JP2017109963A - Manufacturing method of particulate agrochemical composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a particulate agrochemical composition having reduced detachment of an agrochemical active component and high certainty of solidification prevention during long term storage.SOLUTION: There is provided a manufacturing method of a particulate agrochemical composition having a process (a) for wetting a mineral matter fine particle with a water-soluble binder and a mixed aqueous solution of saccharides which is a liquid at ambient temperature, a process (b) for coating the mineral matter fine particle with an agrochemical active component to obtain the particulate agrochemical composition and a process (c) for drying the particulate agrochemical composition, where mass percentage of the particulate agrochemical composition passing through a mesh based on total amount of the particulate agrochemical composition is 75% or more when the resulting particulate agrochemical composition is input into a packaging bag consisting of a material having airtightness, sealing is conducted at a state with reducing pressure in the packaging bag to minus 27000 Pa (±4%) by gauge pressure, it is stored at 15°C constant temperature for 48 hours and the packaging bag is opened and total amount of ingredient thereof, which is the particulate agrochemical composition, is discharged onto the mesh with sieve opening of 1.7 mm without adding impact.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a finely divided pesticide composition, in which exfoliation of an agrochemical active ingredient is reduced and has high certainty of preventing caking during long-term storage.

  As a method for controlling pests at the later stage of Honda in paddy rice cultivation, a method of spraying DL powder or diluting a liquid preparation on the ground or by an unmanned helicopter and water surface application of granules are widely used. Among these methods, DL powder (particle size: 45 μm or less) is used as a main formulation in the latter period of Honda because it can be directly sprayed without diluting the formulation in water and is inexpensive. On the other hand, the DL powder has a large scattering when sprayed, and the impact on the surrounding crops after the implementation of the positive list system has been greatly closed, along with the exposure of pesticides to the sprayer and the impact on the surrounding living environment in residential suburbs. Increasingly, producers are advancing to refrain from spraying DL powder and switching to spraying with less scattering. However, the application of a granule (particle size: 300 to 1700 μm) on the surface of water may cause the effect to be unstable, and there is a problem that the control cost is higher than that of DL powder. Therefore, development of a foliage spraying agent that is inexpensive and has little scattering is desired.

  On the other hand, as an agrochemical formulation with less scattering at the time of spraying than DL powder, there are granule agents (particle size: 45 to 300 μm), and the agrochemical formulation includes four types of formulations having different particle sizes, That is, there are fine particles (particle size: 106 to 300 μm), fine particles F (particle size: 63 to 212 μm), coarse powder (particle size: 45 to 106 μm) and fine particles F (particle size: 180 to 710 μm). (Non-Patent Document 1). Among these, the fine granule F has a good balance of the amount of scattering, cost, and the effect as an agrochemical.

  As described above, the fine granule F is a preparation having a particle size distribution with a particle size of 63 to 212 μm. According to Non-Patent Document 1, the basic composition of a powder including fine granules F is composed of an agrochemical raw material, a binder, and a bulking agent, and contains an active ingredient decomposition inhibitor and the like as necessary. Among these components, PVA (polyvinyl alcohol), starch, resin emulsion and the like are used as the binder. As the extender, silica sand, clay, talc, bentonite, calcium carbonate, etc. are used, and silica sand is often used.

  In addition, as a method for producing a granule, first, a granule larger than the desired formulation is prepared by extrusion granulation, etc., and then pulverized to obtain a product with the required particle size (crush granulation method), suitable There is a method (surface coating method: coating method), etc., which coats an agrochemical raw material with a binder on the surface of silica sand or the like having a fine particle size distribution. Among these production methods, the crushing granulation method is produced by crushing a relatively soft granulated product or natural base, and therefore, drift due to the mixing of fine powder generated by crushing or generation of fine powder due to physical impact. Possibility is high and productivity is not necessarily high. On the other hand, since the crushing process is unnecessary, the surface coating method is suitable as a method for producing a preparation that is sprayed directly on agricultural land like the fine granules F at low cost.

By the way, since the active ingredient is coated on the particle surface of the granule containing the fine granule F produced by the surface coating method, the active ingredient is easily peeled off by the friction during the spraying, and the selection of the binder is important. (Non-Patent Document 1). For example, Patent Document 1 discloses that a non-oil-absorbing mineral powder of 10 μm or less is added to polyvinyl alcohol or lignin sulfone on the surface of a non-oil-absorbing mineral granular carrier. A method for producing a fine granule F is disclosed in which a granular base is produced by coating with a water-soluble binder such as an acid salt, and then impregnated with a liquid pesticide component.

  In Patent Document 2, a foliar absorption type herbicide compound having a cationic group and a water-soluble binder are held in a carrier mainly composed of silica sand or calcium carbonate having a particle size of 0.1 to 0.3 mm. Technology is disclosed. As the water-soluble binder, use of high viscosity organic solvents such as polyethylene glycol and polypropylene glycol, pastes such as carboxymethyl cellulose, dextran, polyvinyl alcohol, and polyvinyl pyrrolidone, and various surfactants are described.

  Agrochemical preparations produced by wetting mineral fine particles with a binder aqueous solution, coating the pesticidal active ingredient and then drying, in particular, fine granules having a particle size distribution of 106-300 μm, and a particle size distribution of 63-212 μm. In the fine granule F which has, various selection and improvement are made | formed about the above binders. However, the expected active ingredient content cannot be obtained due to peeling of fine particles containing agrochemical active ingredients in the drying process, and it still contains exfoliated agrochemical active ingredients when spraying, especially when spraying with a power spreader. In some cases, the fine particles were scattered and had a serious adverse effect on the health of workers and surrounding crops.

  On the other hand, Patent Document 3 discloses a finely divided pesticide composition containing a pesticide active ingredient, a water-soluble binder, and a saccharide that is liquid at room temperature and coated with mineral fine particles. The problem of reducing exfoliation of fine particles containing an active ingredient has been solved temporarily.

Japanese Examined Patent Publication No. 63-11322 JP-A-2005-112836 JP 2010-1000056 A

Agricultural Chemical Society of Japan Agricultural Chemicals Formulation and Application Method Study Group “Agricultural Chemicals Formulation Guide”, Japan Plant Protection Association, October 30, 1997, p. 17-19

  The fine-grained agricultural chemical composition of Patent Document 3 has excellent performance in terms of reducing the separation or dropping of fine particles containing an agricultural chemical active ingredient in the fine granules or fine granules F in which mineral fine particles are coated with an agricultural chemical active ingredient. However, since a saccharide that is liquid at room temperature is used as a part of the binder, the surface of the mineral fine particles coated with the saccharide is always slightly sticky. This stickiness is negligible and does not interfere with the application, but when left standing for a long period of time, the saccharide gradually sticks the mineral fine particles, In some cases, some or all of the finely divided agrochemical composition was consolidated. The finely divided agrochemical composition that has been consolidated into a block shape can be sprayed again as fine particles by loosening, for example, by giving an impact, but this is not preferable because it increases the labor involved in the spraying operation.

In this regard, Patent Document 3 describes that fine powders such as silica (white carbon), clay, calcium carbonate and the like can be added after the agrochemical active ingredient is coated on mineral fine particles to prevent caking. However, these techniques have not been able to reliably prevent consolidation. The consolidation is a phenomenon that occurs only after standing for a long period of at least several months, sometimes one year or more, and is affected by weather conditions such as temperature and humidity during production. For this reason, there is no reproducibility between compositions of the same composition, and accelerated tests such as high temperature storage tests are a phenomenon that does not reflect the actual situation. The presence or absence could not be grasped at an early stage, and there was a problem that packaging and shipment could not be performed until such a risk judgment could be made.
An object of the present invention is to provide a finely divided agrochemical composition that can reduce peeling of an agrochemical active ingredient and has high certainty of preventing caking during long-term storage.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a method for determining the presence or absence of a consolidation risk when stored in a simple, short-time, fine-grained agricultural chemical composition for a long period of time. Incorporation into the process for producing a pesticide composition has led to the completion of a method for producing a finely divided pesticide composition that reduces the peeling of the agrochemical active ingredient and has high certainty of preventing caking during long-term storage. .

That is, the present invention has the following gist.
[1] A step (a) of wetting mineral fine particles with a mixed aqueous solution of a water-soluble binder and a saccharide liquid at room temperature, and a step of obtaining a fine pesticide composition by coating the mineral fine particles with an agrochemical active ingredient (B) and a step (c) of drying the particulate agricultural chemical composition, and the resulting particulate agricultural chemical composition is put in a packaging bag made of an airtight material, and the inside of the packaging bag is gauged Sealed with the pressure reduced to minus 27000 Pa (± 4%) and stored at a constant temperature of 15 ° C. for 48 hours, then opened the packaging bag, and the total amount of the fine pesticide composition as its contents was opened. A fine pesticide composition having a mass percentage of 75% or more with respect to the total amount of the fine pesticide composition passing through the mesh when discharged on a 1.7 mm mesh without impact. Manufacturing method.

[2] The finely divided pesticide according to the above [1], which has a step (d) of mixing a fine powder that can be used as a solid carrier of a pesticide preparation with the finely divided pesticide composition before or after the step (c). A method for producing the composition.
[3] The method for producing a fine particulate agrochemical composition according to the above [2], wherein at least one step (d) is performed after the step (c).
[4] The method for producing a fine pesticide composition according to any one of the above [1] to [3], wherein the saccharide that is liquid at room temperature is a converted liquid sugar containing a reducing sugar.

[5] The particulate pesticide composition according to any one of [1] to [4] above, wherein the pesticidal active ingredient contains one or more pesticidal active ingredients whose water solubility at 20 ° C. is 100 ppm or more. Production method.
[6] The method for producing a fine pesticide composition according to the above [5], wherein the agrochemical active ingredient having a water solubility at 20 ° C. of 100 ppm or more is dinotefuran or tricyclazole.
[7] The method for producing a fine agricultural chemical composition according to any one of [1] to [6], wherein the mineral fine particles are silica sand containing 90% or more of particles having a particle size of 63 to 300 μm.

[8] In any one of the above [2] to [7], the loss on drying is less than 4% by mass when heated at 105 ° C. for 2 hours in air at normal pressure, which can be used as a solid carrier of an agrochemical formulation. The manufacturing method of the fine-grained agricultural chemical composition of description.
[9] The finely divided pesticide composition according to any one of the above [2] to [8], wherein the fine powder that can be used as a solid carrier of the pesticide formulation has an equilibrium moisture value of less than 7% by mass at 25 ° C. and 70% relative humidity. Manufacturing method.
[10] The method for producing a finely divided pesticide composition according to any one of the above [2] to [9], wherein the fine powder that can be used as a solid carrier of the pesticide preparation is silica.

[11] A fine pesticide composition obtained by coating mineral fine particles with an agrochemical active ingredient, and the fine pesticide composition is put into a packaging bag made of an airtight material, and the inside of the packaging bag is gauged. The container was sealed at a reduced pressure of minus 27000 Pa (± 4%) and stored at a constant temperature of 15 ° C. for 48 hours, and then the packaging bag was opened. A fine pesticide composition in which the fine pesticide composition passing through the mesh is 75% by mass or more of the total amount of the fine pesticide composition when discharged on a 7 mm mesh without applying an impact.

[12] A fine agricultural chemical composition formed by coating mineral fine particles with an agricultural chemical active ingredient is put in a packaging bag made of a material having airtightness, and the inside of the packaging bag is reduced to minus 27000 Pa (± 4%) by gauge pressure. After sealing under reduced pressure and storing at a constant temperature of 15 ° C. for 48 hours, the packaging bag is opened, and the total amount of the fine pesticide composition as the contents is impacted on a mesh having a mesh opening of 1.7 mm. The amount of solid agrochemical composition that passes through the mesh is examined for a mass percentage of 75% or more of the total amount of the fine agrochemical composition. How to evaluate.

  ADVANTAGE OF THE INVENTION According to this invention, after reducing peeling of an agrochemical active component, the fine-grained agrochemical composition which can prevent the caking during long-term storage with high certainty is provided. In addition, since the particulate pesticide composition provided in the present invention can be expected to be solidified even if stored for a long period of time, it can be expected in the pre-packaging / shipping stage. It is possible to stably provide a fine particulate pesticide composition.

Hereinafter, the particulate pesticide composition of the present invention will be specifically described.
In the present invention, a certain component is “covered with mineral fine particles” means that a certain component is present directly or indirectly via other components on a part or all of the surface of the mineral fine particles. In other words, a case where a certain component is also present inside the mineral fine particles depending on the shape of the mineral fine particles is included.

  The agrochemical active ingredient used in the present invention is not particularly limited, and includes agrochemical active ingredients used in the agricultural field such as insecticides, fungicides, herbicides, nematicides, plant growth regulators, and the like. One kind or a combination of two or more kinds can be used.

Next, known insecticides, acaricides, nematicides, and synergists compounds that may be mixed or used together are exemplified.
Acrinathrin, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, acequinocyl, acetamiprid, acetoprole, acetoprole, acetoprole (Acephate), azocyclotin, abamectin, afidopyropen, afoxolaner, amidoflumet, amitraz, alanycarb, aldicarb, aldicarb (Aldoxycarb), allethrin (including d-cis-trans- and d-trans-isomers), isazophos, isamidophos, isocarbophos, isoxathion, isofenphos- methyl), isoprocarb, ivermectin, ivermectin, imicyafos, imidacloprid, imiprothrin, indoxacarb, insoxavalerate, esfenvalerate, ethiofeneth ), Ethiprole, ethylene dibromide, etoxazole, etofenprox, ethoprophos, etrimfos, emamectin benzoate, endosulfan, and enpentolin (Empenthrin), oxamyl, oxydemeton-methyl, oxydeprofos, omethoate, cadusafos, kappa Lutulin (kappa-tefluthrin), kappa-bifenthrin, karanjin, cartap, carbaryl, carbosulfan, carbofuran, gamma-BHC (gamma-BHC) ), Xylylcarb, quinalphos, quinoprene, chinomethionat, coumaphos, cryolite, clothianidin, clofentezine, chromafenozide, chromaafenozide Chlorantraniliprole, chlorethoxyfos, chlordane, chloropicrin, chlorpyrifos, chlorpyrifos-methyl, chlorfenapyr, Chlorfenvinphos, chlorfluazuron, chlormephos, chloroprallethrin, cyanophos, diafenthiuron, diamidafos, cyantraniliprolol (Cyantraniliprole), dienochlor, cyenopyrafen, dioxabenzofos, diofenolan, cyclaniliprole, dicrotophos, dichlofenthion, prothrin ), Dichlorvos, 1,3-dichloropropene, dichloromezotiaz, dicofol, dicyclanil, disulfoton, dinotev Dinotefuran, dinobuton, cyhalodiamide, cyhalothrin [including gamma-form, lambda-form], cyphenothrin [including (1R) -trans-form], cyfluthrin ( cyfluthrin (including beta-form), diflubenzuron, cyflumetofen, diflovidazin, cyhexatin, cypermethrin [alpha-form, beta-form, theta-form, zeta- Body], dimethylvinphos, dimefluthrin, dimethoate, silafluofen, cyromazine, spintoram, spinosad, spirodiclofen, spirocloclofen Tetramat (spirotetramat), spiromesifen (sp iromesifen), sulcofuron-sodium, sulfulamid, sulfluramid, sulfoxaflor, sulfluramid, sulfotep, diazinon, thiacloprid, thiamethoxam, thiamethoxam, thiamethoxam tioxazafen), thiodicarb, thiocyclam, thiosultap, thionazine, thiofanox, thiometon, tetrachlorvinphos, tetradifon, tetraniri Tetraniliprole, tetramethylfluthrin, tetramethrin, tebupirimfos, tebufenozide, tebufenpyrad, Tefluthrin, teflubenzuron, demeton-S-methyl, temephos, deltamethrin, terbufos, tralomethrin, transfluthrin, Triazamate, triazophos, trichlorfon, triflumuron, triflumezopyrim, trimethacarb, tolfenpyrad, nared, nitenpyram, nitenpyram ), Noviflumuron, Verticillium lecanii, hydroprene, Pasturiapenetrans, bamidothion, parathion ion, parathion-methyl, halfenprox, halofenozide, bioallethrin, bioallethrin s-cyclopentenyl, bioresmethrin, bistriflu Ron (bistrifluron), hydramethylnon, bifenazate, kappa-bifenthrin, piflubumide, piperonyl butoxide, pymetrozine, pyracrofos, pyraclofo (Pyrafluprole), pyridaphenthion, pyridaben, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, pyrimicarb (Pirimicarb), pyrimidifen, pyriminostrobin, pyrimiphos-methyl, pyrethrin, famphur, fipronil, fenazaquin, fenamiphos , Fenitrothion, phenoxycarb, phenoxycarb, phenothrin [including (1R) -trans-form], fenobucarb, fenthion, phenthoate, fenvalerate (Fenvalerate), fenpyroximate, fenbutatin oxide, fenpropathrin, fonofos, sulfuryl fluoride, butocarboxim, Butoxycarboxim, buprofezin, furathiocarb, prallethrin, fluacrypyrim, fluazaindolizine, fluazuron, fluenesulfone, sodium fluoroacetate (Sodium fluoroacetate), floxamethamide (fluxametamide), flucycloxuron (flucycloxuron), flucythrinate, flusulfamide (flusulfamide), fluvalinate (including tau-form), flupradidifurone (flupyradifurone), flupirazofos ( flupyrazofos, flufiprole, fluhexafon, flufenerim, flufenoxystrobin, flufenoxuron, flufenoxuron Rubendiamide, flumethrin, fluralaner, prothiofos, protrifenbute, flonicamid, propaphos, propargite, profenfos, profenofos broflanilide, profluthrin, propetamphos, propoxur, flometoquin, bromopropylate, hexathhiazox, hexaflumuron, pechymyces tenuis ten Paecilomyces fumosoroceus, heptafluthrin, heptenophos, permethrin, benclothiaz, Bensultap, benzoximate, bendiocarb, benfuracarb, beverura tenella, beauveria bassiana, beauberia brongniartii, hoxim phoxim, phosalone, fosthiazate, phosthietan, phosphamidon, phosmet, polynactins, formetanate, phorate, malathion, Milbemectin, mecarbam, mesulfenfos, methomyl, metaflumizone, metamidophos, metham, methiocarb Methidathion, methyl isothiocyanate, methyl bromide, methoxychlor, methoxyfenozide, methothrin, methothrin, metofluthrin, epsilon-metofluthrin, epsilon-meto (Methoprene), metolcarb, mevinphos, meperfluthrin, monacrosporium phymatophagum, monocrotophos, momfluorothrin, epsilon-il onmfluorothrin momfluorothrin), Little A (litlure-A), Little A (Litlure-B), Aluminum phosphide, Zinc phosphide, Hydrogen phosphine, Le Lufenuron, rescalure, resmethrin, lepimectin, rotenone, fenbutatin oxide, lime nitrogen (calcium cyanide), nicotine-sulfate, (Z) -11-tetradecenyl acetate, (Z) -11-hexadecenal, (Z) -11-hexadecenyl acetate, (Z) -9,12-tetradecadienyl acetate, (Z) -9-tetradecen-1- All, (Z, E) -9,11-tetradecadienyl acetate, (Z, E) -9,12-tetradecadienyl acetate, Bacillus popilliae, Bacillus subtillis ), Bacillus sphaericus, Bacillus thuringiensis, subspecies, isawai Bacillus thuringiensis subsp. Aizawai), Bacillus thuringiensis subsp. Israelensis, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tennebrionis (Bacillus) thuringiensis subsp.Tenebrionis), Bt protein (cry1Ab, cry1AC, cry1fa, cry2Ab, mCry3A, cry3Ab, cry3Bb, Cry34 / 35Ab1), CL900167 (code number), bis- (2-chloro-1-methylethyl) ether (DCIP) 1,1,1-trichloro-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 embedding, 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 (Code number).

Next, known fungicidal compounds that may be mixed or used together are exemplified.
Azaconazole, acibenzolar-S-methyl, azoxystrobin, anilazine, amisulbrom, ametoctradin, aldimorph, isothianil , Isopyrazam, isofetamid, isoprothiolane, ipconazole, iprodione, iprovalicarb, iprobenfos, imazalil, octylinal salt ), Iminoctadine-triacetate, imibenconazole, edifenphos, etaconazole, ethaboxam, ethirimol , Ethoxyquin, etridiazole, enestroburin, enoxastrobin, epoxiconazole, organic oils, oxadixyl, oxazinylazole ), Oxathiapiprolin, oxycarboxin, oxine-copper, oxytetracycline, oxpoconazole-fumarate, oxolinic acid ), Copper dioctanoate, octhilinone, ofurace, orysastrobin, ortho-phenylphenol, kasugamycin, captafol, carpropamide (ca) rpropamid, carbendazim, carboxin, carbonone, carvone, quinoxyfen, quinomethionat, captan, quinconazole, quintozene, guazatine , Cufraneb, coumoxystrobin, kresoxim-methyl, clozylacon, chlozolinate, chlorothalonil, chloroneb, cyazofamid, cyazofamid diethofencarb), diclocymet, dichlorfluanid, diclomezine, dicloran, dichlorophen, dithianon, diiconazole, Niconazole M (diniconazole-M), zineb, dinocap, dipymetitrone, diphenylamine, difenoconazole, cyflufenamid, diflumetorim, cyproconazole , Cyprodinil, simeconazole, dimethirimol, dimethyl disulfide, dimethomorph, cymoxanil, dimoxystrobin, ziram, silthiofam , Streptomycin, spiroxamine, sedaxane, zoxamide, dazomet, thiazinil, thiabendazole, Uram (thiram), thiophanate, thiophanate-methyl, thifluzamide, tecnazene, tecloftalam, tetraconazole, debacarb, tebuconazole , Tebufloquin, terbinafine, dodine, dodemorph, triadimenol, triadimefon, triazoxide, triazoxide, trichlamide, triclopyricarb Tricyclazole, triticonazole, tridemorph, triflumizole, trifloxystrobin, triforine, trilfluanide (t olylfluanid, tolclofos-methyl, tolnifanide, tolprocarb, nabam, natamycin, naftifine, nitrapyrin, nitrothal-isopropyl ), Nuarimol, copper nonyl phenol sulphonate, Bacillus subtilis (strain: QST 713), validamycin, valifenalate, picarbutrazox ), Bixafen, picoxystrobin, pydiflumetofen, bitertanol, binapacryl, biphenyl, piperalin, hymexazol, piper Oxystrobin, pyraclostrobin, pyraziflumid, pyrazophos, pyrametostrobin, pyriofenone, pyrisoxazole, pyrifenox (pyrifenox) pyributicarb, pyribencarb, pyrimethanil, pyroquilon, vinclozolin, ferbam, famoxadone, phenazine oxide, fenamidone, feninstrobin ), Fenarimol, fenoxanil, ferimzone, fenpiclonil, fenpyrazamine, fenbuconazole nazole), fenfuram, fenpropidin, fenpropimorph, fenhexamid, folpet, phthalide, bupirimate, fuberidazole, Blasticidin-S, furametpyr, furalaxyl, furancarboxylic acid, fluazinam, fluindapyr, fluoxastrobin, fluopicolide ), Fluopyram, fluoroimide, fluxapyroxad, fluquinconazole, furconazole, furconazole-cis, fludioxonil, flusixonil Flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, flufenoxystrobin, flumetover, flumorph, proquinazid, Prochloraz, procymidone, prothiocarb, prothioconazole, bronopol, propamocarb-hydrochloride, propiconazole, propineb, probenazole probenazole, bromuconazole, flemtoquin, hexaconazole, benalaxyl, benalaxyl-M, benodanil, benomyl (Benomyl), pefurazoate, penconazole, penciclone (pencycuron), benzovindiflupyr (benzovindiflupyr), benthiazole, benchthiavalicarb-isopropyl, penthiopyrad (penthiopyrad), Penflufen, boscalid, fosetyl (alminium, calcium, sodium), polyoxin, polycarbamate, Bordeaux mixture, mancozeb, mandipropamid, mandipropamid Mandestrobin, maneb, microbutanil, mineral oils, mildiomycin, metasulfocarb, metham, metalaxyl (m etalaxyl, metalaxyl-M, metiram, metconazole, mettominostrobin, metrafenone, mepanipyrim, meptyldinocap, mepronilmepro ), Iodocarb, laminarin, phosphorous acid and salts, copper oxychloride, silver, cuprous oxide, second hydroxide Copper hydroxide, potassium bicarbonate, sodium bicarbonate, sulfur, oxyquinoline sulfate, copper sulfate, (3,4-dichloroisothiazole -5-yl) methyl 4- (tert-butyl) benzoate (chemical name, CAS registry number: 123) 214-23-5), 3-((3,4-dichloroisothiazol-5-yl) methoxy) benzo [d] isothiazole-1,1-dioxide (Chemical name, CAS Registry Number: 957144-77-3) ), BAF-045 (code number), BAG-010 (code number), UK-2A (code number), dodecylbenzenesulfonic acid bisethylenediamine copper complex [II] (DBEDC), MIF-1002 (code number), NF -180 (code number), triphenyltin acetate (TPTA), triphenyltin chloride (TPTC), triphenyltin hydroxide (TPTH), non-pathogenic Ervinia carotobola.

Next, known herbicide compounds and plant growth regulator compounds that may be mixed or used together are exemplified below.
Herbicidal active ingredient:
Ioxynil, acronifen, acrolein, azafenidin, acifluorfen (including salts with sodium, etc.), azimsulfuron, asuram, acetochlor (Acetochlor), atrazine, anilofos, amicarbazone, amidosulfuron, amitrole, aminocyclopyrachlor, aminopyralid, amiprofos- methyl), ametrin (alametry), alachlor, alloxydim, isouron, isoxachlortole, isoxaflutole, isoxaflutole, isoxaben, isoproturon (isop) roturon, ipfencarbazone, imazaquin, imazapic (including salts with amines, etc.), imazapyr (including salts such as isopropylamine), imazamethabenz-methyl , Imazamox, imazethapyr, imazosulfuron, indaziflam, indanofan, eglinazine-ethyl, esprocarb, ethamet ham etyl et , Ethalfluralin, ethidimuron, ethoxysulfuron, ethoxyfen-ethyl, ethofumesate, ettobenzanid, endothal-disodium, oxy Oxasulfuron, oxadiazon, oxadiargyl, oxaziclomefone, oxyfluorfen, oryzalin, orthosulfamuron, orbencarb, cfentrol, cafentrol Fentrazone-ethyl, karbutilate, carbetamide, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl, quizalofop-P -tefuryl), quinoclamine, quinclorac, quinmerac, cumyluron, clacyfos, glyphosate (sodium, amine, propylamine, isopropyl) Including salts such as min, dimethylamine or trimesium), glufosinate (including salts such as amine or sodium), glufosinate-P-sodium, clethodim, clodinafop -propargyl), clopyralid, clomazone, chlomethoxyfen, clomeprop, cloransulam-methyi, chloramben, chloridazon, chlorimuron -ethyl), chlorsulfuron, chlorthal-dimethyl, chlorthiamid, chlorphthalim, chlorflurenol-methyl, chlorpropham, chlorbromron chlorbromuron, chloroxuron, chlorotoluron, ketospirodox, saflufenacil, cyanazine, cyanamide, diuron, diethatyl-dic, dicambal ) (Including salts such as amine, diethylamine, isopropylamine, diglycolamine, sodium or lithium), cycloate, cyclooxydim, diclosulam, cyclosulfamuron, cyclopyrimoleate (Cyclopyrimorate), diclolobenil, diclofop-P-methyl, diclofop-methyl, dichlorprop, dichlorprop-P, diquat (Diqua t), dithiopyr, siduron, dinitramine, cinidon-ethyl, cinosulfuron, dinoterb, cyhalofop-butyl, diphenamid , Difenzoquat, diflufenican, diflufenzopyr, simazine, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P (dimethenamid-P) simetryn, dimepiperate, dimefuron, cinmethylin, swep, sulcotrione, sulfentrazone, sulfosulfuron, sulfometuron methyl (sul) fometuron-methyl), sethoxydim, terbacil, daimuron, dalapon, thiazopyr, tiafenacil, thiencarbazone (including sodium salt, methyl ester, etc.), Thiocarbazil, thiobencarb, thidiazimin, thifensulfuron-methyl, desmedipham, desmetryip, tenenylchlor, tebutam, tebutamuron tebuthiuron, tepraloxydim, tefuryltrione, tembotrione, terbuthylazine, terbutryn, terbumeton, topramezone, toramezone Ralcoxidim, triaziflam, triasulfuron, triafamone, tri-allate, trietazine, triclopyr, triclopyr-butotyl, trilopyr-butotyl Freon (tritosulfuron), trifludimoxazin, triflusulfuron-methyl, trifluralin, trifloxysulfuron-sodium, tribenuron-methyl, Tolpyralate, naptalam (including salts with sodium, etc.), naproanilide, napropamide, napropamide, napropamide-M, nicosulfuron, neburo n), norflurazon, vernolate, halauxifen-benzyl, paraquat dichloride, halauxifen-methyl, haloxyfop, haloxyfop-P ), Haloxyfop-etotyl, halosulfuron-methyl, picloram, picolinaphen (picloram, bicyclopyrone), bispyribac-sodium, pinoxaden , Bifenox, piperophos, pyraclonil, pyrasulfotole, pyrazoloxyfen, pyrazosulfuron-ethyl, pyrazolynate, vilanazos (bila) nafos, pyraflufen-ethyl, pyridafol, pyrithiobac-sodium, pyridate, pyriftalid, pyributicarb, pyribenzoxim, pyrimislphan (Pyrimisulfan), pyriminobac-methyl, pyroxasulfone, pyroxsulam, phenisopham, fenuron, fenoxasulfone, phenoxaprop P-ethyl ( fenoxaprop-P-ethyl, fenquinotrione, fenthiaprop-ethyl, fentrazamide, phenmedipham, foramsulfuron, butacrol hlor), butafenacil, butamifos, butyrate, butenachlor, butenalin, butralin, butroxydim, flazasulfuron, flamprop (methyl, ethyl, Including isopropyl ester), flamprop-M (including methyl, ethyl, isopropyl ester), primisulfuron-methyl, fluazifop-butyl, fluazifop-P- butyl, fluazolate, fluometuron, fluoroglycofen-ethyl, flucarbazone-sodium, fluchloralin, flucetosulfuron, fluthiaset methyl -me thyl, flupirsulfuron-methyl-sodium, flufenacet, flufenpyr-ethyl, flupropanate, flupoxame, flumioxazin ( flumioxazin, flumiclorac-pentyl, flumetsulam, fluridone, flurtamone, fluroxypyr, flurochloridone, pretilachlor, procarbazone sodium salt (Procarbazone-sodium), prodiamine, prosulfuron, prosulfocarb, propaquizafop, propachlor, propazine, propanil, propizzami (Propyzamide), propisochlor, propyrisulfuron, propham, profluazole (PROFLUAZOL), propoxycarbazone-sodium, propoxydima, profoxydim, bromacil ), Brompyrazon, promethrin, prometon, bromoxynil (including esters such as butyric acid, octanoic acid or heptanoic acid), bromofenoxim, bromobutide, florasulam (Florasulam), petoxamide, benazolin, penoxsulam, heptamaloxyloglucan, beflubutamid, pebulate, bencarbazone, penji Metalin (pendimethalin), benzfendizone (benzfendizone), bensulide (bensulide), bensulfuron-methyl, benzobicyclon (benzobicyclon), benzofenap (benzofenap), bentazone (bentazone), pentanochlor (Pentanochlor), pentoxazone, benfluralin, benfuresate, fosamine, fomesafen, foramsulfuron, mecoprop
(Including salts such as sodium, potassium, isopropylamine, triethanolamine, dimethylamine), mecoprop-P-potassium, mesosulfuron-methyl, mesotrione, metaza Metazachlor, metazosulfuron, metabenzthiazuron, metamitron, metamihop, methizolin, methyldymuron, metoxuron, tolamus Metsulfuron-methyl, metobromuron, metobenzuron, metolachlor, metribuzin, mefenacet, monolinuron , Molinate, iodosulfuron, iodosulfulon-methyl-sodium, iofensulfuron, iofensulfuron-sodium, lactofen Linuron, rimsulfuron, lenacil, 2,3,6-trichlorobenzoic acid (2,3,6-TBA), 2,4,5-trichlorophenoxyacetic acid (2,4,4) 5-T), 2,4-dichlorophenoxyacetic acid (2,4-D) (including salts such as amine, 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) (amine or Including salts such as thorium), S-ethyldipropylthiocarbamate (EPTC), 2-methyl-4-chlorophenoxyacetic acid (MCPA), MCPA-thioethyl (MCPA-thioethyl), 2-methyl-4-chlorophenoxybutyric acid (MCPB) (including sodium salt, ethyl ester, etc.), SYP-298 (code number), SYP-300 (code number), S-metolachlor, 2,2,2-trichloroacetic acid (TCA ) (Including salts such as sodium, calcium or ammonia).

Plant growth regulator:
1-naphthylacetamide, 1-methylcyclopropene, 2,6-diisopropylnaphthalene, 4-chlorophenoxyacetic acid (4-CPA), 4-oxo- 4- (2-phenylethyl) aminobutyric acid (chemical name, CAS registry number: 1083-55-2), aviglycine, ansimidol, inabenfide, indole acetic acid, Indole butyric acid, uniconazole, uniconazole-P, etychlozate, ethephon, epocholeone, carbonone, cloxyfonac, cloxyfonac Honak potassium salt (cloxyfonac-potassium), cloprop (clo prop), chlormequat, cytokinins, cyclanilide, dikegulac, gibberellin acid, dimethipin, sintofen, daminozide, thiazuron, thidiron -Decyl alcohol (n-decanol), triacontanol, trinexapac-ethyl, paclobutrazol, flumetralin, flurprimidol, flurenol ), Prohydrojasmon, prohexadione-calcium, benzylaminopurine, forchlorfenuron, maleic hydrazide, mepiquat Lido (mepiquat chloride), mefluidide (mefluidide), calcium peroxide.

Next, the known safeguard compound which may be mixed or used together is illustrated.
4-dichloroacetyl-1-oxa-4-azaspiro [4.5] decane (AD-67), N1, N2-diallyl-N2-dichloroacetylglycinamide (DKA-24), 2-dichloromethyl-2-methyl -1,3-dioxane (MG-191), MON 4660 (code number), N- (2-methoxybenzoyl) -4-[(methylaminocarbonyl) amino] benzenesulfonamide (Chemical name, CAS registry number: 129531- 12-0), 2,2-dichloro-N- (1,3-dioxan-2-ylmethyl) -N- (2-propenyl) acetamide (PPG-1292), 3-dichloroacetyl-2,2,5- Trimethyl-1,3-oxazolidine (R-29148), TI-35 (code number), isoxadifen, isoxodifen Isoxadifen-ethyl, oxabetrinil, cloquintcet-mexyl, ciometrinil, dichlormid, dicyclonone, cyprosulfamide, naphthalic acid Anhydrides (1,8-Naphthalic Anhydride), fenchlorazole-O-ethyl, fenchlorazole (FeNclorim), furilazole, fluxofenim (fluxofenim), flurazole, benoxacol (fluxofenim), mefenpyr (Mefenpyr), mefenpyr-ethyl, mefenpyr-diethyl, lower alkyl substituted benzoic acid.

  Among the pesticidal active ingredients, preferably tricyclazole, azoxystrobin, IBP, iminotadine acetate, kasugamycin, validamycin, ferimzone, BPMC, cartap hydrochloride, dinotefuran, clothianidin, imidacloprid, mepronil, pencyclon, EDDP, phenoxanyl, flutolanil , Fusalide, diclocimet, isoprothiolane, dichromedin, MPP, etofenprox, methoxyphenozide, buprofezin, MEP, tebufenozide, PAP, silafluophene, ethiprole, bensultap and the like. Among these, those containing one or more of dinotefuran, tricyclazole, pencyclon and buprofezin are more preferable, those containing dinotefuran and tricyclazole, and those containing pencyclon and / or buprofezin in addition to dinotefuran and tricyclazole. preferable.

  The content of the pesticidal active ingredient in the fine pesticide composition of the present invention is an amount necessary for exhibiting the intended effect and is not particularly limited. For example, the pesticide activity is based on the total amount of the fine pesticide composition. It is 0.01-20 mass% as a total amount of a component, Preferably it is 0.1-5 mass%.

  In a conventional finely divided pesticide composition containing a pesticide active ingredient, a water-soluble binder, and mineral fine particles, when a pesticide active ingredient having a water solubility of 100 ppm or more at 20 ° C. is formulated, the pesticide activity during the production process and spraying While the peeling of the fine particles containing the component is very large, the peeling mitigating effect in the fine granular agricultural chemical composition of the present invention is particularly remarkable in the agricultural chemical active ingredient having a water solubility at 20 ° C. of 100 ppm or more.

  The finely divided pesticide composition of the present invention can be used in any combination of one or more of the above pesticidal active ingredients according to the purpose.

  If necessary, the pesticidal active ingredient in the finely divided pesticidal composition of the present invention can be mixed and ground in advance with clay, calcium carbonate, talc, acid clay, diatomaceous earth, silica and the like and added as a bulk powder.

  The saccharide that is liquid at room temperature in the finely divided pesticide composition of the present invention is generally called molasses. As the type of saccharides, sugar cane molasses, sugar beet molasses, refined molasses molasses, ice molasses, and invert sugar containing reducing sugar, such as sucrose, hydrolyzed into glucose and fructose Examples thereof include those containing invert sugar together with non-reducing sugars such as sugar and sucrose. Of these, those containing 20% by mass or more of reducing sugar are preferable, more preferably those containing 40% by mass or more of reducing sugar, and liquid sugar containing about 50% by mass of reducing sugar is particularly preferable. A liquid sugar containing 45 to 54% by mass of reducing sugar is also particularly preferable.

  Moreover, although content of the said saccharide | sugar is not limited, For example, it is 0.05-1 mass% on the basis of whole quantity of a fine-grained agricultural chemical composition, Preferably it is 0.1-0.7 mass%, More preferably It is 0.15-0.4 mass%. If the saccharide content is insufficient, the anti-peeling effect of the pesticidal active ingredient may be insufficient, while if the saccharide content is excessive, the risk of consolidation may increase.

Examples of the mineral fine particles in the fine granular agricultural chemical composition of the present invention include quartz sand, pumice, calcium carbonate, clay and the like, and preferably quartz sand.
In the present invention, it is preferable that the particle size distribution of mineral fine particles is 90% or more of particles having a size of 63 to 300 μm. Mineral fine particles having an upper limit of particle size distribution of 300 μm retain the adhesion to target crops in foliage treatment and uniformity in soil treatment, and obtain the expected biological effect. In addition, the mineral fine particles whose particle size distribution has a lower limit of 63 μm has a small scattering at the time of spraying, and the influence on the sprayer and surrounding crops can be eliminated.

  In the present specification, when dealing with the particle size and particle size distribution of the finely divided pesticide composition, “particle size” means a particle size determined by a sieving method using a sieve having a predetermined mesh, “63 to The term “300 μm particles” or “particles having a particle size of 63 to 300 μm” means particles obtained by sieving with a sieve having openings of 300 μm and 63 μm. “Particle size distribution” means the cumulative weight percentage of the specified particle size range obtained by the sieving method. When dealing with the particle size and particle size distribution of individual components including agrochemical active ingredients, “Distribution” means an integrated volume percentage of a predetermined particle size range determined by a laser diffraction method (measured by a wet method; SK Laser Micron Sizer LMS-2000e (manufactured by Seishin Enterprise Co., Ltd.)).

  The content of mineral fine particles in the fine pesticide composition is, for example, 85 to 99 mass%, preferably 90 to 95 mass%, based on the total amount of the fine pesticide composition.

  The particulate pesticide composition of the present invention contains a water-soluble binder. As the water-soluble binder, known ones such as polyvinyl alcohol, polyvinyl pyrrolidone, and carboxymethyl cellulose can be used, and polyvinyl alcohol is particularly preferable. The content of the water-soluble binder is, for example, 0.1 to 1% by mass, preferably 0.3 to 0.8% by mass, based on the total amount of the fine granular agricultural chemical composition.

Moreover, in this invention, after coat | covering the pesticidal active ingredient on the mineral fine particle containing 90% or more of particles having a particle size of 63 to 300 μm, the fine pesticidal composition coated with the pesticidal active ingredient is dried. Before or after, fine powder that can be used as a solid carrier for agrochemical preparations such as silica, clay, calcium carbonate and the like can be added and mixed, and the caking prevention effect of the resulting finely divided agrochemical composition can be remarkably enhanced. As the fine powder, silica is particularly preferable.
The fine powder used as the solid carrier of the agrochemical preparation is preferably easy-dispersible as a powder, that is, low agglomeration. Since such agglomeration of fine powder may occur via moisture adsorbed on the surface of the fine powder particles, a fine powder having low affinity with water is preferable in order to avoid it. Specifically, for example, a fine powder that can be used as a solid carrier of the agrochemical preparation is preferably one that exhibits a mass loss of less than 4% by mass when dried at 105 ° C. for 2 hours in air at normal pressure. .

  The fine powder used as the solid carrier of the agrochemical formulation is also preferably one having an equilibrium moisture content of less than 7% by mass in an atmosphere at 25 ° C. and a relative humidity of 70%. The equilibrium moisture content means the moisture content measured by the Karl Fischer method for a sample exposed to a predetermined constant temperature and constant humidity atmosphere condition for one week or more. The atmosphere at 25 ° C. and the relative humidity of 70% is a method of setting with a commercially available constant temperature and humidity chamber (for example, a constant temperature and humidity chamber manufactured by Espec Corp.), a desiccator storing a 64% by mass glycerin aqueous solution, Although the method etc. which are set by adjusting temperature to 25 degreeC can be illustrated, it is not limited to these.

  The amount used when adding fine powder that can be used as a solid carrier of the agrochemical formulation is preferably 0.1 to 1% by mass, more preferably 0.2 to 0.1% by mass, based on the total amount of the finely divided agrochemical composition. It is 0.8 mass%, Most preferably, it is 0.3-0.6 mass%. If the amount of fine powder added is excessive, the consolidation risk is reduced, but the agrochemical active ingredient may be peeled off.

In the finely divided agrochemical composition of the present invention, one or more surfactants, stabilizers, pH adjusters, colorants and the like can be added as auxiliary agents other than those described above, as necessary. .
Examples of the surfactant include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene fatty acid diester, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, Oxyethylene alkyl phenyl ether, polyoxyethylene dialkyl phenyl ether, polyoxyethylene alkyl phenyl ether formalin condensate, polyoxyethylene polyoxypropylene block polymer, alkyl polyoxyethylene polypropylene block polymer ether, polyoxyethylene alkylamine, polyoxyethylene Fatty acid amide, polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzyl Nyl ether, polyoxyalkylene styryl phenyl ether, acetylene diol, polyoxyalkylene-added acetylene diol, polyoxyethylene ether type silicone, ester type silicone, fluorosurfactant, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, etc. Ionic surfactants; alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl benzene sulfonates, lignin sulfonates, alkyl sulfosuccinates , Naphthalene sulfonate, alkyl naphthalene sulfonate, salt of formalin condensate of naphthalene sulfonic acid, formal of alkyl naphthalene sulfonic acid Anionic surfactants such as salts of fatty acid condensates, fatty acid salts, polycarboxylates, N-methyl fatty acid sarcosinates, resinates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates; Cationic surfactants such as alkylamine salts such as laurylamine hydrochloride, stearylamine hydrochloride, oleylamine hydrochloride, stearylamine acetate, stearylaminopropylamine acetate, alkyltrimethylammonium chloride, alkyldimethylbenzalkonium chloride; amino acids Amphoteric surfactants such as molds or betaines.

  Examples of the stabilizer include fatty acids, ascorbic acid, hydrocarbon solvents, urea, and the like. Examples of the pH adjuster include citric acid, trisodium citrate, sodium carbonate, phosphoric acid and the like. Examples of the colorant include inorganic pigments such as iron oxide, titanium oxide, and Prussian blue, organic dyes such as alizarin dyes, azo dyes, and metal phthalocyanine dyes.

  The finely divided pesticide composition of the present invention is particularly useful as a foliage spray for the purpose of controlling pests of late stage pests in paddy rice cultivation, a soil treatment for the purpose of controlling pests in the soil in fields, etc. Is not limited to these. Moreover, the application amount is not particularly limited, but is, for example, 1 to 30 kg per 10 ares, and preferably 3 to 20 kg can be applied.

  The particulate agrochemical composition of the present invention can be evaluated for its potential caking risk when stored for a long time as well as its caking property immediately after production by the following method. That is, a fine pesticide composition is put into a packaging bag made of an airtight material, and the inside of the packaging bag is sealed with a gauge pressure reduced to minus 27000 Pa (± 4%), at a constant temperature of 15 ° C. After storing for 48 hours, the packaging bag is opened, and the entire amount of the fine pesticide composition as the contents is discharged on a mesh having a mesh opening of 1.7 mm, without impact, and simply discharged by gravity. If the finely divided pesticide composition that passes through the mesh is 75% by mass or more of the total amount of the finely divided pesticide composition, the finely divided pesticide composition does not solidify even when stored for a long period of time.

Here, as a packaging bag used for the said test, the material which has airtightness and can be processed into a bag shape or a bag shape is preferable. Here, having airtightness means that the oxygen permeability is 1 ml / m ² · 24 h or less. Although it will not specifically limit if it is a packaging material which has such a characteristic, An aluminum bag, an aluminum laminated bag, etc. can be used especially preferable. Examples of the equipment used for decompression and sealing of the packaging bag include, but are not limited to, a heat sealer having a deaeration function (for example, a deaeration sealer manufactured by Fuji Impulse).

  In addition, as a specific means for performing the above-mentioned “discharge the whole amount of the finely divided pesticide composition on a mesh having a mesh opening size of 1.7 mm without applying an impact”, for example, immediately above the opening of the opened packaging bag A method of covering the mesh, inverting gently and reversing the top and bottom, then slowly pulling up the packaging bag and using gravity to transfer only the fine pesticide composition onto the mesh can be mentioned. Shake the packaging bag to force the fine pesticide composition to discharge, hit the package to discharge the contents, drop the fine pesticide composition onto the mesh from a high place, etc. When an operation of applying an impact to a finely divided pesticide composition is performed, even if a solid finely divided pesticide composition is present, it is loosened, which may hinder accurate evaluation. In the present invention, the above consolidation risk evaluation method may be referred to as a “decompression test”.

The above-mentioned finely divided pesticide composition, which is excellent in storage stability and is prevented from peeling off the pesticidal active ingredient at the time of spraying, is composed of mineral fine particles in a mixed aqueous solution of a water-soluble binder and a saccharide that is liquid at room temperature as described below. Can be produced by a method comprising the step (a) of wetting the step, the step (b) of coating the mineral fine particles with an agrochemical active ingredient, and the step (c) of drying the coated mineral fine particles.
In the above step (a), the mineral fine particles are wetted with a mixed aqueous solution of a water-soluble binder and a saccharide that is liquid at room temperature. For example, the water-soluble binder is dissolved in water, and the saccharide that is liquid at room temperature. Is carried out by adding and mixing mineral fine particles to an aqueous solution obtained by adding and mixing. In this case, the amount of the mineral fine particles added is preferably 0.1 to 20% by weight, more preferably the concentration in the aqueous solution in order to reduce the drying load in step (c) and efficiently perform the drying. 1 to 10% by weight. In addition, for this step (a), for example, a commercially available apparatus such as a dissolver (manufactured by PRIMIX, product name “TK Robotics”) can be used.

In addition, the coating of the mineral fine particles with the pesticidal active ingredient in the step (b) is usually performed using an apparatus for stirring and mixing. Examples of such apparatuses include a mixer in which a screw revolves along the inner wall of a conical container (for example, a Nauta mixer manufactured by Hosokawa Micron Corporation), a mixer in which two cylindrical containers combined with a V shape rotate (for example, , Fuji Powder Co., Ltd. V-type mixer), mixers in which the blades on the bottom and sides of the container rotate at high speed (for example, a vertical granulator made by POWREC, a high speed mixer made by Fukae Powtech), etc. It is done.
Stirring and mixing in the step (b) are performed at room temperature or a temperature of 0 to 100 ° C. for 1 to 10 minutes, for example.

Drying in the step (c) is preferably performed at a temperature of room temperature to 300 ° C, more preferably 60 to 120 ° C, preferably 30 seconds to 24 hours, more preferably 1 minute to 2 hours. Thereby, the water contained in the mineral fine particles coated with the pesticidal active ingredient obtained in the step (b) is removed, and preferably 0 to 5% by weight, more preferably per total mass of the fine pesticidal composition. Is 0 to 1.5% by weight.
As an apparatus used in the step (c), a dryer (for example, a fluidized bed dryer manufactured by Fuji Powder Co., Ltd.) that flows grains by feeding hot air, and the apparatus itself vibrates while feeding hot air. However, it is not limited to these, for example, a dryer for flowing the particles (for example, a vibratory fluid dryer manufactured by Fuji Powder Co., Ltd., a vibratory dryer manufactured by Shinko Electric Co., Ltd.).

Furthermore, when adding the fine powder which can be used as a solid support | carrier of an agricultural chemical formulation to a fine-grained agricultural chemical composition, in addition to process (a)-(c), the manufacturing method of this invention coat | covers an agricultural chemical active ingredient further. A step (d) of mixing the fine mineral substance particles and fine powder that can be used as a solid carrier of the agricultural chemical preparation.
This step (d) may be performed before the step (c), but is preferably performed after the step (c). Alternatively, step (d) may be performed a plurality of times before and after step (c). Moreover, you may perform a process (d) intermittently in multiple times after a process (c). The fine particulate agrochemical composition of the present invention can significantly reduce its consolidation risk by carrying out the step (d).

  Whether or not the consolidation risk of the fine pesticide composition is sufficiently reduced can be evaluated by the above-described decompression test. That is, the produced fine pesticide composition is subjected to a pressure reduction test, and if the fine pesticide composition passing through the mesh is 75% by mass or more of the total amount of the fine pesticide composition, it can be packaged as a good product. If the above is less than 75% by mass, a decompression test is performed after further performing step (d), and this may be repeated until the above is 75% by mass or more. By doing in this way, a necessary and sufficient process (d) can be performed to a fine-grained pesticide composition, and the fine-grained pesticide composition with a little concern of caking is manufactured stably and provided. It becomes possible.

Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. In Examples and Comparative Examples, “part” means part by weight and “%” means mass% unless otherwise specified.
“Silica (A)” is a Karl Fischer sample that was exposed to constant temperature and constant humidity conditions of 5.7%, 25 ° C., and 70% relative humidity when heated at 105 ° C. for 2 hours. Is a silica having a water content measured by the method of 8.9%, and “silica (B)” has a mass loss of 3.6% at 25 ° C. and a relative humidity of 70% when heated at 105 ° C. for 2 hours. About the sample exposed to constant humidity atmosphere conditions for one week or more, it is a silica whose moisture content measured by Karl Fischer method is 5.6%.

[Example 1]
A binder aqueous solution in which 0.66 parts of polyvinyl alcohol is dissolved in a predetermined amount of water and 0.1 part of a liquid sugar (trade name Nitto High Sweet Deluxe, manufactured by Mitsubishi Chemical Foods) containing about 50% reducing sugar is mixed. , Was added to 92.24 parts of silica sand containing 90% or more of 63-212 μm particles, and the whole was moistened. To this, 0.35 parts of dinotefuran, 0.5 part of tricyclazole and 2.15 parts of calcium carbonate were added in advance and mixed for coating. Further, 4 parts of silica (A) was added and mixed for coating. did. Thereafter, it is dried with a fluidized bed dryer at a hot air temperature of 80 ° C. for 5 minutes, sieved with a sieve having openings of 212 μm and 63 μm, excluding particles of 212 μm or more and particles of 63 μm or less. Obtained. The pressure reduction test result of the fine granular agrochemical composition was 86.6%.

[Example 2]
A binder aqueous solution prepared by dissolving 0.66 part of polyvinyl alcohol in a predetermined amount of water and mixing 0.25 part of a liquid sugar (trade name Nitto High Sweet Deluxe, manufactured by Mitsubishi Chemical Foods) containing about 50% of a reducing sugar. Were added to 93.69 parts of silica sand containing 90% or more of 63-212 μm particles, and the whole was moistened. To this, 0.35 parts of dinotefuran, 0.5 part of tricyclazole and 1.15 parts of calcium carbonate were added in advance, mixed and coated, and further 3 parts of silica (A) was added and mixed. did. Then, it dried for 5 minutes with a fluidized bed dryer at a hot air temperature of 80 ° C., and sieved with a sieve having openings of 212 μm and 63 μm to remove particles of 212 μm or more and particles of 63 μm or less. Furthermore, 0.4 part of silica (B) was added and mixed and coated until the reduced pressure test result was 75% or more to obtain a finely divided pesticide composition. The final reduced pressure test result of the finely divided pesticide composition was 94.9%.

[Example 3]
A binder aqueous solution in which 0.66 parts of polyvinyl alcohol is dissolved in a predetermined amount of water and 0.1 part of a liquid sugar (trade name Nitto High Sweet Deluxe, manufactured by Mitsubishi Chemical Foods) containing about 50% reducing sugar is mixed. , Was added to 92.24 parts of silica sand containing 90% or more of 63-212 μm particles, and the whole was moistened. To this, a raw powder prepared by mixing 0.35 parts of dinotefuran, 0.5 parts of tricyclazole, 1.5 parts of pencyclone and 0.65 parts of calcium carbonate in advance is mixed and coated, and further 4 parts of silica (A). Was mixed and coated. Thereafter, it is dried with a fluidized bed dryer at a hot air temperature of 80 ° C. for 5 minutes, sieved with a sieve having openings of 212 μm and 63 μm, excluding particles of 212 μm or more and particles of 63 μm or less. Obtained. The pressure reduction test result of the fine granular agrochemical composition was 77.8%.

[Example 4]
A binder aqueous solution prepared by dissolving 0.66 part of polyvinyl alcohol in a predetermined amount of water and mixing 0.25 part of a liquid sugar (trade name Nitto High Sweet Deluxe, manufactured by Mitsubishi Chemical Foods) containing about 50% of a reducing sugar. , 63-212 μm particles were added to 92.59 parts of silica sand containing 90% or more, and the whole was moistened. To this, 0.35 parts of dinotefuran, 0.5 parts of tricyclazole, 1.5 parts of pencyclon, and 0.65 parts of calcium carbonate were added in advance, mixed and coated, and 3 parts of silica (A) was further added. Added and mixed coated. Then, it dried for 5 minutes with a fluidized bed dryer at a hot air temperature of 80 ° C., and sieved with a sieve having openings of 212 μm and 63 μm to remove particles of 212 μm or more and particles of 63 μm or less. Further, 0.5 part of silica (B) was added and mixed and coated until the reduced pressure test result was 75% or more to obtain a fine-grained agricultural chemical composition. The final reduced pressure test result of the finely divided pesticide composition was 90.9%.

[Comparative Example 1]
A binder aqueous solution prepared by dissolving 0.66 part of polyvinyl alcohol in a predetermined amount of water and mixing 0.25 part of a liquid sugar (trade name Nitto High Sweet Deluxe, manufactured by Mitsubishi Chemical Foods) containing about 50% of a reducing sugar. , 63-212 μm particles were added to 94.09 parts of silica sand containing 90% or more, and the whole was moistened. The raw powder in which 0.35 part of dinotefuran, 0.5 part of tricyclazole and 1.15 part of calcium carbonate were mixed in advance was added and mixed, and 3 parts of silica (A) was further added and mixed. Thereafter, it was dried with a fluidized bed dryer at a hot air temperature of 80 ° C. for 5 minutes, and sieved with a sieve having openings of 212 μm and 63 μm, and particles of 212 μm or more and particles of 63 μm or less were removed to obtain a fine agricultural chemical composition. . The result of the reduced pressure test of the fine granular agrochemical composition was 61.5%.

[Comparative Example 2]
A binder aqueous solution prepared by dissolving 0.66 part of polyvinyl alcohol in a predetermined amount of water and mixing 0.25 part of a liquid sugar (trade name Nitto High Sweet Deluxe, manufactured by Mitsubishi Chemical Foods) containing about 50% of a reducing sugar. , 63-212 μm particles were added to 93.09 parts of silica sand containing 90% or more, and the whole was moistened. To this was added 0.35 parts of dinotefuran, 0.5 parts of tricyclazole, 1.5 parts of pencyclone and 0.65 parts of calcium carbonate, and mixed and coated, and 3 parts of silica (A) was further added. And mixed coated. Thereafter, it was dried with a fluidized bed dryer at a hot air temperature of 80 ° C. for 5 minutes, and sieved with a sieve having openings of 212 μm and 63 μm, and particles of 212 μm or more and particles of 63 μm or less were removed to obtain a fine agricultural chemical composition. . The result of the reduced pressure test of the fine granular pesticide composition was 62.3%.

[Test Example 1] Stability test over time 3 kg of each of the finely divided pesticide compositions of Examples and Comparative Examples are packaged in aluminum kraft bags, left in a warehouse without air conditioning equipment for one year, then opened and the contents Was discharged, and the state of the finely divided pesticide composition was confirmed. The results are shown in Table 1.

[Test Example 2] Pesticide active ingredient peelability test In order from the top, a multi-stage sieve with mesh openings of 212 μm, 63 μm, and 45 μm (each having a sieve diameter of 200 mm) was used. Each 50 g of the finely divided pesticide composition of Example 2 was precisely weighed and placed on the upper stage sieve (opening 212 μm) and shaken for 20 minutes. And all the fine powder which passed the lower sieve (mesh opening is 45 micrometers) was collect | recovered and weighed accurately. Subsequently, the recovered fine powder and the pesticidal active ingredient contained in the initial fine granular pesticidal composition used in the test were quantified by analysis to determine the content of each pesticidal active ingredient. Subsequently, the peeling rate of the agrochemical active ingredient was calculated by the following formula. The results are shown in Table 2.

Ａ：回収された微粉の重量（ｇ）
Ｂ：回収された微粉中の農薬活性成分含有率（％）
Ｃ：当初の微粒状農薬組成物重量（ｇ）
Ｄ：当初の微粒状農薬組成物中の農薬活性成分含有率（％）

A: Weight of collected fine powder (g)
B: Pesticide active ingredient content rate (%) in the collected fine powder
C: Initial weight of finely divided pesticide composition (g)
D: Pesticide active ingredient content rate (%) in the initial fine granular pesticide composition

  From the results of Tables 1 and 2 above, the finely divided pesticide compositions of the examples did not solidify after long-term storage, and further, the peeling of the pesticide active ingredients was reduced as compared with the comparative example conventional products. It is recognized that

  The particulate pesticide composition provided in the present invention is less likely to be peeled off from various pesticidal active ingredients and has high certainty of preventing caking during long-term storage, so that it can be anticipated at the stage prior to packaging / shipping. Therefore, it becomes possible to stably provide a particulate agricultural chemical composition with good storage stability to consumers.

Claims (12)

  A step (a) of wetting mineral fine particles with a mixed aqueous solution of a water-soluble binder and a saccharide liquid at room temperature, and a step (b) of obtaining a fine pesticide composition by coating the mineral fine particles with an agrochemical active ingredient And (c) drying the finely divided pesticide composition, and the resulting finely divided pesticide composition is placed in a packaging bag made of an airtight material, and the inside of the packaging bag is minus by gauge pressure. After sealing under reduced pressure at 27000 Pa (± 4%) and storing for 48 hours at a constant temperature of 15 ° C., the packaging bag was opened, and the total amount of the fine pesticide composition as the contents was 1.7 mm. A method for producing a fine pesticide composition having a mass percentage of 75% or more based on the total amount of the fine pesticide composition passing through the mesh when discharged on the mesh without impact .   The particulate pesticide composition according to claim 1, further comprising a step (d) of mixing a fine powder that can be used as a solid carrier of a pesticide preparation with the particulate pesticide composition before or after the step (c). Production method.   The method for producing a finely divided agrochemical composition according to claim 2, wherein at least one step (d) is performed after the step (c).   The manufacturing method of the fine-grained agricultural chemical composition in any one of Claims 1-3 whose saccharide | sugar liquefied at normal temperature is the conversion type liquid sugar containing a reducing sugar.   The manufacturing method of the fine-grained agricultural chemical composition in any one of Claims 1-4 in which an agricultural chemical active ingredient contains 1 type, or 2 or more types of agricultural chemical active components whose water solubility in 20 degreeC is 100 ppm or more.   The manufacturing method of the fine-particulate agricultural chemical composition of Claim 5 whose agricultural chemical active ingredient whose water solubility in 20 degreeC is 100 ppm or more is dinotefuran or tricyclazole.   The method for producing a fine pesticide composition according to any one of claims 1 to 6, wherein the mineral fine particles are silica sand containing 90% or more of particles having a particle size of 63 to 300 µm.   The finely divided pesticide according to any one of claims 2 to 7, which has a loss on drying of less than 4% by mass when heated at 105 ° C for 2 hours in air at normal pressure, which can be used as a solid carrier for an agrochemical formulation. A method for producing the composition.   The manufacturing method of the fine-grained agricultural chemical composition in any one of Claims 2-8 whose equilibrium water value in 25 degreeC and 70% of relative humidity of the fine powder which can be used as a solid carrier of an agricultural chemical formulation is less than 7 mass%.   The manufacturing method of the fine-grained agricultural chemical composition in any one of Claims 2-9 whose fine powder which can be used as a solid carrier of an agricultural chemical formulation is a silica.   A fine pesticide composition obtained by coating mineral fine particles with an agrochemical active ingredient, the fine pesticide composition is put in a packaging bag made of an airtight material, and the inside of the packaging bag is minus 27000 Pa in gauge pressure. (± 4%) was sealed under reduced pressure and stored at a constant temperature of 15 ° C. for 48 hours. Then, the packaging bag was opened, and the total amount of the fine pesticide composition as the contents was 1.7 mm. A fine pesticide composition in which the fine pesticide composition passing through the mesh is 75% by mass or more based on the total amount of the fine pesticide composition when discharged without impact on the mesh.   A state where a fine agricultural chemical composition formed by coating mineral fine particles with an agricultural chemical active ingredient is put in a packaging bag made of an airtight material, and the inside of the packaging bag is decompressed to minus 27000 Pa (± 4%) by a gauge pressure. After sealing for 48 hours at a constant temperature of 15 ° C., the packaging bag is opened, and the entire amount of the fine pesticide composition as the contents is subjected to an impact on a mesh having an opening of 1.7 mm. A method for evaluating the consolidation risk over time of a finely divided pesticide composition, examining whether the mass percentage of the finely divided pesticide composition passing through the mesh is 75% or more with respect to the total amount of the finely divided pesticide composition .