of the present invention to which sugars such as glucose and dextrin are added as compared with the preparation of the comparative example without addition of sugar. ing.

[Test Example 4] Severe test (3)
Each solid granule obtained in Examples 7 and 8 and Comparative Example 3 was used as a sample for this test. The sample was put in an aluminum bag with a chuck, placed in a 54 ° C. thermostat, stored for 14 days, and subjected to a severe test. Table 3 shows the results of measuring the content of halosulfuron methyl in the sample before and after the test and calculating the rate of change with time (decomposition rate). The content of halosulfuron methyl was quantified by an internal standard method by liquid chromatography.

Rate of change over time (decomposition rate)% = (R−S) / R × 100
R: Content of halosulfuron methyl in the sample before the severe test S: Content of halosulfuron methyl in the sample after the severe test Table 3 ――――――――――――――――― ――――――――――――――――――――
Sugar content (%) Degradation rate of halosulfuron methyl (%)
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Example 7 Glucose 2.98 5.1
Example 8 Dextrin 3.10 4.8
Comparative Example 3 None 2.75 54.6
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As is apparent from the results in Table 3, the pesticidal solid preparation of the present invention to which sugars such as glucose and dextrin are added has an extremely low decomposition rate of halosulfuron methyl compared to the preparation of the comparative example to which no sugar is added. Yes.

Claims (4)

Agrochemical solid formulation containing sulfonylurea herbicidal active ingredient, citric acid and sugar (except for agrochemical solid formulation containing carbonate or bicarbonate) . Agrochemical solid preparation according to claim 1 Symbol placement sugar is glucose or dextrins. Against solid preparation content of sugar, according to claim 1 or 2 SL placing pesticide solid preparation is 5 to 20 wt%. The agrochemical solid preparation according to any one of claims 1 to 3, wherein the solid preparation is a granule.