JP2012158566A - Stabilized herbicide solid preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new herbicide solid preparation.SOLUTION: This herbicide solid preparation includes pyrazosulfuron ethyl, mesotrione, a hydrophobic liquid and an acid. Decomposition of pyrazosulfuron ethyl and mesotrione is inhibited and stabilized by containing the hydrophobic liquid and the acid. Citric acid is preferable as the acid. Jumbo agent or granular agent is preferable as the form of the herbicide solid preparation.

Description

  The present invention relates to a solid agricultural chemical formulation that suppresses and stabilizes the decomposition of pyrazosulfuron ethyl and mesotrione, which are herbicidal active ingredients.

  The herbicidally active ingredients pyrazosulfuron ethyl and mesotrione themselves are stable with little degradation, but when formulated into ordinary agrochemical solid formulations such as granule wettable powder, granules, jumbo agents, etc. May be degraded during storage of the formulation. Therefore, a technique for suppressing and stabilizing the decomposition of pyrazosulfuronethyl and mesotrione is desired.

  Conventionally, as a method of suppressing and stabilizing the decomposition of the sulfonylurea herbicidal active ingredient, a method of adding zinc oxide (Patent Document 1), a method of adding sodium polyacrylate having an average molecular weight of 2000 to 50000 and basic white carbon (Patent Document 2), a method of adding fats and oils to a water-suspendable agricultural chemical composition (Patent Document 3) is known.

  Further, as a method for suppressing and stabilizing the decomposition of mesotrione, a method of adding an electrolyte to a mesotrione aqueous premix suspension (Patent Document 4) is known.

JP-A-8-225416 Japanese Patent Application Laid-Open No. 11-269016 Special table 2010-502561 gazette Special table 2008-504354

  The problem to be solved by the present invention is as described above, and an object of the present invention is to provide a technology for a solid agricultural chemical formulation that stabilizes both pyrazosulfuron ethyl and mesotrione.

  In view of such a demand, the present inventors diligently studied a novel stabilization method of pyrazosulfuron ethyl and mesotrione, and these active ingredients are remarkably stabilized by adding a hydrophobic liquid and an acid. I found out.

  That is, the present invention relates to an agricultural chemical solid preparation (hereinafter referred to as the present preparation) described in [1] to [7] below.

[1] An agrochemical solid preparation containing pyrazosulfuron ethyl, mesotrione, a hydrophobic liquid and an acid.
[2] The agrochemical solid preparation according to the above [1], wherein the acid is citric acid.

  [3] The agricultural chemical solid preparation according to the above [1] or [2], wherein the content of the hydrophobic liquid with respect to the agricultural chemical solid preparation is 1 to 20% by weight.

  [4] The agricultural chemical solid preparation according to any one of [1] to [3], wherein the acid content relative to the agricultural chemical solid preparation is 0.05 to 10% by weight.

[5] The agrochemical solid preparation according to any one of [1] to [4], wherein the solid preparation is a jumbo agent or a granule.
[6] The agrochemical solid preparation according to any one of [1] to [5], wherein the hydrophobic liquid is liquid paraffin.

  [7] The agrochemical solid preparation according to the above [6], wherein the liquid paraffin is normal paraffin or isoparaffin.

  In a solid agricultural chemical formulation, decomposition of pyrazosulfuronethyl and mesotrione can be suppressed and stabilized.

Examples of the hydrophobic liquid used in this invention, xylene, alkyl (C ₉ or C _10, etc.) benzene, phenylxylylethane and alkyl (C ₁ or C _3, etc.) aromatic hydrocarbons such as naphthalene, machine oils, liquid Aliphatic hydrocarbons such as paraffin and naphthene, aromatic and aliphatic hydrocarbon mixtures such as kerosene, fatty acid methyl ester, succinic acid dialkyl ester, glutamic acid dialkyl ester, adipic acid dialkyl ester and phthalic acid dialkyl ester Examples include fats and oils such as ester, soybean oil, rice oil, linseed oil, rapeseed oil, coconut oil, cottonseed oil and castor oil.

The hydrophobic liquid used in the present invention is preferably liquid paraffin, and examples thereof include normal paraffin and isoparaffin.
Examples of the acid used in the present invention include organic acids and inorganic acids. 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, preferably citric acid. Examples of inorganic acids include sulfuric acid, sulfurous acid, and bisulfite.

  Examples of the dosage form of the agrochemical solid preparation of the present invention include granules, jumbo agents in which particles that float and diffuse on the water surface are packaged with a water-soluble film, and wettable powders and granular wettable powders that are diluted in water when used. Can do. Of these, granules and jumbo agents 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 hydrophobic liquid and acid of this invention, It may mix with an agrochemical active ingredient and may add separately. For example, in the case of kneaded granules, agrochemical active ingredients, hydrophobic liquids, acids and other adjuvants are mixed, mixed with appropriate water, kneaded, molded by methods such as extrusion granulation, dried and sized And a method of sieving.

  In the solid agricultural chemical formulation of the present invention, the content of pyrazosulfuron ethyl and mesotrione is 0.05 to 10 parts by weight with respect to 100 parts by weight of the solid agricultural chemical formulation.

The content of the hydrophobic liquid is preferably 1 to 20 parts by weight, more preferably 4 to 10 parts by weight with respect to 100 parts by weight of the agricultural chemical solid preparation.
The acid content is preferably 0.05 to 10 parts by weight, more preferably 1 to 5 parts by weight, with respect to 100 parts by weight of the agricultural chemical solid preparation.

  The solid agricultural chemical formulation of the present invention may contain an agricultural chemical active ingredient other than pyrazosulfuron ethyl and mesotrione. Examples of the agrochemical active ingredient other than pyrazosulfuron ethyl and mesotrione that can be contained in the preparation of the present invention include the following.

  Herbicides: metazosulfuron, halosulfuron methyl, bensulfuron methyl, imazosulfuron, azimsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron Ethoxysulfuron, pyraclonil, tefuryltirone, pyrimisulfan, penoxsulam, aminopyralid, bencarbazone, flucetosulfuron monosulfuron, monosulfuron , Monosulfuron-methyl, pinoxaden, propoxycarbazone-sodium, pyrasulfotole, pyroxasulfone (Pyroxasulfone), pyroxsulam, tembotrione, thiencarbazone-methyl, topramezon, esprocarb, benthiocarb, molinate, dimepiperate, dimepiperate (Pyributicarb), mefenacet, butachlor, pretilachlor, tenylchlor, bromobutide etobenzanide, dimron, cumyluron, bentazone, 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) ), Lomeprop, naproanilide, oxadiazon, pyrazolate, pyrazoxyfen, benzofenap, oxadiargyl, dimethametryn, dimethametryn, periphos ), Anilofos, butamifos, bensulide, dithiopyr, pyriminobac methyl, CNP, chlormethoxynil, cyhalofop butyl, bifenox ), Caffenstrole, pentoxazone, indanofan, oxaziclomefone, fentrazamide, butenachlor, AC Benzobicyclon, benfuresate, cymmethylin, simazine, dichlobenil, diuron, chloro IPC (chlorpropham), atrazine, alachlor, Isouron, chlorphtalim, cyanazin, trifluralin, butamifos, propyzamide, promethrin, pendimethalin, metolachlor, metolachlor metribuzin, linuron, lenacil, propanil, MCPA, ioxynil octanoate, ashram, quizalofop-ethyl, propaquizafop, kizaroho Putefryl (quizalofop-tefuryl), sethoxydim, thifensulfuron-methyl, fenoxaprop-ethyl, phenmedipham, fluazifop-butyl, bentazone (Bentazone), SAP (bensulide), TCTP (chlorthal-dimethyl, tetorachlorothiophene), amiprophosmethyl, ametrin, isoxaben, orbencarb, carbutilate, dithiopyr , Siduron, thiazafluron, napropamide, prodiamine, benefin, methyl dymron, 2,4-PA, MCPPA, flazasulfuron, methos Ruflon Mechi Metsulfuron-methyl, imazaquin, imazapyr, tetrapropion (flupropanate), tebuthiuron, bromacil, hexaazinone, glyphosate-ammonium, glyphosate isopropylamine salt (Glyphosate-iso-propylammonium), glyphosate-trimesium, glyphosate-sodium, glyphosate-potassium, bialaphos, glufosinate-ammonium, MCC.

  Fungicide: acibenzolar, ampropyfos, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, Benzamacril, binapacryl, biphenyl, bitertanol, bethoxazine, bordeaux mixture, blasticidin-S, bromoconazole, buprimate (Bupirimate), buthiobate, calcium polysulfide, captafol, captan, copper oxychloride, carpropamid, carbendazim, calb Xin (carboxin), chinomethionat, clobenthiazone, chlorfenazol, chloroneb, chlorothalonil, clothalinil, cufraneb, simoxanil, cymoxanil Proconazole, cyprodinil, cyprofuram, debacarb, dichlorophen, dichlorobutrazol, diclhlofluanid, diclomedine, diclomedine, dicloran Diethofencarb, dicrocymet, difenoconazole, diflumetorim, dimethirimol, dimethomorph, diniconazole ( diniconazole), dinicoazole-M (diniconazole-M), dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazolonone ), Edifenphos, epoxiconazole, etaconazole, etirimol, etridiazole, famoxadone, fenarimol, febuconazole, fenam (fenam) , Fenpiclonil, fenpropidin, fenpropimorph, fentin, ferbam, ferimzone, fluazinam, fludioxo Fludioxonil, fluoroimide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum ( fosetyl-aluminium, fuberidazole, fluralaxyl, fenamidone, fenhexamid, guazatine, hexachlorobenzene, hexaconazole, hymexazol, Imazalil, imibenconazole, iminoctadine, ipconazole, iprobenfos, iprodione, isoprothiolane, Iprovalicarb, kasugamycin, kresoxim-methyl, mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metalaxyl Metconazole, metiram, metinominostrobin, microbutanil, nabam, nickel bis (dimethyldithiocarbamate), nitrothal-isopropyl , Nuarimol, octhilinone, offurace, oxadixyl, oxycarboxin, oxpoconazole fumarate, pefurzoate, pen Penconazole, pencicuron, phthalide, piperalin, polyoxins, probenazole, prochloraz, procymidone, propamocarb hydrochloride, propamocarb hydrochloride, propicocarb hydrochloride Propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen, quintozene, sulfur, spiroxamine ), Tebuconazole, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram ), Tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, triridemorph, triflumizole, 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) 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.

  Among the above-mentioned pesticidal active ingredients, halosulfuron methyl and metazosulfuron are similar in chemical structure to pyrazosulfuron ethyl, and therefore, when included in the preparation of the present invention, decomposition is inhibited in the same manner as pyrazosulfuron ethyl. .

  These agrochemical active ingredients other than pyrazosulfuron ethyl and mesotrione 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 agrochemical active ingredient other than pyrazosulfuron ethyl and mesotrione 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, thickeners, sugars, micro hollow bodies, 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 thickener include heteropolysaccharides such as xanthan gum (xanthan gum), welan gum and rhamzan gum, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, sodium polyacrylate and polyacrylamide, water soluble polymer compounds such as methyl cellulose, Cellulose derivatives such as carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose, smectite clay minerals such as montmorillonite, saponite, hectorite, bentonite, beidellite, nontronite, sauconite, stevenside, laponite, magnesium aluminum silicate and synthetic smectite Can be mentioned.
Examples of the sugar 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 micro hollow body include shirasu balloon, acrylonitrile copolymer micro balloon, phenol resin micro balloon, glass balloon, fly ash balloon, pearlite and the like.

  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.) 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 Keiwa Furnace Co., Ltd.), Neocarrier K (trade name / manufactured by Asada Flour Milling Co., Ltd.), Fubasami K clay (trade name / And Fuyuki Sami Clay Co., Ltd.) and Special Snow F Clay (trade name / 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 / Yoshio Shionogi Co., Ltd.), Carplex # 67 (trade name / Yoshio Shionogi Co., Ltd.), Carplex # 1120 (trade name / Shiono). Yoshigi Pharmaceutical Co., Ltd., Carplex #XR (trade name / Shinogi Pharmaceutical 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 (brand name / Tokuyama Soda Co., Ltd.), Toxeal CU-N (brand name / Tokuyama Soda Co., Ltd.), Toxeal P (brand name / Tokuyama Soda Co., Ltd.), Toxeal NR (brand name / Tokuyama Soda Co., Ltd.) ), Nipsey 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) ), Cyroid 65 (trade name / Fuji Devison Chemical), Cyroid 308 (trade name / Fuji Devison Chemical), Mizukacil P-705 (trade name / Mizusawa Chemical Co., Ltd.), Mizukacil P-802 (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.), for example, Carplex CS-5 (trade name / Yoshio Shiono) Pharmaceutical Co., Ltd., Carplex CS-7 (trade name / Yoshio Shionogi Co., Ltd.) and Carplex CS-701 (trade name / Yoshio Shionogi Co., Ltd.) Sintered products of silica, such as Aerosil 130 (trade name / Nippon Aerosil Co., Ltd.), Aerosil 200 (trade name / Nippon Aerosil Co., Ltd.), Aerosil 380 (trade name / Nippon Aerosil Co., Ltd.) and Aerosil MOX80 (trade name) / Nippon Aerosil Co., Ltd.) anhydrous silica such as FLORITE R (trade name / Tokuyama Soda Co., Ltd.), FLORITE RN (trade name / Tokuyama Soda Co., Ltd.), Toyohero TH (trade name / Toyo Denka Co., Ltd.) Kogyo Co., Ltd.), Zonolite (trade name / Onoda Chemical) and Microcell E (trade name / Johns Manville) and other hydrous calcium silicates, for example, SIPERNAT D17 (trade name / Nippon Aerosil Co., Ltd.), Nipsil SS-10 (Product name / Nippon Silica Co., Ltd.), Nip Seal SS-20 (Product name / Nippon Silica Co., Ltd.) And nip seal SS-30P (trade name / Nihon Silica Co., Ltd.) and other surface-treated silicas such as Aerosil R972 (trade name / Nippon Aerosil Co., Ltd.), Aerosil R202 (trade name / Nippon Aerosil Co., Ltd.) And surface-treated silica made from anhydrous silica such as 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. Further, the “pulverized product of pyriftalide” is a mixed product of 91 parts of pyriftalide having a purity of 99.2% and 9 parts of hydrous amorphous silicon dioxide (trade name: Carplex XR, manufactured by Evonik Degussa Japan).

[Example 1] 0.814 parts of pyrazosulfuron ethyl ground product (purity 99.1%), 2.93 parts of mesotrione (purity 76.7%), 4 parts of pyriphthalide ground product (purity 90.2%) .16 parts, 7.0 parts of dextrin (trade name: dextrin NDS, manufactured by Nissho Chemical Co., Ltd.), 3.0 parts of sodium carboxymethylcellulose (trade name; Cellogen 7AN, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 4.6 parts of crystalline silicon dioxide (trade name: Carplex XR, manufactured by Evonik Degussa Japan), 20.0 parts of glass balloon (trade name: Glass Bubbles S38, manufactured by Sumitomo 3M), potassium chloride (manufactured by Yoneyama Chemical) 6.3), bentonite mineral fine powder (trade name: Kunigel V2, manufactured by Kunimine Co., Ltd.) 20.0 parts, anhydrous citric acid 2.5 parts, diatomaceous earth (trade name: Radiola) Ito # 200, Showa Chemical Industry Co., Ltd.) 7.5 parts was mixed. To this, a mixed liquid of 11.56 parts of pretilachlor (purity 97.3%) and 8.0 parts of liquid paraffin (trade name; Moresco White P-70, manufactured by Moresco) was added and mixed. Here, 1.0 part of dialkylsulfosuccinic acid sodium salt (trade name: Aerol CT-1L, manufactured by Toho Chemical Co., Ltd.) and 1 of decaglycerin monolaurate (trade name; Poem J-0021, manufactured by Riken Vitamin) A mixture of 5 parts dissolved in 22 parts of water was added and mixed. Next, the mixture was granulated using an extrusion granulator equipped with a screen having a diameter of 1.5 mm and then dried at 60 ° C. After the dried product was sized, it was sieved with a 1,000 to 2,000 μm sieve to obtain an agrochemical granule.
[Example 2]
0.814 parts of pyrazosulfuron ethyl ground product (purity 99.1%), 2.93 parts of mesotrione (purity 76.7%), 4.16 parts of pyriphthalide ground product (purity 90.2%), dextrin (Trade name: dextrin NDS, manufactured by Nissho Chemical Co., Ltd.) 5.0 parts, magnesium aluminum silicate (trade name: Beegum K, manufactured by RTVanderbilt Company, Inc.) 1.0 parts, hydrous amorphous silicon dioxide (Product name: Carplex XR, manufactured by Evonik Degussa Japan) 11.6 parts, Glass balloon (Product name: Glass Bubbles S38, manufactured by Sumitomo 3M), 20.0 parts, Potassium chloride (made by Yoneyama Chemical) 6. 3 parts, glucose (grade reagent, manufactured by Junsei Chemical Co., Ltd.) 5.0 parts, anhydrous citric acid 2.5 parts, clay mineral fine powder (trade name: Neocarrier K, manufactured by Asada Flour Milling Co., Ltd.) 2 1.4 parts were mixed. To this, a mixed liquid of 11.56 parts of pretilachlor (purity 97.3%) and 8.0 parts of liquid paraffin (trade name; Moresco White P-70, manufactured by Moresco) was added and mixed. Here, 0.5 part of dialkylsulfosuccinic acid sodium salt (trade name: Aerol CT-1L, manufactured by Toho Chemical Co., Ltd.) and 0 of fatty acid glycol ester (trade name; New Calgen TG30, manufactured by Takemoto Oil & Fat Co., Ltd.) A mixture of 5 parts dissolved in 20 parts of water was added and mixed. Next, the mixture was granulated using an extrusion granulator equipped with a screen having a diameter of 1.5 mm and then dried at 60 ° C. After the dried product was sized, it was sieved with a 1,000 to 2,000 μm sieve to obtain an agrochemical granule.
Example 3
4.3 parts of pyrazosulfuron ethyl (purity 99.1%) finely pulverized to about 5 microns, 65.7 parts of H fine powder (trade name, manufactured by Keiwa Furnace Co., Ltd., silicon dioxide), and petroleum-based paraffin 30.0 parts of a wax (melting point: 69 to 72 ° C.) was melted and kneaded using a kneader at about 100 ° C. Thereafter, the mixture was cooled to about 75 ° C., extruded and granulated with a screen having a hole having a diameter of 1.2 mm, and pulverized with a pin mill to obtain a pyrazosulfuron ethyl paraffin premix.

7.14 parts of this pyrazosulfuron ethyl paraffin premix, 1.17 parts of mesotrione (purity 76.7%), 1.66 parts of pulverized pyriftalide (purity 90.2%), dextrin (trade name: PA Index Y, manufactured by Matsutani Chemical Co., Ltd.) 10.0 parts, hydrous amorphous silicon dioxide (trade name: Carplex XR, manufactured by Evonik Degussa Japan), 5.0 parts, bentonite mineral fine powder (trade name) : Kunigel V2, Kunimine Co., Ltd. 25.0 parts, sodium tripolyphosphate 1.0 part, anhydrous citric acid 1.0 part, clay mineral fine powder (trade name: Neocarrier K, Asada Milling Co., Ltd. 39.99 parts) was mixed. A mixed solution of 4.62 parts of pretilachlor (purity 97.3%) and 3.2 parts of liquid paraffin (trade name: Moresco White P-70, manufactured by Moresco Co., Ltd.) was added thereto and mixed. A mixed solution prepared by dissolving 0.5 part of dialkylsulfosuccinic acid sodium salt (trade name: Aerol CT-1L, manufactured by Toho Chemical Co., Ltd.) in 10 parts of water was added and mixed. Next, the mixture was granulated using an extrusion granulator equipped with a 1.0 mm diameter screen and dried at 60 ° C. After the dried product was sized, it was sieved with a 710 to 1,400 μm sieve to obtain an agrochemical granule.
Example 4
In Example 3, the same treatment as in Example 3 was performed, except that the amount of dextrin was increased to 15.0 parts and the clay mineral fine powder was reduced to 34.99 parts.
Example 5
In Example 4, the same treatment as in Example 4 was performed except that 15.0 parts of dextrin was changed to 15.0 parts of glucose.
Example 6
Example 3 is the same as Example 3 except that the liquid paraffin was increased to 5.0 parts, the hydrous amorphous silicon dioxide was increased to 7 parts, and the clay mineral fine powder was reduced to 36.19 parts. The same process was performed.
Example 7
The same treatment as in Example 6 was performed except that the liquid paraffin was changed to triacylglycerol (trade name: rice white squeezed oil, manufactured by Borso Oil & Fat Co., Ltd.) in Example 6.
Example 8
The same treatment as in Example 6 was performed, except that the liquid paraffin was changed to ditridecyl phthalate (trade name: Vinicizer 20, manufactured by Kao Corporation) in Example 6.
Example 9
The same treatment as in Example 3 was performed except that the liquid paraffin in Example 3 was changed to methyl oleate (trade name: Exepal M-OL, manufactured by Kao Corporation).
Example 10
The same treatment as in Example 6 was performed except that the liquid paraffin was changed to phenylxylylethane (trade name: Hysol SAS, manufactured by Shin Nippon Oil Co., Ltd.) in Example 6.
Example 11
The same treatment as in Example 6 was performed except that the liquid paraffin was changed to diisodecyl adipate (trade name: Vinicizer 50, manufactured by Kao Corporation) in Example 6.
Example 12
The same treatment as in Example 6 was performed, except that the liquid paraffin was changed to trinormal alkyl trimellitic acid (trade name: Trimex N-080, manufactured by Kao Corporation) in Example 6.
Example 13
The same treatment as in Example 3 was performed except that the liquid paraffin was changed to cetyl 2-ethylhexanoate (trade name: Exepal HO, manufactured by Kao Corporation) in Example 3.
Example 14
The same treatment as in Example 3 was performed except that the liquid paraffin was changed to 2-ethylhexyl palmitate (trade name: Exepal EH-P, manufactured by Kao Corporation) in Example 3.
Example 15
The same treatment as in Example 3 was performed except that the liquid paraffin was changed to octyldodecyl myristate (trade name: Exepal OD-M, manufactured by Kao Corporation) in Example 3.
Example 16
In Example 3, the same process as in Example 3 was performed, except that the liquid paraffin was changed to 2-ethylhexyl stearate (trade name: Exepal EH-S, manufactured by Kao Corporation).
Example 17
The same treatment as in Example 3 was performed except that the liquid paraffin was changed to isotridecyl stearate (trade name: Exepal TD-S, manufactured by Kao Corporation) in Example 3.

[Comparative Example 1]
The same treatment as in Example 1 was performed except that liquid paraffin was removed and diatomaceous earth was increased to 15.5 parts.
[Comparative Example 2]
In Example 1, the same treatment as in Example 1 was performed except that citric acid was removed and diatomaceous earth was increased to 10.0 parts.
[Comparative Example 3]
In Example 2, the same treatment as in Example 2 was performed except that liquid paraffin was removed and the clay mineral fine powder was increased to 29.4 parts.
[Comparative Example 4]
In Example 2, the same treatment as in Example 2 was performed except that citric acid was removed and the amount of clay mineral fine powder was increased to 23.9 parts.

[Test example] Severe test Each granule obtained in Examples 1 and 2 and Comparative Examples 1 to 4 was used for this test. A sample was put in an aluminum bag, stored in a thermostat at 54 ° C. for 14 days, and a severe test was performed. The content of the herbicidal active ingredient in the sample before and after the test was measured, and the degradation rate was calculated using the following formula. The results are shown in Tables 1 and 2. The content of the herbicidal active ingredient was quantified by an internal standard method by liquid chromatography.

Decomposition rate (%) = (R−S) / R × 100
R: Content of herbicidal active ingredient in sample before severe test S: Content of herbicidal active ingredient in sample after severe test

Further, the moisture in the grains was measured by the following method using a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd.).
About 100 mg of each granule was used as a measurement sample amount, and measurement was performed under the condition of a water vaporization temperature of 120 ° C. As the Karl Fischer reagent, Hydranal Coulomat AG (manufactured by Sigma Aldrich) and Hydranal Coulomat CG (manufactured by Sigma Aldrich) were used.

Table 1 ――――――――――――――――――――――――――――――――――――――
Moisture content in grains (%) Decomposition rate of mesotrione (%)
―――――――――――――――――――――――――――――――――――――
Example 1 1.2-0.3
Example 2 1.0-0.4
Example 3 0.9 4.0
Example 4 1.4 2.7
Example 5 1.1 1.9
Example 6 1.3 2.2
Example 7 1.2 5.6
Example 8 1.1 3.3
Example 9 1.0 3.0
Example 10 1.7 4.9
Example 11 1.1 3.7
Example 12 1.1 4.3
Example 13 1.1 2.8
Example 14 1.3 2.3
Example 15 1.3 3.0
Example 16 1.1 3.2
Example 17 1.2 2.2
Comparative Example 1 1.3 2.6
Comparative Example 2 1.1 39.6
Comparative Example 3 1.2 1.9
Comparative Example 4 0.8 6.6
―――――――――――――――――――――――――――――――――――――

Table 2 ―――――――――――――――――――――――――――――――――――――
Moisture content in grains (%) Decomposition rate of pyrazosulfuron ethyl (%)
―――――――――――――――――――――――――――――――――――――
Example 1 1.2 10.5
Example 2 1.0 8.4
Example 3 0.9 7.1
Example 4 1.4 9.6
Example 5 1.1 8.6
Example 6 1.3 10.7
Example 7 1.2 9.2
Example 8 1.1 7.0
Example 9 1.0 11.0
Example 10 1.7 6.5
Example 11 1.1 8.6
Example 12 1.1 9.6
Example 13 1.1 10.6
Example 14 1.3 10.2
Example 15 1.3 9.8
Example 16 1.1 10.9
Example 17 1.2 11.3
Comparative Example 1 1.3 18.1
Comparative Example 2 1.1 11.1
Comparative Example 3 1.2 22.1
Comparative Example 4 0.8 10.1
―――――――――――――――――――――――――――――――――――――

As is apparent from the results in Tables 1 and 2, the agrochemical solid preparation of the present invention to which a hydrophobic liquid and citric acid were added was more mesotrione and pyra than the comparative preparation without the hydrophobic liquid or citric acid. The decomposition rate of zosulfuron ethyl was extremely suppressed.

  The preparation of the present invention can be used for controlling weeds.

Claims (7)

  An agrochemical solid preparation containing pyrazosulfuron ethyl, mesotrione, a hydrophobic liquid and an acid.   The agrochemical solid preparation according to claim 1, wherein the acid is citric acid.   The content ratio of the hydrophobic liquid with respect to an agricultural chemical solid formulation is 1 to 20 weight%, The agricultural chemical solid formulation of Claim 1 or 2.   The pesticide solid preparation according to any one of claims 1 to 3, wherein the acid content relative to the solid pesticide preparation is 0.05 to 10% by weight. 5. The agrochemical solid preparation according to any one of claims 1 to 4, wherein the solid preparation is a jumbo agent or a granule. The agrochemical solid preparation according to any one of claims 1 to 5, wherein the hydrophobic liquid is liquid paraffin. Liquid paraffin is normal paraffin or isoparaffin, The agricultural chemical solid formulation of Claim 6.