JP2008074836A - Agricultural granular composition for application to flooded paddy field - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an agricultural granular composition for application to a flooded paddy field, excellent in diffusion underwater in the flooded paddy field; and a package prepared by packaging the composition with a water soluble film. <P>SOLUTION: The agricultural granular composition for application to a flooded paddy field, excellent in diffusion underwater in a flooded paddy field contains an agrochemical active ingredient, a surfactant and glassy hollow bodies having an Na<SB>2</SB>O content of 4 wt.% or less. A package prepared by packaging the composition with a water soluble film is also provided. A breakage rate under pressure of the glassy hollow bodies contained in the agricultural granular composition for application to a flooded paddy field is preferably less than 60%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

Agricultural water surface application with good diffusibility on the surface of flooded sewage paddy fields, comprising a pesticide active ingredient, a surfactant, and a glassy hollow body having a Na ₂ O content of 4% by weight or less The present invention relates to a granular composition and a package in which the composition is packaged with a water-soluble film.

  If the agricultural water surface granular composition is poorly diffusible on the surface of a flooded sewage paddy field, the pesticidal active ingredient is unevenly distributed, which may lead to phytotoxicity and a decrease in biological activity.

As an example of improving the diffusibility by incorporating a hollow particulate carrier into an agricultural water surface application granular composition, a method of blending a glassy hollow body such as a ceramic closed hollow body, a shirasu balloon, a microballoon, or a pearlite ( For example, Patent Documents 1 to 3 are known. However, when the agricultural water surface application granular composition is packaged with a water-soluble film, it has not been known so far that depending on the type of the glassy hollow body, the solubility of the film decreases and the diffusibility deteriorates. . Further, depending on the type of the vitreous hollow body, it has not been known so far that the vitreous hollow body is broken during granulation and a granular composition having sufficient floatability cannot be obtained.
JP 2001-163705 A Japanese Patent Laid-Open No. 06-345603 JP 09-249504 A

  SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and an object of the present invention is to provide an agricultural water surface granular composition having good diffusibility on the surface of a flooded sewage paddy and a package in which the composition is packaged with a water-soluble film. Is to provide.

The inventors of the present invention have found that a packaging body in which an agricultural water surface granular composition containing an agrochemical active ingredient, a surfactant and a glassy hollow body is packaged with a water-soluble film is stored at a high temperature when stored at a high temperature. It has been found that the solubility of the water-soluble film is lowered, the bag breaking time is increased, and the diffusibility of the agricultural water surface application granular composition may be deteriorated. Therefore, as a result of intensive research, the present inventors have used a vitreous hollow body having a Na ₂ O content of 4% by weight or less among the vitreous hollow bodies. It has been found that the bag breaking time of the water-soluble film is not prolonged, and the diffusibility of the agricultural water surface applied granular composition is hardly deteriorated.

  In addition, the present inventors include a vitreous hollow body having a specific pressure fracture rate in an agricultural water surface applied granular composition, whereby the vitreous hollow body is formed by the pressure when extruding the granular composition. It has been found that it becomes difficult to be destroyed and the floating property in the flooded sewage paddy field is improved.

  That is, the present invention provides an agricultural water surface granular composition (hereinafter referred to as the present invention composition) described in [1] to [5] below, and a package (referred to below as [6] and [7]). This is referred to as a package of the present invention.

[1] An agricultural water surface applied granular composition containing a vitreous hollow body having an agrochemical active ingredient, a surfactant, and an Na ₂ O content of 4% by weight or less.

[2] The granular composition for agricultural water surface application according to the above [1], wherein the glassy hollow body has a Na ₂ O content of 2% by weight or less.

  [3] The granular composition for agricultural water surface application according to the above [1] or [2], wherein the pH of the 5% aqueous dispersion of the glassy hollow body is 9.0 or less.

  [4] The agricultural water surface granular composition according to any one of [1] to [3], wherein the pressure fracture rate of the glassy hollow body is less than 60%.

  [5] The agricultural water surface granular composition according to any one of [1] to [4], wherein the glassy hollow body is a soda-lime glassy hollow body.

  [6] A package in which the agricultural water surface granular composition according to any one of [1] to [5] is packaged with a water-soluble film.

  [7] The package according to [6], wherein the water-soluble film material is polyvinyl alcohol.

  Since the composition and package of the present invention have good diffusibility in flooded sewage paddy fields, phytotoxicity hardly occurs and biological effects are good.

The vitreous hollow body used in the present invention is not particularly limited as long as the Na ₂ O content is 4% by weight or less. The upper limit of the Na ₂ O content is preferably 3% by weight or less and more preferably 2% by weight or less for the purpose of preventing the solubility of the water-soluble film from being lowered as much as possible when the package of the present invention is stored at a high temperature. preferable. The lower limit of the content of Na ₂ O, for example, 0.1 wt% or more, and at least 0.5 wt%. Examples of the vitreous hollow body having a Na ₂ O content of 4% by weight or less include Fuji Balloon (trade name: manufactured by Fuji Silysia Chemical), which is a hollow particulate material mainly composed of soda-lime glass. . The Na ₂ O content of the glassy hollow body is a value measured by the ICP emission method.

The reason why the solubility of the water-soluble film is difficult to decrease when the packaging body of the present invention is stored at a high temperature by using a glassy hollow body having a Na ₂ O content of 4% by weight or less is not clear, It is estimated that First, Na ₂ O contained in the vitreous hollow body reacts with water contained in the water-soluble film or the composition of the present invention to produce sodium hydroxide. Since the alcohol part of polyvinyl alcohol, which is the material of the water-soluble film, is partially esterified, the ester part is saponified by the generated sodium hydroxide, and the water solubility of polyvinyl alcohol is reduced (polyvinyl alcohol saponification). When water is excessively advanced, the solubility of water decreases. “Water-soluble polymer” (Supervisor: Ikuo Nakamura, publisher: Chemical Industry Co., Ltd., issue date: July 1, 1978, p. 76), etc. And technical common sense). As a result, the solubility of the water-soluble film decreases.

  The glassy hollow body used in the present invention has a 5% aqueous dispersion having a pH of 9.0 for the purpose of preventing as much as possible a decrease in solubility of the water-soluble film when the package of the present invention is stored at a high temperature. The following are preferred, those of 5.0 to 9.0 are more preferred, and those of 6.0 to 8.5 are most preferred.

The glassy hollow body used in the present invention preferably has a pressure fracture rate of less than 60% for the purpose of improving the floatability of the composition of the present invention in a flooded sewage paddy field. % Is preferable, and 15% to 40% is more preferable. The pressure fracture rate of the glassy hollow body is a value obtained from a volume change when a hydrostatic pressure of 300 kg / cm ² is applied.

  The volume median diameter of the vitreous hollow body used in the present invention is usually 10 μm to 100 μm, preferably 20 μm to 80 μm, and more preferably 30 μm to 50 μm.

  Although content of the glassy hollow body in this invention composition can be selected suitably, the range of 15.0-30.0 weight part is preferable with respect to 100 weight part of this invention composition.

  The agrochemical active ingredient used by this invention is not specifically limited, The general name of the agrochemical active ingredient used by this invention is illustrated below.

  Herbicides: pyrazosulfuron ethyl, halosulfuron methyl, bensulfuron methyl, imazosulfuron, azimsulfuron, cinosulfuron, cyclosulfamuron ), Ethoxysulfuron, pyraclonil, tefuryltirone, mesotrione, pyrimisulfan, penoxsulam, aminopyralid, bencarbazone, full Cetosulfuron, monosulfuron, monosulfuron-methyl, pinoxaden, propoxycarbazone-sodium salt, pyrasulfo Tall (pyrasulfotole), pyroxasulfone (pyroxasulfone), pyroxsulam (pyroxsulam), tembotrione (tembotrione), thiencarbazone-methyl (thiencarbazone-methyl), topramezon (topramezon), esprocarb (esprocarb), benthiocarb (benthiocarb), molinate (molinate) ), Dimepiperate, pyributicarb, mefenacet, butachlor, pretilachlor, tenylchlor, bromobutide etobenzanid, yluron, ururylyl , Bentazone, bentazone salt, 2,4-D, 2,4-D salt, 2,4-D ester, MCP, MCP salt, MCP ester, MCPB, MCPB salt, MCPB S Ter, phenothiol (MCPA-thioethyl), chromeprop, cloproprop, naproanilide, oxadiazon, pyrazolate, pyrazoloxy, benzofenap, oxadiargyl, dimethametry ), Cimetryn, piperophos, anilofos, butamifos, bensulide, dithiopyr, pyrinobac methyl, CNP, chlormethoxynil, cyhalo Hophalobutyl (cyhalofop butyl), bifenox, caffenstrole, pentoxazone, indanofan, oxaziclomefone, fentrazamid e), butenachlor, ACN, benzobicyclon, benfuresate, cimmethylin, simazine, dichlobenil, diuron, chloro IPC (chlorpropham), atrazine atrazine, alachlor, isouron, chlorphtalim, cyanazin, trifluralin, butamifos, propyzamide, promethrin, pendimethalin , Metolachlor, metribuzin, linuron, lenacil, propanil, MCPA, ioxynil octanoate, ashlam, quizalofop-ethyl, The Ropakiza hop (propaquizafop), quizalofop-tefuryl, sethoxydim, thifensulfuron-methyl, fenoxaprop-ethyl, phenmedipham, fluazif Hop butyl (fluazifop-butyl), bentazone (bentazone), SAP (bensulide), TCTP (chlorthal-dimethyl, tetorachlorothiophene), amiprophosmethyl, amethrin (ametryn), isoxaben, orbencarb, Carbutilate, dithiopyr, siduron, thiazafluron, napropamide, prodiamine, benefin, methyl dymron, 2,4-PA, MCPPA , Frazasulf Ron (flazasulfuron), metsulfuron-methyl, imazaquin, imazapyr, tetrapion (flupropanate), tebuthiuron, bromacil, hexazinone, glyphosate ammonium salt (gphosate-ammonium salt) ammonium), glyphosate isopropylamine salt (glyphosate-iso-propylammonium), glyphosate-trimesium, glyphosate sodium salt (glyphosate-sodium), glyphosate potassium salt (glyphosate-potassium), bialaphos, glufosinate ( 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), cype Methperin (cypermethrin), cyromazine, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diacloden, diflubenzuron ), Dimethylvinphos, diofenolan, disulfoton, dimethoate, EPN, esfenvalerate, ethiofencarb, ethiprole, etofenprox, Etrimfos, fenitrothion, fenobucarb, fenoxycarb, 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.

  These pesticidal active ingredients can be used alone or in admixture of two or more, and the ratio in the case of mixing can be freely selected. Although content of the agrochemical active ingredient in this invention composition can be selected suitably, the range of 0.1-50 weight part is preferable with respect to 100 weight part of this invention composition.

  Examples of the surfactant used in the composition of the present invention 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 acrylate, 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. Although content of surfactant in this invention composition can be selected suitably, the range of 0.5-20 weight part is preferable with respect to 100 weight part of this invention composition.

  Various adjuvants can be further contained in the composition of the present invention. Adjuvants that can be used include binders, solid carriers, solvents, and the like.

  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.) 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 / 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) ), 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.

  The water-soluble film used in the package of the present invention is suitably a film that rapidly dissolves or disperses in water. Examples of the film material include polyvinyl alcohol, polyoxypolyalkylene glycol, hydroxypropylcellulose, hydroxypropylmethylcellulose, Examples include methylcellulose, sodium carboxymethylcellulose, sodium polyacrylate, alginic acid, gelatin, pullulan, solubilized starch and the like. Moreover, the thickness of the water-soluble film used is not particularly limited, but generally about 20 μm to 100 μm is preferable.

As a method for producing the composition of the present invention, for example, an agrochemical active ingredient, a surfactant, a glassy hollow body having a Na ₂ O content of 4% by weight or less, and, if necessary, other auxiliary agents and water are mixed. Then, the method of drying after granulation using a granulator is mentioned. The granulation can be produced using a fluidized bed granulator, a spray drying granulator, an agitation granulator, a compression granulator, a rolling granulator, an extrusion granulator or the like.

  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, and “pH” of the vitreous hollow body is a value of a 5% aqueous dispersion. Also, “Compound A” is 3-chloro-N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -1-methyl-4- (5-methyl-5,6-dihydro-1,4,2 -Dioxazin-3-yl) -1H-pyrazole-5-sulfonamide. The purity of Compound A is 98.6%, and 3-chloro-N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -1-methyl-4- (6-methyl-5,6-dihydro as an impurity 1.0% of -1,4,2-dioxazin-3-yl) -1H-pyrazole-5-sulfonamide.

[Example 1]
Pyrazosulfuron ethyl (generic name) 5.0 parts, soda-lime glassy hollow body (pressure fracture rate 35%, pH 7.2, Na ₂ O 1.5 wt%) 25.0 parts, bentonite 30.0 parts 37.0 parts of diatomaceous earth was mixed. Here, 3.0 parts of acetylene diol (trade name: Surfynol SE-F, manufactured by Air Products) and water were added and mixed. Subsequently, after granulating using an extrusion granulator equipped with a screen having a diameter of 1.5 mm, it was dried at 50 ° C. to obtain 100 parts of an agricultural water surface applied granular composition.

[Example 2]
25.0 parts of soda-lime glassy hollow body (pressure fracture rate 35%, pH 7.2, Na ₂ O 1.5% by weight) of Example 1 was soda-lime glassy hollow body (pressure fracture rate 20%, 100 parts by weight of an agricultural water surface applied granular composition was obtained in the same manner except that it was changed to 25.0 parts (pH 8.3, Na ₂ O 1.5 wt%).

Example 3
In the same manner as in Example 1 except that pyrazosulfuronethyl (generic name) was changed to 5.0 parts of Compound A, 100 parts of an agricultural water surface applied granular composition was obtained.

Example 4
A mixed solution of 2.0 parts of dimetamethrin (generic name) and 0.6 parts of diisobutyl adipate (trade name: Vinicizer 40, manufactured by Kao), soda-lime glassy hollow body (pressure fracture rate 20%, pH 8.3, Na ₂ O 1.5% by weight) 25.0 parts, 30.0 parts of bentonite were mixed diatomaceous earth 44.4 parts. Here, 3.0 parts of acetylene diol (trade name: Surfynol SE-F, manufactured by Air Products) and water were added and mixed. Subsequently, after granulating using an extrusion granulator equipped with a screen having a diameter of 1.5 mm, it was dried at 50 ° C. to obtain 100 parts of an agricultural water surface applied granular composition.

Example 5
The soda-lime glassy hollow body of Example 1 (pressure fracture rate 35%, pH 7.2, Na ₂ O 1.5% by weight) was soda-lime glassy hollow body (pressure fracture rate 60%, pH 6.7, Na ₂ O 1.5 wt%) except for changing 25.0 parts were obtained in the same manner agricultural submerged application particulate composition 100 parts.

Example 6
Pyrazosulfuron ethyl (generic name) 5.0 parts, soda-lime glassy hollow body (pressure fracture rate 35%, pH 7.2, Na ₂ O 1.5% by weight) 25.0 parts, sodium carboxymethyl cellulose (product) Name: Serogen PR, manufactured by Daiichi Kogyo) 5.0 parts, sodium salt of special aromatic sulfonic acid formalin condensate (trade name: Demol SN-B, manufactured by Kao) 5.0 parts, 5.0 parts of potassium chloride, 30.0 parts of bentonite and 22.0 parts of diatomaceous earth were mixed. Here, 3.0 parts of acetylene diol (trade name: Surfynol SE-F, manufactured by Air Products) and water were added and mixed. Subsequently, after granulating using an extrusion granulator equipped with a screen having a diameter of 1.5 mm, it was dried at 50 ° C. to obtain 100 parts of an agricultural water surface applied granular composition.

[Comparative Example 1]
The soda-lime glass hollow body of Example 1 (pressure fracture rate 35%, pH 7.2, Na ₂ O 1.5% by weight) was soda-lime glass hollow body (pressure fracture rate 44%, pH 9.4, Na ₂ O (6.8 wt%) In the same manner except that it was changed to 25.0 parts, 100 parts of an agricultural water surface applied granular composition was obtained.

[Test example]
30 g of the agricultural water surface granular composition obtained in Examples 1 to 6 and Comparative Example 1 was placed in a water-soluble film (trade name: VF-HP4000, manufactured by Kuraray Co., Ltd.) to obtain a package. The floating diffusivity was measured immediately after production and after storage for 30 days in a thermostatic bath at 50 ° C. The floating diffusivity was measured under the following measurement conditions.

[Measurement of floating diffusivity]
Water is poured into a 0.8 m ² water tank to a depth of 4 cm, and the package is put therein. The time until the packaging body broke and the agricultural water surface applied granular composition started to diffuse was measured. Further, the amount of sedimentation 15 minutes after the addition was visually evaluated.

The results are shown in Table 1. However, the symbols in the table represent the following meanings: A: Pressurized fracture rate of the hollow particulate carrier B: Time to break the water-soluble film immediately after production C: Water-soluble film after storage at 50 ° C. for 30 days Bag breaking time D: Amount of sediment immediately after production
Table 1 ――――――――――――――――――――――――――
A B C D
――――――――――――――――――――――――――
Example 1 35% 9 seconds 12 seconds 0%
Example 2 20% 10 seconds 14 seconds 0%
Example 3 20% 10 seconds 14 seconds 0%
Example 4 20% 10 seconds 12 seconds 0%
Example 5 60% 12 seconds 12 seconds 80%
Example 6 35% 13 seconds 12 seconds 0%
Comparative Example 1 44% 9 seconds 90 seconds 0%
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  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an agricultural water surface granular composition having good diffusibility on the surface of a flooded sewage paddy and a package in which the composition is packaged with a water-soluble film.

Claims (7)

An agricultural water surface granular composition containing a vitreous hollow body having an agrochemical active ingredient, a surfactant, and a Na ₂ O content of 4% by weight or less. The granular composition for agricultural water surface application according to claim 1, wherein the content of Na ₂ O in the glassy hollow body is 2% by weight or less.   The granular composition for agricultural water surface application according to claim 1 or 2, wherein the pH of the 5% aqueous dispersion of the vitreous hollow body is 9.0 or less.   The granular composition for agricultural water surface application according to any one of claims 1 to 3, wherein the pressure fracture rate of the glassy hollow body is less than 60%.   The granular composition for agricultural water surface application according to any one of claims 1 to 4, wherein the glassy hollow body is a soda-lime glassy hollow body.   A package in which the agricultural water surface granular composition according to any one of claims 1 to 5 is packaged with a water-soluble film.   The package according to claim 6, wherein the water-soluble film is made of polyvinyl alcohol.