WO2017065015A1 - Granular agrochemical composition - Google Patents

Abstract

The present invention addresses the problem of providing a granular agrochemical composition capable of floating on a water surface, wherein the granular agrochemical composition has excellent self-dispersion properties and improved dispersion and suspension of an active agrochemical component following disintegration on the water surface. The granular agrochemical composition that overcomes this problem: contains an active agrochemical component, silica, a surfactant, hollow bodies, and a solid carrier; has a particle size distribution such that particles measuring 3 mm or more in diameter account for 80% or more; and has the property of floating on a water surface and disintegrating on the water surface within 30 minutes, wherein the granular agrochemical composition is characterized in that the silica is a polymethyl silylated silica in which the surface of hydrophilic silica is modified with dimethyl silyl groups or trimethyl silyl groups.

Description

Granular pesticide composition

The present invention relates to a granular agrochemical composition, and more particularly, to a granular agrochemical composition capable of uniformly diffusing an agrochemical active ingredient by, for example, spraying a small amount directly onto a water surface such as a paddy field.

Conventionally, agrochemical compositions used in paddy fields and the like are generally granules, powders, emulsions, wettable powders, and flowables. Of these agrochemical compositions, granules and powders have been sprayed directly without diluting 1-4 kg of water per 10a, but in recent years there has been a call for labor saving in spraying pesticides. Therefore, it is possible to reduce the spraying amount as a pesticide composition by increasing the content of the pesticide active ingredient in the pesticide composition, or to spray it by simply throwing it from the shore without entering the paddy field. Things are sought.

Various labor-saving agricultural chemical compositions have been studied and such techniques have been disclosed in response to such demands. For example, Patent Document 1 discloses an agricultural chemical active ingredient and a surfactant. Water-floating large-sized granular pesticide composition characterized by having a particle size distribution in which particles having a particle diameter of 3 mm or more are 80% or more and having a property of floating on the water surface and disintegrating on the water surface within 30 minutes Is disclosed. The agrochemical composition has a high self-diffusibility, and by spraying a small amount of the agrochemical composition of about 250-500 g per 10 a paddy field, the agrochemical active ingredient is uniformly distributed throughout the paddy field. It can be thrown in and can be said to be an ideal pesticide composition for labor saving application.

The self-diffusion property in the granular agrochemical composition of Patent Document 1 refers to the disintegration of the agrochemical active ingredient that formed the granular agrochemical composition by disintegrating the granular agrochemical composition while floating on a water surface such as paddy field for a predetermined time. It is the performance that particles diffuse to a place away from the treatment point and are distributed over a wide area of the water surface. The self-diffusion property of this granular pesticide composition depends on the property that the surfactant in the granular pesticide composition spreads quickly to the entire gas-liquid interface such as paddy fields. It is established in the form of piggybacking the granular agrochemical composition in the middle of the collapse to the wave brought to. However, even if the granular agrochemical composition collapses, the dispersibility and suspension of the agrochemical active ingredient that constituted it is poor, that is, the agrochemical active ingredient is in a state where it does not disperse by forming an aggregate, The agglomerates may fall off from the granular pesticide composition in the middle of disintegration and settle in place, and the desired self-diffusion property may not be exhibited as a granular pesticide composition. It was.

By the way, amorphous silica is one of the substances known as auxiliary agents used in agricultural chemical formulations, and the information is disclosed in Non-Patent Document 1, for example. Amorphous silica is classified into wet silica (precipitated silica) and dry silica (fumed silica) depending on the production method. Wet silica is usually a porous fine powder having a particle size of about 1-10 μm, and has a high oil absorption capacity due to its porous structure, and can hold about 200-340 mL of liquid per 100 g of wet silica. In the field of agrochemical formulation technology, it is widely used as a liquid pesticide active ingredient and an adsorbent carrier for auxiliary materials. On the other hand, dry silica usually has a very fine particle diameter of about 5-50 nm and has a correspondingly high specific surface area, but has no porous structure, so it does not have the ability to carry liquid inside the particles, Oil absorption capacity is low. In addition, the amorphous silica has a silanol group which is a hydrophilic group in the molecule, regardless of whether it is produced by a wet method or a dry method. There are also those in which the hydroxy group on the surface of the silica particles is chemically substituted with a hydrophobic group, and such silica is difficult to wet with water and is called hydrophobic silica.

Non-Patent Document 1 discloses the use of granules as an aggregation inhibitor as one of the uses of amorphous silica in the technical field of agricultural chemical formulations. However, in the granular agrochemical composition of Patent Document 1, when the blending of amorphous silica was examined, a granular agrochemical composition using any of hydrophilic wet silica, hydrophobic wet silica, hydrophilic dry silica, and hydrophobic dry silica. In some cases, the agglomeration inhibitory effect of the pesticidal active ingredient may be insufficient, or rather the aggregation may be remarkable, and further, the disintegration of the granular agrochemical composition on the water surface may be prevented. It did not come.

JP 2002-179507 A

JPO Standard Technology Collection (Agricultural Chemicals Technology) Database: Solid Carrier

The main object of the present invention is to provide a granular pesticide composition excellent in self-diffusion property in a water-floating granular pesticide composition, in which the dispersion suspension of the pesticide active ingredient after the above collapsed on the water surface is improved. It is.

As a result of diligent research, the present inventors have found that a granular agrochemical composition containing hydrophobic silica in which the surface of hydrophilic silica is modified with a dimethylsilyl group or a trimethylsilyl group can solve the above problems, and the present invention It came to be completed.

That is, the present invention has the following contents.

[1] A pesticidal active ingredient, silica, a surfactant, a hollow body, and a solid carrier, a particle size distribution in which particles having a particle size of 3 mm or more are 80% or more, and floating on the water surface, A granular agrochemical composition having a property of collapsing on the water surface within 30 minutes, wherein the silica is polymethylsilylated silica in which the surface of hydrophilic silica is modified with dimethylsilyl groups or trimethylsilyl groups. A granular pesticide composition.

[2] The granular agrochemical composition as described in 1 above, wherein the hydrophilic silica which is a raw material of polymethylsilylated silica is dry silica.

[3] The granular pesticide composition as described in 1 or 2 above, wherein the polymethylsilylated silica has a specific surface area of 10 to 1000 m ² / g.

[4] The granular agrochemical composition according to any one of the above 1-3, wherein the blending ratio of the polymethylsilylated silica in the granular agrochemical composition is 1-10% by mass based on the total amount of the granular agrochemical composition.

[5] The granular agrochemical composition according to any one of the above 1-4, wherein the polymethylsilylated silica is obtained by modifying the surface of hydrophilic silica with a trimethylsilyl group.

[6] The above 1-5, wherein the pesticidal active ingredient is one or more selected from the group consisting of pyrimisulphan, pyroxylone, phenoxasulfone, fenquinotrione, phentolazamide, benzobicyclon, and benzophenap The granular agrochemical composition according to any one of the above.

According to the present invention, the composition contains an agrochemical active ingredient, and those having a particle size of 3 mm or more have a particle size distribution of 80% or more and a property of floating on the water surface, and are disintegrated on the water surface within 30 minutes. It is possible to provide a granular agrochemical composition that improves the dispersion and suspension of the agrochemical active ingredient after being disintegrated on the water surface, that is, excellent in self-diffusion. Moreover, the granular agrochemical composition of this invention is excellent also in disintegration.

In this specification, when dealing with the particle size and particle size distribution of a granular agrochemical composition, “minor axis” means the length of a short part in the shape of the granule, and “major axis” is the length of a long part. Specifically, these are the shortest and longest values respectively measured by sandwiching any two ends of the granular agrochemical composition with calipers. “Particle size” means a particle size obtained by a sieving method using a sieve having a predetermined opening, and “Particle size distribution” means an integrated weight percentage of a prescribed particle size range obtained by a sieving method. . On the other hand, when dealing with the particle size and particle size distribution of individual components including agrochemical active ingredients, the “average particle size” means the volume average size obtained by the laser diffraction method, and the “particle size distribution” means the laser diffraction method. (Accumulated by wet method; SK Laser Micron Sizer LMS-2000e (manufactured by Seishin Enterprise)). The “specific surface area” means a specific surface area determined by a BET method (nitrogen adsorption method) based on ISO 9277: 2010 (JIS method Z8830: 2013).

The granular agrochemical composition of the present invention is an extruded granulated agrochemical composition comprising an agrochemical active ingredient, polymethylsilylated silica, a surfactant, a hollow body, and a solid carrier. The particle size distribution is 3% or more and the particle size distribution is 80% or more and the property of floating on the water surface, and the disintegration time is within 30 minutes. Such a granular agrochemical composition is first mixed with raw materials constituting the granular agrochemical composition, added with a predetermined amount of water, kneaded, extruded from a screen having a pore diameter of 3 mm or more, granulated, dried, for example, It can be obtained by taking out granules having a desired particle size using two sieves having different openings.

The agrochemical active ingredient that can be used in the granular agrochemical composition of the present invention is not particularly limited, and may be solid or liquid at room temperature. Although the agrochemical active ingredient which can be used for this invention is listed below, it is not limited to these.

[Herbicidal active ingredient]
Ioxynil, aclonifen, acrolein, azafenidin, acifluorfen (including salts with sodium, etc.), azimsulfuron, acelam, acelam- (Acetochlor), atrazine, anilofos, amicarbazone, amidosulfuron, amitrole, aminocyclopyrachlor (methyl), aminopyrachlor ofos-methyl, amethrin, alachlor, alloxydim, isouron, isoxachlortole, isoxaflutole, isopablon ), Ipfencarbazone, imazaquin, imazapic (including salts with amines, etc.), imazapyr (including salts such as isopropylamine), imazametabenz methyz-methyl (imabine) ), Imazamox, imazeta Imazethapyr, imazosulfuron, indaziflam, indanophan, erinazine-ur, etrincarb, esprocarb. ), Etidimuron, ethoxysulfuron, ethoxyphen-ethyl, etofumesate, etobenzanid, endothal disodium salt (endothal-is) dium), oxadiazon, oxadiaargyl, oxadichromefone, oxyfluorfen, oryzalin, entrabole, fensulfone, ensulfaurone Carbethylate-carbylate, carbbutilate, carbetamide, quizalofop-ethyl, quizalofop-p-ethylp alfop-P-tefuryl, quinoclamamine, quinclorac, quinmerac, cumyluron, clacyfos, glyphosate (sodium, amine, potassium, amine) Including salts such as isopropylamine, dimethylamine or trimesium), glufosinate (including salts such as amine or sodium), glufosinate P-sodium, clethodim, clodinahop Propargyl (clodinafop-propargyl) Clopyralid, Chromazone, Chloromphen, Chloridazon, Chloridazon, Chloridazon, Chloridazon, Chloridazon, Chloridazon, Chloridazon Chlorsulfuron, chlorthal-dimethyl, chlorthiamid, chlorphthalim, chlorflulenol-methyl, chlorpropharm m), chlorbromuron, chloroxuron, chlorotoluron, saflufenacil, cyanazine, cyanamide, diuron, diuron, diuron, e (Dicamba) (including salts such as amine, diethylamine, isopropylamine, diglycolamine, sodium or lithium), cycloate, cycloxydim, diclosulamum, cyclosulfamuron, cyclopyramuron Molate (Cycl pyrimorate, diclobenil, diclohop-P-methyl, diclohop-methyl, dichlorprop, dichlorprop-P, dichlorprop-P diquat, dithiopyr, siduron, dinitramine, cinidon-ethyl, cinosulfuron, dinoterb, cyhalohop butyl (midhlo butyl) , Difenzoq at), diflufenican, diflufenzopyr, simazine, dimethacryl, dimetametrin, dimethenamide (dimethenamide), dimethenamide (dimethenamide), dimethenamide (dimethenamide). Dimethylpiperate, dimeflon, cinmethylin, swep, sulcotrione, sulfentrazone, cetyldim, terdyldim imuron, dalapon, thiazopyr, thiafenacil, thiencarbazone (sodium salt, including methyl ester, etc.), thiocarbazil, thiobendiamin, thiobendimine Ruflon-methyl, desmedifam, desmetrine, tenylchlor, tebutam, tebuthiuron, tepraloxyme furritrie), tembotrione, terbuthylazine, terbutrimon, terbumethylone, turbutiton, Tri-allate, trietazine, triclopyr, triclopyr-butotyl, trifludimoxazine, tritosulfuron lfuron), triflusulfuron-methyl, trifluralin, trifloxysulfuron-sodium, tribenuron-methylol, tylururone-methylol. (Including salts with sodium, etc.), naproanilide, napropamide, napropamide-M, neburon, norflurazon, vernarate, u Halxife N-methyl, haloxyhop, haloxyhop-P, haloxyhop-etolyl, halosulfuron-methyl, pi ), Bicyclopyrone, bispyribac-sodium, pinoxaden, bifenox, piperophos, pyraulonyl, pyrasulfol, pyrasulfol azoxyfen), pyrazosulfuron-ethyl, pyrazolynate, bilanafos, pyraflufen-ethyl, pyriforol sodium, pyriforol salt , Pyriftalid, pyributicalcarb, pyribenzoxim, pyrimisulfan, pyriminobac-methyl, pyroxasulfone pylosulfone (Pyroxsuram), phenisopham, phenuron, fenoxasulfone, fenoxaprop-P-ethyl, fenquinotrione, fenquinotriethyl -Ethyl), fentrazamide, fenmedifam, foramsulfuron, butachlor, butafenacil, butamifos, butyrate butylate, butyrate butylate ), Butralin, butroxydim, flazasulfuron, flampprop (including methyl, ethyl, isopropyl ester), flampprop-M (methyl, ethyl, isopropyl) Esters), fluazifop-butyl, fluazifop-P-butyl, fluazolate, fluometuron, fluorglycolene-fluorocarbene Sodium salt (flucarbazone-sodium), fluchloraline (f uchloralin, flucetosulfuron, fluthiacet-methyl, flupyrsulfuron-methyl-sodium, flufenacet, flufenpyrethyl. ), Flupropanate, flupoxame, flumioxazin, flumicrolac-pentyl, flumesumram, fluridone flurone, fluridine flurone luroxypyr, flurochloridone, pretilachlor, procarbazone sodium salt, prodiamine, prosulfacarb, zaproprop , Propazine, propanil, propyzamide, propisochlor, propyrisulfuron, propharm, proflurazol, profluzol Thorium salt (propoxycarbazone-sodium), proxoxydim, bromacil, brompyrazon, promethrin, promethon, bromoxynyl, butanoic acid ), Bromophenoxime, bromobutide, floraslam, petoxamide, benazolin, penoxsulam, peptoxamlam, heptamuram p flubutamid, pebrate, bencarbazone, pendimethalin, benzfendizone, benzsulfide, benzosulfuron methyl, benzosulfuron-benzoyl Nap (benzofenap), bentazone, pentanochlor, pentoxazone, benfluralin, benfurestate, fosamine, fomesafene, omesafen Mecoprop (including salts such as sodium, potassium, isopropylamine, triethanolamine, dimethylamine), mecoprop-P-potassium, mesosulfuron-methyl, mesotrione ( mesotrione, metazachlor, metazosulfuron, metabenzthiazuron, metamitron, methitron, methizolone, methizolone, methizolone (Met osulam, metobromuron, metobenzuron, metolachlor, metribuzin, mefenacet, monolinuron, molinulon, molinulon, molinulon, molinulon Sodium salt (iodosulfuron-methyl-sodium), iofensulfuron, iofensulfuron-sodium salt, lactofen, linuron, 2, lenacil, 2, lenacil -Trichlorobenzoic acid (2,3,6-TBA), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 2,4-dichlorophenoxyacetic acid (2,4-D) (amine, (Including salts such as diethylamine, triethanolamine, isopropylamine, sodium or lithium), 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), AE-F-150944 (code number), 4, 6-dinitro-O-cresol (DNOC) (including salts such as amine or sodium), S-ethyldipropylthiocarbamate (EPTC), 2-methyl-4-chlorophenoxyacetic acid (MCPA), MCPA thioethyl (MCPA) -Thioethyl), 2-methyl-4-chlorophenoxybutyric acid (MCPB) (sodium salt, ethyl ester) ), SYP-298 (code number), SYP-300 (code number), S-metolachlor, 2,2,2-trichloroacetic acid (TCA) (salt such as sodium, calcium or ammonia) including).

[Insecticide active ingredient]
Acrinathrin, Azadirachtin, Azamethiphos, Azinophos-ethyl, Azeinosylacetin, Acequinocetyl (Acephate), azocyclotin, abamectin, afidopyropen, amidoflumet, amitraz, alanib, alicalb, aldib Aldoxycarb, allethrin [including d-cis-trans-form and d-trans-form], isazophos, isamifofos, isocarbophos, isoxathion methyl, isoxathion methyl, isoxathion (Isofenphos-methyl), isoprocarb, ivermectin, imicyafos, imidacloprid, imiprothrin, indoxacarb, indoxacarb offencarb, ethifotin, etemoforthos, etemoforthos, etemoforthos Endosulfan, empentrin, oxamyl, oxydimethon-methyl, oxydeprofos, omethoate, cassafote, cadusafotes (Kappa-tefluthrin), kappa-bifenthrin, caranjin, cartap, carbaryl, carbosulfan, carbofuran (HC) ), Xylylcarb, quinalphos, quinoprene, quinomethionate, coumafos, cryolite, lothianzine, rothenidin, crotiandin ide), chlorantraniliprole, chloroethoxyphos, chlordane, chloropicrin, chlorpyrifos, chlorpyrifos, chlorpyrifos, chloropyrifos, chloropyrifos, chloropyrifos, chloropyrifos Vinfenfos, chlorfluazuron, chlormefos, cyanophos, diafenthiuron, diamidafos, cyantraniprole (cyan) traniliprole, dienochlor, cenopyrafen, dioxabenphos, diphenolan, cyclaniprole, diclotophos, dicrotophos, , Dichlorovos, dichloromezothiaz, 1,3-dichloropropene, dicofol, dicyclanil, disulfoton, dinote Dinotefuran, dinobuton, cyhalothrin [including gamma-form, lambda-form], cyphenothrin [including (1R) -trans-form], cyfluthrin [cyfluthrin [cyfluthrin] Diflubenzuron, cyflumetofen, diflovidazin, cyhexatin, cypermethrin [alpha-, beta-, beta-, beta-, beta-, beta-, beta-, beta, Dimethylvinphos, dimethylfluthrin , Dimethoate, silafluofen, cyromazine, spinetoram, spinosad, spirodicrofen, spirotetraspirosulfuron Salt (sulcofuron-sodium), sulfluramide (sulfluramid), sulfoxafluor (sulfoxafloor), sulfotep (sulfotep) (diazinon), thiacloprid (thiacloxid), thiamethoxam (thiamethoxoxa (thiamethoxax) azafen, thiodicarb, thiocyclam, thiosultap, thionazine, thiophanox, thiomethonte, tetrachlorvinphos Tetroliliprole, tetramethylfluthrin, tetramethrin, tebupyrimfos, tebufenozide, tebufenpyrthful ), Teflubenzuron, demethon-S-methyl, temephos, deltamethrin, terbufos, tralomethrin, ns, transfluthrin ), Triazophos, trichlorfon, triflumuron, triflumezopyrim, trimethacarbin, tolfenpyraden, tolfenpyraden ram), novaluron, noviflumuron, verticillium lecanii, hydroprene, pasturia penion, pastiothion, paradoxion Methyl (parathion-methyl), halfenprox, halofenozide, bioallethrin, bioarethrin S-cyclopentenyl thibipentyl (bi-ethrinthylene) n), bistrifluron, hydramethylnon, bifenazate, bifenthrin, piflubumide, piperonylpyroxypyropyridine Role, pyridafenthione, pyridaben, pyridalyl, pyrifluquinazone, pyriprole, pyriprofen, pyriprox Rimicarb, pyrimidifen, pyriminostrobin, pirimiphos-methyl, pyrethrine, fimulin, p ), Fenitrothion, phenoxycarb, phenothiocarb, phenothrin [including (1R) -trans-form], fenobucarb, fenthion, fention, fention, fention, fention nthoate), fenvalerate, fenpyroximate, fenbutatin oxide, fenpropathrin, fofofos, carboxysulfuride, sulfoyl fluoride , Butoxycarboxim, buprofezin, furathiocarb, praretrin, fluacrylpyrim, fluazuluon, fluazuron Sodium fluoroacetate, flucycloxuron, flucytrinate, flusulfamide, fluvalinate [including tau-form], flupiradi fluazo ), Flufiprole, flufenerim, fluphenoxystrobin, flufenoxuron, fluhexafon, flubenamide (flubenamide), flubenamidemide lumethrin, protrifenbute, prothiofos, flonicamid, propofos, propargite, profenofos, brofurolido , Propoxur, flometoquin, bromopropyrate, hexathiazox, hexaflumuron, pequilomyces tenuipes (Paecilomyces) uipes), Pecilomyces fumosoroseus, heptafluthrin, heptenophos (permethrinb), permethrin (benmethothib), benclothiaz (benmethothib) ), Benfuracarb, beauveria tenella, beauberia bassiana, beauberia bronniati, x, salon phosalone, phosthiazate, phosthietan, phosphamidone, phosmet, polynactin complex, formatenate, ect, m Mecarbam, mesulfenfos, methomyl, methaflumizone, methamidophos, methamofion, methicarb, methithion , Methyl isothiocyanate, methyl bromide, methoxychlor, methoxyphenozide, methothrine, methofrine, methofrine, , Meperfluthrin, monacrosporium phymatopagum, monocrotophos, momfluorothrin, little a A (litl) re-A), Little A B (Little-B), Aluminum Phosphide, Zinc Phosphide, Hydrogen Phosphine, Lufenuron, Rescalure, Resmethrin , Lepimectin, rotenone, fenbutatin oxide, calcium cyanide, nicotine sulfate, (Z) -11-tetradecenyl = acetate, (Z) -11-hexadenal Z) -11-hexadecenyl = acetate, (Z) -9,12-tetradecadienyl = aceta (Z) -9-tetradecen-1-ol, (Z, E) -9,11-tetradecadienyl acetate, (Z, E) -9,12-tetradecadienyl acetate, Bacillus Popilie (Bacillus popilliae), Bacillus subtilis, Bacillus sphaericus, Bacillus thuringiensis subspecies Izawai (Bacillus thuringiensissis Aizawai), Bacillus thuringiensis subsp. Islaelensis, Bacillus thuringiensis subsp. Kurstakis, B. burs. thuringiensis subsp. 1,1,1-G Chloro-2,2-bis (4-chlorophenyl) ethane (DDT), dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate (DEP), 4,6-dinitro-o-cresol (DNOC), O , O-diethyl-O- [4- (dimethylsulfamoyl) phenyl] -phosphorothionate (DSP), ethyl-p-nitrophenylthionobenzenephosphonate (EPN), nuclear polyhedrosis virus embedded body, NA-85 (code number), NA-89 (code number), NC-515 (code number), RU15525 (code number), ZDI-2501 (code number), XMC, Z-13-icosen-10-one, ZXI8901 (code number), ME5382.

[Bactericidal active ingredient]
Azaconazole, acibenzolar-S-methyl, azoxystrobin, anilazine, amisulbisoyl, amethoctrazine , Isopyrazam, isofetamid, isoprothiolane, ipconazole, iprodione, iprovalicas, iprobenizar, iprobenfos il), iminoctadine-tribesate, iminoctadate acetate, imibenconazole, ethifenfos, ethaconazol, ethaconazol ), Ethoxyquin, etridiazole, enestroburin, enoxastrobin, epoxiconazole, organic oils, x dixyl), oxazinylazole, oxathiapiproline, oxycarboxin, oxyquinoline copper (oxine-copper), oxytetracycline benzopoxycolpanol -Fumarate, oxolinic acid, copper dioctanoate, octilinone, offrace, orysastrobin, o-phenylphenol, o-phenylphenol, o-phenylphenol Hall (captafol), carpropamide (carbendazim), carboxin (carboxin), carbonone (carvone), quinoxyfen (quinoxene), cinomethionate (c) quintozine, guazatine, cufuraneb, cuoxystrobin, cresoxime-methyl, cloziracone, chlorozolate, chlozolinate il), chloroneb, cyazofamid, diethofencarb, diclocymet, diclofluanid, diclomezine, diclolanzine , Diniconazole, diniconazole-M, dineb, dinocap, dipymethitrone, diphenylamine, difenaconone, difenoconazole Flufenamide (cyflufenamid), diflumetrim, cyproconazole, cyprodinil (cyprodinil), simeconazole, dimethyldisulfide (dimethimol), dimethyldisulfide Xylostrobin, ziram, silthiofam, streptomycin, spiroxamine, sedaxane, zoxamide, Zomet, thiadinil, thiabendazole, thiuram, thiophanate, thiophanate-methyl, thioflumate, teflumide, c Conazole, debacarb, tebuconazole, tebufloquin, terbinafine, dodine, didemorph, diol, torconol Triadimethon, triazoxide, trichlamide, triclopyrcarb, tricyclole, triticolazole, triticonazole, triticonazole, triticonazole, triticonazole, triticonazole, triticonazole (Trifloxystrobin), triforine, tolylfluanid, tolclofos-methyl, tolnifanide, tolprocarbna, nabam, nabam namycin, naphthifine, nitrapyrin, nitrothal-isopropyl, nuarimol, copper nonylphenol sulphonate sulphate 713), validamycin, varifenate, picarbutrazox, bixafen, picoxystrobin, bittertanol, binapalol cryl), biphenyl, piperalin, hymezazole, pyroxystrobin, pyracrostrobin, pyraziflumoid, pyrazoflumid, pyrazoflumid, pyrazoflumid Pyriophenone, pyrisoxazole, pyrifenox, pyributicalcarb, pyribencarb, pyrimethanil, piromethanil, piromethanil nclozolin, ferbam, famoxadone, phenazine oxide, fenamidone, fenaminestrobin, fenilmol, fenimole, z ), Fenpyrazamine, fenbuconazole, fenfuram, fenpropidin, fenpropimorph, fenhexamid, phorpemidid. Folpet, phthalide, bupirimate, fuberidazole, blasticidin-S, furamethpyr, furaxyl, furaxyl, furaxyl (Fluazinam), fluoxastrobin, fluopicolide, fluopyram, fluorimide, fluxapiroxad, fluquinconazole (flucoconazole) ole), fluconazole-cis, fludioxonil, flusilazole, flusulfamide, fluthianil, flutoranol, flutrianol, flutrianol ), Flumetover, fluromorph, proquinazid, prochloraz, procymidone, prothiocarb, prothioconazole, prothioconazole on Bronopol, propamocarb-hydrochloride, propiconazole, propinebole, probenazole, bromconazole, and bromconazole. (Bronopol), propamocarb-hydrochloride, propiconazole (propiconazole), propinebole (probenazole), bromconazole (z). Benalaxyl-M, benodanyl, benomyl, pefurazoate, penconazole, pencyclon, benzobindiflupyr (benzyl) hizole, Benchavaricarb-isopropyl, pentiopyrad, penflufen, boscalid, fosetyl, polycium, polycium, polycium, polycium polycarbamate, Bordeaux liquid, mancozeb, mandipropamide, mandestrobin, manneb, microbutanil, mycrobutilmin Rudiomycin, metasulfocarb, metham, metalaxyl, metalaxyl M
laxyl-M), methylam, metconazole, metminostrobin, metraphenone, mepanipirim, meptyldinop cup, meptyldinop cup Laminarin, phosphorous acid and salts, basic copper chloride, silver, cuprous oxide, cupric hydroxide, copper hydroxide Potassium hydrogen carbonate (potassium bicarbonate) , Sodium bicarbonate, sulfur, oxyquinoline sulfate, copper sulfate, (3,4-dichloroisothiazol-5-yl) methyl 4- (tert-butyl) Benzoic acid ester (chemical name, CAS registry number: 1231214-23-5), 3-((3,4-dichloroisothiazol-5-yl) methoxy) benzo [d] isothiazole-1,1-dioxide (chemical) Name, CAS registration number: 957144-77-3), BAF-045 (code number), BAG-010 (code number), dodecylbenzenesulfonic acid bisethylenediamine copper complex [II] (DBEDC), MIF-1002 (code number) ), Trifeacetate Niltin (TPTA), triphenyltin chloride (TPTC), triphenyltin hydroxide (TPTH), non-pathogenic Ervinia carotobola.

[Plant growth regulating active ingredient]
1-methylcyclopropene, 1-naphthylacetamide, 2,6-diisopropylnaphthalene, 4-chlorophenoxyacetic acid (4-CPA), benzylaminopurine (1) benzylaminopurine, ancymidol, aviglycine, carbonone, chlormequat, cloprop, xoxyphonac, cloxyphonac, cloxyphonac Cyclanilide, rhinoceros Cytokinins, daminozide, dikegluc, dimethipin, etephone, epocholone, ethichlorol, luflurinate, luflurinate ), Forchlorfenuron, gibberellins, inabenfide, indole acetic acid, indole butyric acid, maleic hydrazide maleic ydrazide), mefluidide, mepiquat chloride, n-decyl alcohol (n-decanol), paclobutrazol, prohexadione calcium salt (prohexadione-calcium), prohexadione-calcium prohydrojasmon, sintofen, thidiazuron, triacontanol, trinexapac-ethyl, uniconazole, 4-oxo-Pol, -(2-Phenylethyl) aminobutyric acid ( Chemical name, CAS registration number: 1083-55-2), calcium peroxide.

Among the pesticidal active ingredients exemplified above, pyrimisulphan, pyrokilone, phenoxasulfone, fenquinotrione, fentolazamide, benzobicyclon and benzophenap are particularly suitable for the present invention.

These agrochemical active ingredients can be used alone or in admixture of two or more. The total blending ratio of the pesticidal active ingredient is not particularly limited, but is usually 1-70% by mass, preferably 3-60% by mass, more preferably 5-50% by mass based on the total amount of the granular agrochemical composition.

に示すように末端のヒドロキシ基が存在する。この粒子表面のヒドロキシ基には、適当な表面処理剤で化学処理することによって様々な残基を導入することができ、前記表面処理剤としては、例えばジメチルジクロロシラン、ポリジメチルシロキサン、環状ジメチルポリシロキサン、オクチルシラン、ヘキサメチルジシラザン、ヘキサデシルシラン、メタクリルシラン、更には各種のシリコーンオイル、アミノシラン等が知られている。使用する表面処理剤の選択によって前記ヒドロキシ基に導入される残基は異なり、ジメチルジクロロシランで化学処理した場合は、一例として下記式（ＩＩ）

に示すジメチルシリル基で表面が修飾された疎水性シリカ、すなわち本発明に使用されるポリメチルシリル化シリカが得られ、オクチルシランやヘキサデシルシランなどのアルキルシランで化学処理した場合は、一例として下記式（ＩＩＩ）

（式中のＲはアルキル基を表す）
に示すアルキルシリル基で表面が修飾された疎水性シリカが得られ、ジメチルシロキサン、ジメチルポリシロキサンまたは環状ジメチルポリシロキサンで化学処理した場合は、一例として下記式（ＩＶ）

（式中のｎは負でない整数を表す）
に示すジメチルポリシロキサン基で表面が修飾された疎水性シリカが得られ、ヘキサメチルジシラザンで化学処理した場合は、一例として下記式（Ｖ）

に示すトリメチルシリル基で表面が修飾された疎水性シリカ、すなわち本発明に使用されるポリメチルシリル化シリカが得られる。 The granular agrochemical composition of the present invention contains, as an essential component, polymethylsilylated silica in which the surface of hydrophilic silica is modified with a dimethylsilyl group or a trimethylsilyl group. Here, the molecular structure of hydrophilic silica is composed of an infinite number of continuous Si—O bonds, and the particle surface has the following formula (I):

There is a terminal hydroxy group as shown in FIG. Various residues can be introduced into the hydroxyl group on the particle surface by chemical treatment with an appropriate surface treatment agent. Examples of the surface treatment agent include dimethyldichlorosilane, polydimethylsiloxane, and cyclic dimethylpolysiloxane. Siloxane, octylsilane, hexamethyldisilazane, hexadecylsilane, methacrylsilane, various silicone oils, aminosilane, and the like are known. The residue introduced into the hydroxy group varies depending on the selection of the surface treatment agent to be used. When chemically treated with dimethyldichlorosilane, the following formula (II)

As an example, a hydrophobic silica whose surface is modified with a dimethylsilyl group shown in the following, that is, polymethylsilylated silica used in the present invention is obtained and chemically treated with an alkylsilane such as octylsilane or hexadecylsilane. Formula (III) below

(Wherein R represents an alkyl group)
In the case where a hydrophobic silica having a surface modified with an alkylsilyl group is obtained and chemically treated with dimethylsiloxane, dimethylpolysiloxane or cyclic dimethylpolysiloxane, the following formula (IV) is given as an example.

(Where n represents a non-negative integer)
In the case where a hydrophobic silica having a surface modified with a dimethylpolysiloxane group is obtained and chemically treated with hexamethyldisilazane, the following formula (V) is given as an example.

The hydrophobic silica whose surface is modified with the trimethylsilyl group shown in the following, that is, the polymethylsilylated silica used in the present invention is obtained.

The polymethylsilylated silica that can be used in the granular agrochemical composition of the present invention is one in which the surface of the hydrophilic silica is modified with a dimethylsilyl group or a trimethylsilyl group, and in particular, the surface is modified with a trimethylsilyl group. .

The inventors of the present invention have described the granular agrochemical composition of Patent Document 1 to which the polymethylsilylated silica is added, the granular agrochemical composition to which hydrophilic silica is added and the hydrophilic silica with a hydrophobic group other than the polymethylsilyl group. It has been found that the dispersibility and suspendability of the pesticidal active ingredient after disintegrating on the water surface is remarkably improved as compared with the granular pesticidal composition to which the treated hydrophobic silica is added. Furthermore, it was shown that the granular agrochemical composition of this invention is excellent also in disintegration. The effect of the present invention was specific to the granular agricultural chemical composition in which polymethylsilylated silica was selected.

The hydrophilic silica used as the raw material for the polymethylsilylated silica can be produced by either a dry method or a wet method, but it is preferable that the single particle is a nanoparticle having a particle diameter of less than 1 μm. What was manufactured by the dry method with which the hydrophilic silica of this is easy to be obtained is preferable. Since dry silica single particles are extremely prone to agglomeration, the usual particle size measurement method such as laser diffraction method is used to determine whether the measured value is the particle size of single particles or secondary particles formed by aggregation of single particles. It may be difficult to determine the particle size. Therefore, when the polymethylsilylated silica used in the present invention is expressed by a specific surface area that is a parameter independent of the aggregation state of the particles, the specific surface area is not particularly limited, but is usually about 10 to 1000 m ² / g, preferably 100-500m ² / g, more preferably 100-250m ² / g. The polymethylsilylated silica used in the present invention may not have all the hydroxy groups of hydrophilic silica substituted with dimethylsilyl groups or trimethylsilyl groups as in the formula (II) or formula (V), Polymethylsilylated silica containing a certain amount of unreacted hydroxy groups can also be used. The degree of substitution is not particularly limited, but the carbon content of the polymethylsilylated silica derived from the carbon atom of the methyl group is usually about 0.1-10% by mass, preferably 0.5-8% by mass, Preferably, it is 1-6% by mass. The carbon content can be measured, for example, using an elemental analyzer such as a trade name “SUMIGGRAPH NC-22F” (manufactured by Sumitomo Analysis Center). The blending ratio of polymethylsilylated silica in the granular pesticidal composition of the present invention is not particularly limited, but is usually about 2-10% by mass, preferably 4-8% by mass based on the total amount of the granular pesticidal composition.

Also, in the granular agrochemical composition of the present invention, a surfactant is blended in order to disintegrate the grains on the water surface and diffuse the agrochemical active ingredient into water. As the surfactant that can be used, those generally used in agricultural chemical compositions can be used.

Examples of specific surfactants include polyethylene glycol higher fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene aryl phenyl ethers, sorbitan monoalkylates, acetylene alcohols and acetylenic diols and their Nonionic surfactants such as alkylene oxide adducts; alkylaryl sulfonates, dialkyl sulfonates, lignin sulfonates, naphthalene sulfonates and their condensates, alkyl sulfates, alkyl phosphates, alkylaryls Sulfate ester salt, alkylaryl phosphate ester salt, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene alkyl aryl ether sulfate ester Anionic surfactants such as thiol salts, polyoxyethylene arylphenyl ether sulfates, polycarboxylic acid type polymer surfactants; cationic surfactants such as tetraalkylammonium salts, alkylamines, alkylpyrimidinium salts; Examples include amphoteric surfactants such as alkyl betaines, alkyl amine oxides, alkyl imidazolinium betaines, and amino acids; and silicone surfactants and fluorine surfactants. Note that the surfactant that is liquid at room temperature may be used by adsorbing to an oil-absorbing material such as wet silica or diatomaceous earth.

The above surfactants can be used alone or in admixture of two or more. The total blending ratio of these surfactants is not particularly limited, but is usually 0.1-15% by mass, preferably 0.5-12.5% by mass, more preferably based on the total amount of the granular agrochemical composition. 1-10% by mass.

It is essential that the granular agricultural chemical composition of the present invention floats on the water surface. Examples of methods for imparting water surface floatability to granular agrochemical compositions include, for example, perlite made of pearlite or obsidian, foamed shirasu made of shirasu, phylite baked in an aluminosilicate system, sodium silicate or borax. Balloon, pumice, granular diatomaceous earth, granular activated carbon, wood powder, cork powder, kenaf pieces, phenol microballoon made of phenol resin, ecosphere made of epoxy resin, polyurethane foam made of polyurethane resin, microballoon made of polyacrylonitrile resin And a method of containing a hollow body having one or a plurality of independent air chambers, such as fly ash produced as ash during thermal power generation, and a method of containing a water-repellent substance such as stearic acid and its salts. The former independent one or more More preferable is a method of containing a hollow body having a chamber. As the hollow body, a plastic balloon having a thermoplastic polymer as a wall material is floated from a small amount of less than 5% by mass on the basis of the total amount of the granular composition. It is particularly preferable in that it can secure the properties and has a secondary effect of improving the granulation property when the raw material kneaded product is extruded and granulated.

Examples of the thermoplastic polymer used as the wall material of the plastic balloon include hard and soft polyvinyl polymers such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polystyrene, high density, medium density, and low density polyethylene, and ethylene. / Polystyrene polymer such as vinyl acetate copolymer; Unmodified polypropylene; Polyacetal polymer of homopolymer or copolymer; Acrylic polymer such as polymethyl methacrylate and methacryl / styrene copolymer; Cellulose acetate Polycarbonate; polyester polymer such as polyethylene terephthalate; polyamide polymer such as nylon 6 and nylon 66; thermoplastic polyurethane; ethylene trifluoride chloride, tetrafluoride ethylene, tetrafluoroethylene / hexafluoropropylene copolymer Combined, four foot Fluorine polymers such as ethylene / perfluoroalkoxyethylene copolymer, ethylene tetrafluoride / ethylene copolymer, and vinylidene fluoride can also be mentioned, but polyacrylonitrile or polyacrylonitrile-based polymer containing acrylonitrile as a monomer unit A copolymer is preferred. Specific examples of the polyacrylonitrile copolymer include styrene / acrylonitrile copolymer, styrene / butadiene / acrylonitrile copolymer, vinylidene chloride / methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / acrylonitrile / methacrylonitrile. Examples include copolymers, methyl methacrylate / acrylonitrile copolymers, acrylonitrile / methacrylonitrile / itaconic acid copolymers, and the like. The particle size of the hollow body is not particularly limited, but is usually 1-600 μm, preferably 3-300 μm, more preferably 5-100 μm.

The blending amount of these hollow body materials is not particularly limited as long as the granular agrochemical composition obtains water surface floatability, but if it is blended more than necessary, it becomes brittle particles and may be crushed during storage, transportation or use. Since there are cases where it is not preferable, for example, the amount of dust generated during production increases, it is desirable to add the minimum amount necessary. For this reason, the upper limit of the amount of the hollow body is generally up to about 30% by mass, preferably 15% by mass or less, more preferably 5% by mass or less, based on the total amount of the granular agricultural chemical composition. When the hollow body is a plastic balloon, the granular agrochemical composition can obtain water surface floatability even with a blending amount of 5% by mass or less. Moreover, the minimum of the compounding quantity of the said hollow body is 0.3 mass%, and it is preferable that it is 0.5 mass% or more. If the blending ratio is less than 0.3% by mass, the granular agrochemical composition may not exhibit water surface floatability.

Furthermore, in the granular agrochemical composition of the present invention, a solid carrier is blended. As the solid carrier, a water-soluble carrier or a water-insoluble carrier can be used, and these can be used in combination. Water-soluble carriers include, for example, organic or inorganic acid salts such as ammonium sulfate, ammonium bicarbonate, ammonium nitrate, ammonium chloride, potassium chloride, sodium sulfate, magnesium sulfate, sodium citrate, sodium carbonate, sodium bicarbonate, citric acid, succinic acid Organic acids such as sucrose, saccharides such as lactose, urea and the like. Mineral fine powder is generally used as the water-insoluble carrier, and examples thereof include clays, calcium carbonate, bentonite, talc, diatomaceous earth, and calcium stearate.

The solid carriers can be used alone or in admixture of two or more. The total blending ratio of these solid carriers is not particularly limited, but is usually 0.1-96.6% by mass, preferably 10-70% by mass, based on the total amount of the granular agricultural chemical composition.

In the granular agrochemical composition of the present invention, an auxiliary agent is blended as necessary as other components. Examples of the auxiliary agent that is an optional component include phytotoxicity reducing agents, decomposition inhibitors, binders, and disintegration aids for pesticidal active ingredients.

Specific examples of the safeners for active ingredients of agricultural chemicals include benoxacol, furilazole, dichlormide, dicyclonone, N1, N2-diallyl-N2-dichloroacetylglycinamide (DKA-). 24), 4-dichloroacetyl-1-oxa-4-azaspiro [4.5] decane (AD-67), 2,2-dichloro-N- (1,3-dioxane-2-ylmethyl) -N- ( 2-propenyl) acetamide (PPG-1292), 3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine (R-29148), croquint set-mexyl, naphthalic anhydride (1,8-Naphth lic Anhydride, mefenpyr-diethyl, mefenpyr, mefenpyr-ethyl, fenchlorazole-O-ethyl, 2-chlorodimethyl -2-Methyl-1,3-dioxane (MG-191), Ciomethrinil, flurazole, fluxofenim, isoxadifen, isoxadifen-ethyl, MON 46 (MON) code MON46 Oxabetrilin, cyprosul Cyprosulfamide, lower alkyl substituted benzoic acid, TI-35 (code number) or N- (2-methoxybenzoyl) -4-[(methylaminocarbonyl) amino] benzenesulfonamide (Chemical name, CAS registry number: 129531) -12-0).

Specific examples of the agricultural chemical active ingredient decomposition inhibitors include desiccants such as zeolite, quicklime and magnesium oxide, antioxidants such as phenolic compounds, amine compounds, sulfur compounds and phosphoric acid compounds, salicylic acid compounds and benzophenone compounds. And the like.

Specific examples of the binder include carboxymethylcellulose sodium salt, dextrin, water-soluble starch, xanthan gum, guar seed gum, sucrose, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid sodium salt, polyoxyethylene having an average molecular weight of 6,000 to 5 million, and the like. Can be mentioned.

Specific examples of the disintegration aid include sodium triphosphate, sodium hexametaphosphate, metal stearate, cellulose powder, dextrin, methacrylate ester copolymer, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compound, sulfonated styrene Examples thereof include an isobutylene / maleic anhydride copolymer and a starch / polyacrylonitrile graft copolymer.

Each of the above adjuvants can be used alone or in admixture of two or more. When these adjuvants are blended, the total blending ratio of the adjuvants is usually about 0.1-20% by mass, preferably 0.5-10% by mass, based on the total amount of the granular agricultural chemical composition.

The granular agrochemical composition of the present invention is usually a granular composition that floats on the water surface containing the components described above, but each of the aforementioned components and blending amounts is a composition having a particle size of 3 mm or more. In this case, the disintegration time on the water surface is adjusted to be within 30 minutes, preferably within 20 minutes, and more preferably within 15 minutes. When the disintegration time exceeds 30 minutes, the granular agrochemical composition is blown by the wind, which is not preferable. In order to further reduce the influence of blowing, when the granular pesticide composition floats on the water surface, the portion exposed on the water surface is 40% or less of the entire granular pesticide composition, preferably 20% or less. It is desirable to adjust the amount of each of the above components.

In addition, the granular agrochemical composition of the present invention is rapidly dispersed and suspended in the water surface or water after disintegration on the water surface, preferably immediately after disintegration, at least 1 hour after the granular agrochemical composition is sprayed on the water surface at the latest. Eliminates visible undispersed particles on the water surface and in the water. It is difficult to visually determine the presence or absence of undispersed particles having a particle size that cannot be confirmed with the naked eye, for example, less than 100 μm. Since it can float in water for a long time, even if it exists, self-diffusion of the pesticidal active ingredient, which is a subject of the present invention, can be achieved without any problems.

The manufacturing process of the granular agrochemical composition of this invention follows a well-known method. That is,
[A] mixing all the raw materials constituting the granular agrochemical composition to obtain a mixture;
[B] adding a predetermined amount of water to the mixture obtained in step [a] and kneading the mixture;
[C] A step of discharging and granulating the kneaded product obtained in the step [b] from a screen having a pore diameter of 3 mm or more using an extrusion granulator;
[D] drying the granulated product obtained in step [c];
[E] sieving the dried granulated product obtained in step [d];
The granular agrochemical composition of this invention can be obtained by passing through.

In step [a], all raw materials constituting the granular agricultural chemical composition including the agricultural chemical active ingredient, polymethylsilylated silica, surfactant, hollow body and solid carrier are mixed. For mixing, a known mixer such as a Nauta mixer or a vertical mixer can be used. All the raw materials are mixed in the mixer for a predetermined time to obtain a mixture.

Next, water is added to the mixture obtained in step [a] and kneaded (step [b]). In kneading, a known kneader such as a kneader, a ribbon mixer, or a vertical mixer can be used. The amount of water to be added is not particularly limited, but usually about 10-15% by mass in the mixture may be added in an external ratio. This mixture is kneaded for a predetermined time in the kneader to obtain a kneaded product.

The kneaded product is discharged from a screen having a pore diameter of 3 mm or more, preferably 3 to 10 mm, more preferably 3 to 8 mm using an extrusion granulator (step [c]). The granular agrochemical composition of the present invention preferably has an external shape composed of a curved surface with a ratio of the minor axis to the major axis of 1-3, and the ratio of minor axis to major axis is 1-2. It is more preferable. By selecting the external shape as described above, it is possible to prevent generation of fine powder due to wear or collision between the granular pesticide compositions when transporting the granular pesticide composition or when spraying using a power spreader or the like. Can do. As a means for giving the external shape to the granular agrochemical composition, for example, the granulated product obtained in the step [c] was cut into a desired length, placed in a horizontally placed drum, and composed of a curved surface. A method of rotating the drum until it becomes an external shape to give a motion of rolling into a granulated product can be mentioned.

It is also effective for preventing the generation of the fine powder that the compression disintegration strength per grain of the agricultural chemical composition is 0.1 kgf or more, preferably 0.3 kgf or more. This compressive collapse strength is a load value when a grain collapses when a load is applied to one grain at a constant gravitational acceleration. The compression disintegration strength per grain can be measured using a commercially available load tester, a tensile compression tester, or the like.

Next, the obtained granulated product is dried (step [d]). The drying temperature for drying the granulated product is not particularly limited, but is about 40-95 ° C., and the residual water content is usually 0.3-3 mass based on the total amount of the granular agrochemical composition. % Until it has a water content of about 0.3-1.5% by mass, preferably about 0.3-1.5% by mass. When the moisture is in such a range, both the powdering and stickiness of the granular agrochemical composition are suppressed. The specific gravity is not particularly limited, but is preferably 0.3-1 and more preferably 0.3-0.5 from the viewpoint of water surface floatability, ease of packaging, and securing the number of grains.

Finally, the dried granulated product is sieved, and the dried granulated product having a desired particle size is selected to obtain the granular agrochemical composition of the present invention (step [e]). The granular agrochemical composition of the present invention is required to contain more particles having a particle size of 3 mm or more, that is, to have a particle size distribution in which particles having a particle size of 3 mm or more are 80% or more. More preferably, the particle size of −10 mm is 80% or more, and in particular, the particle size of 3-8 mm is 80% or more. By making the preparation have the above particle size distribution, even when sprayed from the shore, it is possible to easily obtain a spray area of 5-50% of the total paddy area at a distance of 1 m or more from the shore. As a secondary effect of making the particle size 3 mm or more, misuse can be prevented because it can be easily discriminated from the granule for paddy rice seedling box containing many particles having a particle size of usually about 0.8 mm. Can be mentioned. Even if a misuse is noticed after treating the paddy rice seedling box, only the preparation of the present invention floats on the surface of the water by putting the whole seedling box in water, so that the damage of misuse can be minimized.

Preferred examples of the composition of the granular agrochemical composition of the present invention include, for example, 8% by mass or more of an active ingredient having a water surface application effect as a component, a particle size of 3-8 mm, and a specific gravity of 0.3-0. 5, the ratio of the minor axis to the major axis is 1-2, the particle surface has an external shape formed by a curved surface, disintegrates within 20 minutes after being sprayed on the water surface, and immediately after the collapse on the water surface and water Examples include those in which there are no visible undispersed particles.

There is no particular limitation on the method for spraying the granular pesticide composition of the present invention described above on the surface of a paddy field or the like. For example, a method of holding and throwing the granular pesticide composition with a hand wearing vinyl gloves, While using a power spreader, a method that uses a power spreader to continuously discharge from the jet head, or a method that opens and closes the shutter lever instantaneously to spray and sprays, or a handle For example, a method of throwing a cylindrical container by shaking, a method of using a hand-held type granulator, and a method of spraying in a streak shape or a spot using a radio control helicopter. Alternatively, a predetermined amount of the obtained granular agrochemical composition may be packaged with a water-soluble film such as polyvinyl alcohol and put into a paddy field or the like together with the package as a so-called jumbo agent form.

Conventionally, in rice cultivation in paddy fields, in the case of so-called early cultivation, algae is generated in paddy fields even if the surface floating granular agricultural chemical composition is locally sprayed within 1-2 weeks after transplanting. There is almost no diffusibility of the pesticidal active ingredient, and the desired effect can be obtained. However, in so-called normal season cultivation after May, the water temperature rises and algae are generally generated at the appropriate time for spraying pesticides. This algae significantly inhibits the spread of pesticide active ingredients. Therefore, the desired effect of agricultural chemicals is often not obtained. In particular, when a water-floating granular pesticide composition is locally sprayed on a paddy field where algae are blown by wind, the portion where the algae is blown hardly obtains the effect of the pesticide. In addition, even when a rice-floating pesticide composition is locally sprayed after several weeks after transplantation, the growth of paddy rice progresses and the strain grows, diffusion of the pesticide active ingredient is hindered. Thus, the labor-saving spraying composition on which local spraying is a premise was a composition sprayed when rice plants are small.

On the other hand, the granular pesticide composition of the present invention has good diffusion of the pesticide active ingredient in the paddy field where algae is generated, or in the paddy field where rice plants have grown to some extent, and the desired pesticide effect can be obtained. It can be said that it is a water-floating granular pesticide composition, and by spraying this to a specific position in a paddy field and within a specific area, it is possible to achieve a uniform pesticide active ingredient with almost no hindrance to labor saving when spraying pesticides. It can be spread. That is, the diffusible granular pesticide composition having a particle size of 3 mm or more according to the present invention is 80% or more, floats on the water surface, and disintegrates on the water surface within 30 minutes. By spraying over the above distance, preferably at a distance of 2 m or more from the shore, 5-50% of the total paddy area, preferably 10-50%, it is uniformly distributed in the paddy field. Can be sprayed.

In addition, although there is no problem even if the granular pesticide composition of the present invention is sprayed over 50% or more of the total paddy field area, it is meaningless for the purpose of labor-saving pesticide spraying, and sprayed over an area of 50% or less. Is desirable. Furthermore, naturally, even in a paddy field free from algae, a paddy field before transplanting, or a paddy field with a small rice stock, the diffusion of the pesticidal active ingredient by the granular pesticide composition of the present invention is good, and An effect is obtained.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In addition, in the following Examples, a part represents a mass part.

[Example 1]
Hydrophobic silica with a specific surface area of about 140 m ² / g and carbon content of about 2.3% by mass obtained by surface treatment of hydrophilic silica produced by a dry process with trimethylsilyl group (trade name “AEROSIL RX200”, Nippon Aerosil) 6 parts), aryl sulfonate 10 parts, polycarboxylate 2 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts 3 parts of bentonite, 1 part of urea and 24 parts of calcium carbonate were added, kneaded with a predetermined amount of water, and then extruded and granulated from a screen with an opening diameter of 5 mm, and the length was about 10 mm with a scraper. Cut. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 2]
Hydrophobic silica with a specific surface area of about 140 m ² / g and carbon content of about 2.3% by mass obtained by surface treatment of hydrophilic silica produced by a dry process with trimethylsilyl group (trade name “AEROSIL RX200”, Nippon Aerosil) 6 parts), aryl sulfonate 10 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, urea 1 And 26 parts of calcium carbonate were mixed, a predetermined amount of water was added and kneaded, and then cut into a length of about 10 mm with a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 3]
Hydrophobic silica with a specific surface area of about 35 m ² / g and a carbon content of about 0.7% by mass obtained by surface treatment of hydrophilic silica produced by a dry process with trimethylsilyl group (trade name “AEROSIL RX50”, Nippon Aerosil) 6 parts), aryl sulfonate 10 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, urea 1 And 26 parts of calcium carbonate were mixed, a predetermined amount of water was added and kneaded, and then cut into a length of about 10 mm with a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 4]
48 parts of Pyroxylone, Hydrophobic silica produced by dry process with a trimethylsilyl group surface-treated with a specific surface area of about 260 m ² / g and a carbon content of about 2.5% by weight hydrophobic silica (trade name “AEROSIL R812”, Nippon Aerosil 6 parts), aryl sulfonate 10 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, urea 1 And 26 parts of calcium carbonate were mixed, a predetermined amount of water was added and kneaded, and then cut into a length of about 10 mm with a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 5]
Hydrophobic silica with a specific surface area of about 220 m ² / g and a carbon content of about 3.5% by weight obtained by subjecting hydrophilic silica produced by a dry method to surface treatment with a trimethylsilyl group (trade name “AEROSIL R812S”, Nippon Aerosil) 6 parts), aryl sulfonate 10 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, urea 1 And 26 parts of calcium carbonate were mixed, a predetermined amount of water was added and kneaded, and then cut into a length of about 10 mm with a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 6]
Hydrophobic silica having a specific surface area of about 210 m ² / g and a carbon content of about 4% by mass obtained by surface treatment of hydrophilic silica produced by a dry process with trimethylsilyl group (trade name “AEROSIL RX300”, manufactured by Nippon Aerosil Co., Ltd.) 6 parts, aryl sulfonate 10 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, urea 1 part and After mixing 26 parts of calcium carbonate, adding a predetermined amount of water and kneading, it was cut into a length of about 10 mm by a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 7]
Hydrophobic silica with a specific surface area of about 110 m ² / g and a carbon content of about 0.9% by mass obtained by surface treatment of hydrophilic silica produced by a dry process with dimethylsilyl groups (trade name “AEROSIL R972”, Japan) Aerosil) 6 parts, aryl sulfonate 10 parts, polycarboxylate 2 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 Part, 3 parts of bentonite, 1 part of urea and 24 parts of calcium carbonate, kneaded by adding a predetermined amount of water, and then extruding and granulating from a screen having an opening diameter of 5 mm, and a length of about 10 mm by a scraper. Cut to. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 8]
2 parts of pyrimylsulfan, 8 parts of phenoxasulfone, 12 parts of benzobicyclone, specific surface area of about 170 m ² / g, carbon content of about 1.2 mass % Hydrophobic silica (trade name “AEROSIL R974”, manufactured by Nippon Aerosil Co., Ltd.) 2 parts, aryl sulfonate 2.1 parts, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, polyacrylate 2 parts, After mixing 1 part of carboxymethylcellulose salt, 5 parts of phosphate cross-linked starch, 3 parts of polyalkylene glycol, 15 parts of diatomaceous earth, 5 parts of bentonite and 39 parts of clay, kneading with a predetermined amount of water, the opening diameter is 5 mm. While extruding and granulating from a screen, it was cut into a length of about 10 mm by a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 22% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 9]
Pyridinium Miss Le fan 2 parts, phenoxazine sulfone 8 parts, benzobicyclon 12 parts, about the specific surface area of the produced hydrophilic silica has been surface treated with trimethylsilyl groups by a dry method 140 m 2 / ^g, about 2.3 wt% carbon content 2 parts of silica (trade name “AEROSIL RX200”, Nippon Aerosil Co., Ltd.), 2.1 parts of aryl sulfonate, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, 2 parts of polyacrylate, carboxy After mixing 1 part of methylcellulose salt, 5 parts of phosphate cross-linked starch, 3 parts of polyalkylene glycol, 15 parts of diatomaceous earth, 5 parts of bentonite and 39 parts of clay, kneading with a predetermined amount of water, a screen having an opening diameter of 5 mm While extruding and granulating, it was cut into a length of about 10 mm by a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 22% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 10]
2 parts of pyrimylsulfan, 8 parts of phenoxasulfone, 12 parts of benzobicyclone, a specific surface area of about 220 m ² / g with a surface treatment of hydrophilic silica produced by a dry method with a trimethylsilyl group, and a carbon content of about 3.5% by mass 2 parts of hydrophobic silica (trade name “AEROSIL R812S”, manufactured by Nippon Aerosil Co., Ltd.), 2.1 parts of aryl sulfonate, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, 2 parts of polyacrylate, carboxy After mixing 1 part of methylcellulose salt, 5 parts of phosphate cross-linked starch, 3 parts of polyalkylene glycol, 15 parts of diatomaceous earth, 5 parts of bentonite and 39 parts of clay, kneading with a predetermined amount of water, a screen having an opening diameter of 5 mm While extruding and granulating, it was cut into a length of about 10 mm by a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 22% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 11]
Hydrophobic silica having a specific surface area of about 110 m ² / g and a carbon content of about 0.9% by mass, comprising 3 parts of pyrimisulphan, 12 parts of fenquinotrione, and hydrophilic silica produced by a dry process with a dimethylsilyl group. Product name "AEROSIL R972", manufactured by Nippon Aerosil Co., Ltd.) 2 parts, aryl sulfonate 4 parts, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, shirasu balloon 10 parts, polyacrylate 6 parts, carboxymethyl cellulose salt 1 part, 5 parts of phosphoric acid cross-linked starch, 2 parts of polyalkylene glycol, 15 parts of diatomaceous earth and 36 parts of clay were added, kneaded with a predetermined amount of water, and then extruded and granulated from a screen having an opening diameter of 5 mm. Then, it was cut into a length of about 10 mm with a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 15% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 12]
Hydrophobic silica having a specific surface area of about 110 m ² / g and a carbon content of about 0.9% by mass, comprising 3 parts of pyrimisulphan, 12 parts of fenquinotrione, and hydrophilic silica produced by a dry process with a dimethylsilyl group. Product name "AEROSIL R972", manufactured by Nippon Aerosil Co., Ltd.) 4 parts, aryl sulfonate 4 parts, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, shirasu balloon 10 parts, polyacrylate 6 parts, carboxymethyl cellulose salt 1 part, 5 parts of phosphoric acid cross-linked starch, 2 parts of polyalkylene glycol, 15 parts of diatomaceous earth and 34 parts of clay are mixed, kneaded with a predetermined amount of water, and then extruded and granulated from a screen having an opening diameter of 5 mm. Then, it was cut into a length of about 10 mm with a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 15% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Example 13]
8 parts of fentolazamide, 8 parts of benzobicyclone, 30 parts of benzophenap, hydrophilic silica prepared by dry process with a trimethylsilyl group and having a specific surface area of about 140 m ² / g and a carbon content of about 2.3% by weight Silica (trade name “AEROSIL RX200”, manufactured by Nippon Aerosil Co., Ltd.), 10 parts of aryl sulfonate, 2 parts of polycarboxylate, 1 part of polyoxyalkylene aryl ether sulfate, 1 part of polyoxyalkylene alkyl ether, poly 2 parts of oxyalkylene alkynyl glycol ether, 1 part of plastic balloon, 10 parts of bentonite, 5 parts of urea and 16 parts of calcium carbonate are mixed, kneaded after adding a predetermined amount of water, and then extruded and granulated from a screen having an opening diameter of 5 mm. While cutting with a scraper to a length of about 10 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 46% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 1]
Pyroxylone 48 parts, aryl sulfonate 10 parts, polycarboxylate 2 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, Mix 3 parts of bentonite, 1 part of urea and 30 parts of calcium carbonate, add a predetermined amount of water, knead, and then cut into a length of about 10 mm with a scraper while extruding and granulating from a screen with an opening diameter of 5 mm. did. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 2]
48 parts of Pyroxylone, 6 parts of hydrophilic silica (trade name “Carplex # 101”, manufactured by DSL Japan) manufactured by a wet method with a specific surface area of about 65 m ² / g, 10 parts of aryl sulfonate, polycarboxylate 2 Parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, urea 1 part and calcium carbonate 24 parts, After adding a predetermined amount of water and kneading, it was cut into a length of about 10 mm with a scraper while extruding and granulating from a screen with an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 3]
48 parts of pyroxylone, 6 parts of hydrophilic silica (trade name “Carplex # 80”, manufactured by DSL Japan) with a specific surface area of about 193 m ² / g produced by a wet process, 10 parts of aryl sulfonate, polycarboxylate 2 Parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, urea 1 part and calcium carbonate 24 parts, After adding a predetermined amount of water and kneading, it was cut into a length of about 10 mm with a scraper while extruding and granulating from a screen with an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 4]
48 parts of Pyroxylone, 6 parts of hydrophilic silica (trade name “Carplex # 1120”, manufactured by DSL Japan) manufactured by a wet process with a specific surface area of about 109 m ² / g, 10 parts of aryl sulfonate, polycarboxylate 2 Parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, urea 1 part and calcium carbonate 24 parts, After adding a predetermined amount of water and kneading, it was cut into a length of about 10 mm with a scraper while extruding and granulating from a screen with an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 5]
48 parts of Pyroxylone, 6 parts of hydrophilic silica (trade name “AEROSIL 90G”, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of about 90 m ² / g produced by a dry method, 10 parts of aryl sulfonate, polyoxyalkylene aryl ether sulfate 1 1 part of polyoxyalkylene alkyl ether, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, 3 parts of bentonite, 1 part of urea and 26 parts of calcium carbonate, and kneaded after adding a predetermined amount of water While being extruded and granulated from a screen having an opening diameter of 5 mm, it was cut into a length of about 10 mm by a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 6]
48 parts of Pyroxylone, 6 parts of hydrophilic silica (trade name “AEROSIL 380PE”, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of about 380 m ² / g produced by a dry method, 10 parts of aryl sulfonate, polyoxyalkylene aryl ether sulfate 1 1 part of polyoxyalkylene alkyl ether, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, 3 parts of bentonite, 1 part of urea and 26 parts of calcium carbonate, and kneaded after adding a predetermined amount of water While being extruded and granulated from a screen having an opening diameter of 5 mm, it was cut into a length of about 10 mm by a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 7]
Hydrophobic silica with a specific surface area of about 35 m ² / g and a carbon content of about 6% by mass obtained by surface treatment of hydrophilic silica produced by a dry process with dimethylpolysiloxane group (trade name “AEROSIL RY50”, Nippon Aerosil) 6 parts), aryl sulfonate 10 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, urea 1 And 26 parts of calcium carbonate were mixed, a predetermined amount of water was added and kneaded, and then cut into a length of about 10 mm with a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 8]
Hydrophobic silica (trade name “AEROSIL R104”, with a specific surface area of about 150 m ² / g and a carbon content of about 1.5% by mass obtained by surface treatment of hydrophilic silica produced by a dry method with dimethylpolysiloxane group, 48 parts of pyroxylone Nippon Aerosil Co., Ltd.) 6 parts, aryl sulfonate 10 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, After mixing 1 part of urea and 26 parts of calcium carbonate, adding a predetermined amount of water and kneading, it was cut into a length of about 10 mm with a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 9]
Hydrophobic silica with a specific surface area of about 100 m ² / g and a carbon content of about 4% by mass obtained by subjecting hydrophilic silica produced by dry method to surface treatment with dimethylpolysiloxane group (trade name “AEROSIL RY200”, Nippon Aerosil) 6 parts), aryl sulfonate 10 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, urea 1 And 26 parts of calcium carbonate were mixed, a predetermined amount of water was added and kneaded, and then cut into a length of about 10 mm with a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 10]
Hydrophobic silica (trade name “AEROSIL R816”, having a specific surface area of about 190 m ² / g and a carbon content of about 1.4% by mass, obtained by surface treatment of hydrophilic silica produced by a dry method with hexadecylsilyl group, 48 parts by weight of pyroxylone Nippon Aerosil Co., Ltd.) 6 parts, aryl sulfonate 10 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxyalkylene alkynyl glycol ether 2 parts, plastic balloon 2 parts, bentonite 3 parts, After mixing 1 part of urea and 26 parts of calcium carbonate, adding a predetermined amount of water and kneading, it was cut into a length of about 10 mm with a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 48% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 11]
2 parts of pyrimylsulfan, 8 parts of phenoxasulfone, 12 parts of benzobicyclone, 2.1 parts of aryl sulfonate, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, 2 parts of polyacrylate, carboxymethylcellulose After mixing 1 part of salt, 5 parts of phosphate cross-linked starch, 3 parts of polyalkylene glycol, 15 parts of diatomaceous earth, 5 parts of bentonite and 41 parts of clay, kneading after adding a predetermined amount of water, from a screen having an opening diameter of 5 mm While extruding and granulating, it was cut into a length of about 10 mm by a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 22% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 12]
2 parts of pyrimylsulfan, 8 parts of phenoxasulfone, 12 parts of benzobicyclone, a specific surface area of about 150 m ² / g of a surface-treated hydrophilic silica prepared by a dry process with a dimethylpolysiloxane group, and a carbon content of about 1.5 2 parts by weight of hydrophobic silica (trade name “AEROSIL R104”, made by Nippon Aerosil), 2.1 parts of aryl sulfonate, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, 2 parts of polyacrylate , 1 part of carboxymethylcellulose salt, 5 parts of phosphoric acid crosslinked starch, 3 parts of polyalkylene glycol, 15 parts of diatomaceous earth, 5 parts of bentonite and 39 parts of clay were added and kneaded with a predetermined amount of water, and the opening diameter was 5 mm. While extruding and granulating from the screen, a scraper was cut into a length of about 10 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 22% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 13]
2 parts of pyrimisulphan, 8 parts of phenoxasulfone, 12 parts of benzobicyclone, specific surface area of about 150 m ² / g specific surface area of hydrophilic silica produced by dry method with octylsilyl group, carbon content of about 5.5 mass % Hydrophobic silica (trade name “AEROSIL R805”, made by Nippon Aerosil Co., Ltd.), 2.1 parts of aryl sulfonate, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, 2 parts of polyacrylate, After mixing 1 part of carboxymethylcellulose salt, 5 parts of phosphate cross-linked starch, 3 parts of polyalkylene glycol, 15 parts of diatomaceous earth, 5 parts of bentonite and 39 parts of clay, kneading with a predetermined amount of water, the opening diameter is 5 mm. While extruding and granulating from the screen, it was cut into a length of about 10 mm by a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 22% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 14]
2 parts of pyrimylsulfan, 8 parts of phenoxasulfone, 12 parts of benzobicyclone, a specific surface area of about 100 m ² / g of surface-treated hydrophilic silica produced by a dry process with a dimethylpolysiloxane group, and a carbon content of about 4% by mass 2 parts of silica (trade name “AEROSIL RY200”, manufactured by Nippon Aerosil Co., Ltd.), 2.1 parts of aryl sulfonate, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, 2 parts of polyacrylate, carboxy After mixing 1 part of methylcellulose salt, 5 parts of phosphate cross-linked starch, 3 parts of polyalkylene glycol, 15 parts of diatomaceous earth, 5 parts of bentonite and 39 parts of clay, kneading with a predetermined amount of water, a screen having an opening diameter of 5 mm While extruding and granulating, it was cut into a length of about 10 mm by a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 22% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 15]
3 parts of pyrimisulphan, 12 parts of phenquinotrione, 4 parts of aryl sulfonate, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, 10 parts of shirasu balloon, 6 parts of polyacrylate, 1 part of carboxymethyl cellulose salt , 5 parts of phosphoric acid cross-linked starch, 2 parts of polyalkylene glycol, 15 parts of diatomaceous earth and 38 parts of clay were added, kneaded with a predetermined amount of water, and then extruded and granulated from a screen having an opening diameter of 5 mm, and a scraper. And cut to a length of about 10 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 15% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 16]
3 parts of pyrimisulphan, 12 parts of fenquinotrione, 2 parts of silicone composite powder (trade name “KMP601”, manufactured by Shin-Etsu Chemical), 4 parts of aryl sulfonate, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, Mix 10 parts of shirasu balloon, 6 parts of polyacrylate, 1 part of carboxymethyl cellulose salt, 5 parts of phosphate cross-linked starch, 2 parts of polyalkylene glycol, 15 parts of diatomaceous earth and 36 parts of clay, and knead by adding a predetermined amount of water. After that, it was cut into a length of about 10 mm by a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 15% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 17]
3 parts of pyrimisulphan, 12 parts of phenquinotrione, 4 parts of silicone composite powder (trade name “KMP601”, manufactured by Shin-Etsu Chemical), 4 parts of aryl sulfonate, 2 parts of polyoxyalkylene alkynyl glycol ether, 2 parts of plastic balloon, Mix 10 parts of Shirasu balloon, 6 parts of polyacrylate, 1 part of carboxymethyl cellulose salt, 5 parts of phosphoric acid cross-linked starch, 2 parts of polyalkylene glycol, 15 parts of diatomaceous earth and 34 parts of clay and knead by adding a predetermined amount of water. After that, it was cut into a length of about 10 mm by a scraper while extruding and granulating from a screen having an opening diameter of 5 mm. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 15% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Comparative Example 18]
Fentrazamide 8 parts, benzobicyclone 8 parts, benzophenap 30 parts, aryl sulfonate 10 parts, polycarboxylate 2 parts, polyoxyalkylene aryl ether sulfate 1 part, polyoxyalkylene alkyl ether 1 part, polyoxy 2 parts of alkylene alkynyl glycol ether, 1 part of plastic balloon, 10 parts of bentonite, 5 parts of urea and 22 parts of calcium carbonate are mixed, kneaded after adding a predetermined amount of water, and then extruded and granulated from a screen having an opening diameter of 5 mm. However, it was cut into a length of about 10 mm with a scraper. Put the resulting granulated material in a horizontally placed drum, rotate the drum until it has an external shape composed of curved surfaces, give it a movement to roll into the granulated material, dry with hot air, and add the agrochemical active ingredient A granular agricultural chemical composition having a minor axis of 5 mm and containing 46% by mass was obtained. This granular pesticide composition has a particle size distribution of 80% or more when the particle size is 3 mm or more, the property of floating on the water surface, the ratio of the short diameter to the long diameter is about 2, and the external shape in which the particle surface is curved. Had.

[Test Example 1]
One grain of the agrochemical granular composition obtained in Examples and Comparative Examples was put into a water tank filled with room temperature industrial water, and the time required for the decay of the agrochemical granular composition floating on the water surface was measured. If the agrochemical granular composition settled before the disintegration was completed, this was recorded. In addition, the presence or absence of visible undispersed particles on the water surface and in water was observed 30 minutes and 1 hour after the end of disintegration and the granular agrochemical composition was sprayed on the water surface. However, when it took more than 1 hour for the agricultural chemical granular composition to collapse on the water surface, the test was terminated at that time. The results are shown in Table 1.

According to the present invention, the composition contains an agrochemical active ingredient, and those having a particle size of 3 mm or more have a particle size distribution of 80% or more and a property of floating on the water surface, and are disintegrated on the water surface within 30 minutes. It is possible to provide a granular agrochemical composition that improves the dispersion and suspension of the agrochemical active ingredient after being disintegrated on the water surface, that is, excellent in self-diffusion. Moreover, the granular agrochemical composition of this invention is excellent also in disintegration.

Claims (6)

It contains a pesticide active ingredient, silica, a surfactant, a hollow body, and a solid carrier, and has a particle size distribution of 80% or more having a particle size of 3 mm or more, floating on the water surface, and 30 minutes. A granular agrochemical composition having a property of collapsing on the water surface within, wherein the silica is a polymethylsilylated silica in which the surface of the hydrophilic silica is modified with a dimethylsilyl group or a trimethylsilyl group Agrochemical composition. The granular agrochemical composition according to claim 1, wherein the hydrophilic silica which is a raw material of polymethylsilylated silica is dry silica. The granular agrochemical composition according to claim 1 or 2, wherein the polymethylsilylated silica has a specific surface area of 10 to 1000 m ² / g. The granular agrochemical composition according to any one of claims 1 to 3, wherein a blending ratio of polymethylsilylated silica in the granular agrochemical composition is 1 to 10% by mass based on the total amount of the granular agrochemical composition. The granular agrochemical composition according to any one of claims 1 to 4, wherein the polymethylsilylated silica is obtained by modifying the surface of hydrophilic silica with a trimethylsilyl group. The pesticidal active ingredient is one or more selected from the group consisting of pyrimisulphan, pyroxylone, phenoxasulfone, fenquinotrione, phentolazamide, benzobicyclon, and benzophenap. The granular pesticide composition described in 1.