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    • 专利摘要:
    A granulation composition having the granulationproperties improved without being affected by the content,type or nature of a pesticidal active ingredient, and aprocess for its production, are provided. A granular composition which comprises a pesticidalactive ingredient and a highly pure quartz powder asessential components and which is obtained by anextrusion granulation method. A process for producing thegranular composition, which comprises blending apesticidal active ingredient and a highly pure quartzpowder as essential components, and granulation by anextrusion granulation method. As compared withconventional ones, the granulation properties can beimproved without being affected by the content, type andnature of the pesticidal active ingredient or theprescribed grain diameter of the granular composition.
    公开号:EP1382244A1
    申请号:EP02714570
    申请日:2002-04-09
    公开日:2004-01-21
    发明作者:Kazunori Kurita；Yuji Misumi
    申请人:Kumiai Chemical Industry Co Ltd；
    IPC主号:A01N25-00
    专利说明:
    [0001] The present invention relates to a novel granularcomposition excellent in the granulation properties. BACKGROUND ART
    [0002] A pesticide is, in many cases, formulated into adust, a granule, a wettable powder, an emulsifiableconcentrate, SC, EW or the like and then applied. Amongthem, the dust and the granule are applied as they areformulated or by means of an application machine, whilethe wettable powder, the emulsifiable concentrate, SC andEW are applied after being diluted to a prescribedconcentration mainly by water or the like.
    [0003] The dust is a powdery product formulated bypulverizing a pesticidal active ingredient or having itadsorbed on a highly oil-absorptive powder, followed bypulverization, and blending a mineral carrier such asclay and, if necessary, physical property-improvingagents, etc. Such a powdery product is applied as it isby means of an application machine, whereby there is aproblem such that the powder is likely to scatter at thetime of introducing the dust into the application machineor at the time of the application of the dust, such beingundesirable to the heath of the operator.
    [0004] Accordingly, with respect to a pesticidalformulation of the type which is applied as formulated, there has been an attempt in recent years to change it toa granule.
    [0005] The granule is one prepared by mixing a pesticidalactive ingredient, a binder and, if necessary, otheradjuvants such as a surfactant, followed by granulationinto granules, or one having a pesticidal activeingredient adsorbed or coated on grain nuclei, whereby bythe granulation, a drawback such as dusting or difficultyin dosing of a dust can be eliminated.
    [0006] The emulsifiable concentrate is, in most cases,formulated by dissolving a pesticidal active ingredientin an organic solvent and adding an emulsifier or thelike thereto. Accordingly, so long as the pesticidalactive ingredient is soluble in an organic solvent,formulation is possible. Further, the organic solvent tobe used is, in many cases, flammable and thus has apossible danger of fire, etc., and accordingly, adequatecare is required also for its handling, transportation orstorage. Further, it also has a problem of toxicity orphytotoxicity derived from the use of the organic solvent.
    [0007] On the other hand, as is different from theemulsifiable concentrate, the wettable powder isformulated by pulverizing a pesticidal active ingredientinto fine particles or having it adsorbed on a highlyoil-absorptive fine powder, followed by pulverization andblending a surfactant having dispersibility and wetductility. Accordingly, even a pesticidal active ingredient which is not soluble in an organic solvent,can be formulated, and it requires no organic solvent,whereby there will be no danger of fire or the like inits handling, transportation or storage.
    [0008] However, a conventional common wettable powder hasthe following drawbacks. Namely, it is composed of fineparticles including the pesticidal active ingredient,whereby there are problems such that it is bulky with asmall apparent specific gravity, a fine powder tends toundergo dusting at the time of dilution to prepare anapplication solution, such being undesirable to thehealth of the operator, and a dividing or dosingoperation of the formulation tends to be difficult.
    [0009] A flowable formulation such as SC or EW is aformulation having such drawbacks in dosing and dustingof the wettable powder eliminated as it is formulatedinto a suspended or emulsified formulation, but it is aliquid formulation having a relatively high viscosity,whereby it has a problem relating to discharge from acontainer, deposition of the formulation to the containeror the disposal of the used container.
    [0010] Accordingly, with respect to a formulation to beapplied as diluted with water, there has been an attemptin recent years to granulate the wettable powder. Thegranular wettable powder is one prepared by mixing apesticidal active ingredient, a surfactant and, ifnecessary, other adjuvants, followed by granulation into granules. By the granulation of the wettable powder, theproblems attributable to the drawbacks in dosing, dustingand bulkiness of the wettable powder and attributable tothe viscosity of the flowable formulation can beeliminated.
    [0011] As a granulation method for a granular compositionsuch as a granule or a granular wettable powder, anextrusion granulation method, a spray drying granulationmethod, a fluidized bed granulation method, a tumblinggranulation method, a compression granulation method, acoating granulation method, etc. may be mentioned. Amongthem, a kneading granulation method is a granulationmethod useful for both the granule and the granularwettable powder, and it is a method for granulation bymeans of an extrusion granulator while kneading by addingwater to a mixture comprising a pesticidal activeingredient and a carrier, having other adjuvants such assurfactant and a binder added, as the case requires.This method has a merit such that the granulationinstallation and operation costs are inexpensive amongvarious granulation methods. However, it has a drawbacksuch that the nature of the kneaded product issubstantially influenced by the content of the pesticidalactive ingredient, and, particularly, in the case of agranular wettable powder having a high content of thepesticidal active ingredient, the granulation abilitytends to be remarkably low.
    [0012] As a method to solve such problems, there has beenproposed a method of incorporating a surfactant andbentonite (JP-A-62-263101, JP-A-60-258101), a method ofincorporating a sulfosuccinic acid diester typesurfactant (JP-A-7-126106) or a method of incorporatingcalcium carbonate and a sulfosuccinic acid diester typesurfactant (JP-A-57-209634). However, the method ofincorporating bentonite has a drawback that the alkalinenature of the bentonite is likely to cause decompositionof the pesticidal active ingredient, whereby theapplicable range of the pesticidal active ingredient isvery limited. Further, the granulation properties ofthese conventional granular compositions were very muchinfluenced by the content, the type and the nature of thepesticidal active ingredient and did not necessary showadequate granulation properties.
    [0013] It is an object of the present invention to improvethe granulation properties of a granular compositionwithout being affected by the content, the type and thenature of the pesticidal active ingredient. DISCLOSURE OF THE INVENTION
    [0014] In summary of the present invention, the firstinvention of the present invention is an inventionrelating to a granular composition which comprises apesticidal active ingredient and a highly pure quartzpowder as essential components and which is obtained byan extrusion granulation method.
    [0015] Further, the second invention of the presentinvention is an invention relating to a process forproducing the granular composition of the above firstinvention, which comprises blending a pesticidal activeingredient and a highly pure quartz powder as essentialcomponents, and granulation by an extrusion granulationmethod.
    [0016] The present inventors have conducted a study tosolve the above-mentioned problems of conventionalgranular wettable powders and as a result, they havefound that a granular composition comprising pesticidalactive ingredient particles and a highly pure quartzpowder, preferably further containing a surfactant, iscapable of improving the granulation properties of thegranular composition without being affected by thecontent, the type and the nature of the pesticidal activeingredient, and have accomplished the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
    [0017] Now, the present invention will be described indetail.
    [0018] The pesticidal active ingredient to be used in thepresent invention may be any one so long as it is acompound commonly useful as a pesticide such as aninsecticide, a fungicide, a herbicide or a plant growthregulator, but particularly preferably a solid pesticidalactive ingredient. Further, such compounds may be usedalone or in combination of two or more types. As specific examples, the following may be mentioned, butthe active ingredient is not limited thereto. Further,their geometrical isomers and optical isomers are alsoincluded. As the names of pesticidal active ingredients,classified names disclosed in Noyakubinran 2000, compiledand published by JAPAN PLANT PROTECTION ASSOCIATION orISO names, are used as common names. For those having noclassified names or ISO names, their chemical names areused.
    [0019] Fungicides may, for example, be EDDP, IBP, TPN,isoprothiolane, ipconazole, iprodione, iminoctadinealdecyl acid salt, iminoctadine acetate, imibenconazole,oxadixyl, oxytetracycline, oxolinic acid, kasugamycin,carbendazole, chinomethionate, captan, chloroneb,diethofencarb, diclomezine, dithianon, zineb,diphenoconazole, cyproconazole, dimethirimol, ziram,streptomycin sulfate, dichlofluanid, dazomet, thiadiazin,tiabendazole, thiuram, thiophanate-methyl, tecloftalam,copper telephthalate, triadimefon, triazine, tricyclazole,triflumizole, triforine, tolclofos-methyl, coppernonylphenolsulfonate, validamycin A, bitertanol,hydroxyisoxazole, pyrazophos, pyrifenox, pyroquilon,vinclozolin, fenarimol, phthalide, blasticidin S,fluazinam, fluoroimide, flusulfamide, flutolanil,prochloraz, procymidone, propamocarb hydrochloride,propiconazole, propineb, probenazole, hexaconazole,benomyl, pefurazoate, pencycuron, benthiazole, fosetyl, a polyoxin composite, polycarbamate, formaldehyde, manzeb,maneb, myclobutanil, methasulfocarb, metalaxyl,mepanipyrim, mepronil, hydrated sulfur, live spores ofTrichoderma, copper (basic copper chloride, basic coppersulfate, cupric hydroxide or anhydrous copper sulfate),iron methane arsonate, iron ammonium methane arsonate, 8-hydroxyquinolinecopper, sulfur, zinc sulfate,acibenzolar-S-methyl, azoxystrobin, kresoxim methyl,metominostrobin, carpropamid, thifluzamide, tetraconazole,furametpyr, fludioxonil, dimethomorph, diflumetorim,cyprodinil and fenhexamide.
    [0020] Insecticides may, for example, be BPMC, BPPS, BRP,BT-produced crystal toxin, BT live spore-produced crystaltoxin, CVMP, CVP, CYAP, DDVP, DEP, DMTP, ECP, EPN, ESP,MEP, MIPC, MPP, MTMC, NAC, PAP, PHC, PMP, XMC,acrinathrin, acetamiprid, acephate, amitraz, alanycarb,allethrin, isoxathion, imidacloprid, ethiofencarb, ethion,ethylthiometon, ethofenprox, ethoprophos, oxamyl,okimelanolure, carbam, cartap hydrochloride, carbosulfan,chinomethionat, clofentezine, chloropicrin, chlorpyrifos,chlorpyrifosmethyl, chlorphenapyr, chlorfluazuron,diatomaceous earth, kelthane, cycloprothrin, cyhalothrin,cyfluthrin, cypermethrin, dimethylvinphos, dimethoate,silafluofen, sulprofos, diazinon, thiodicarb, thiocyclam,thiometon, tetradifon, tebufenozide, tebufenpyrad,tefluthrin, teflubenzuron, derris, tralomethrin, rapeseed oil, nitenpyram, vamidothion, halfenprox, bifenthrin, pyraclofos, pyridaphenthion, pyridaben, pirimicarb,pyrimidifen, pirimiphos-methyl, fipronil,phenisobromolate, fenoxycarb, fenothiocarb, fenvalerate,fenpyroximate, fenpropathrin, buprofezin, furathiocarb,flucythrinate, fluvalinate, flufenoxuron, prochloraz,prothiofos, propaphos, profenofos, hexathiazox,permethrin, bensultap, benzoepin, benzomate, benfuracarb,phosalone, fosthiazate, a polynactins composite, machineoil, malathon, methomyl, monocrotophos, resmethrin,levamisole hydrochloride, fenbutatin oxide, moranteltartarate, methyl bromide, pyrethrins, nicotine sulfate,emamectin benzoate, milbemectin spinosad, etoxazole,lufenuron, diafenthiuron, pymetrozine and acequinocyl.
    [0021] Herbicides may, for example, be 2,4-PA, ACN, CAT,CNP, DCNU, DCPA, DPA, MBPMC, MCC, MCP, MCPB, MCPP, MDBA,PAC, SAP, TCTP, ioxynil, asulam, atrazine, amiprofos-methyl,ametryn, alachlor, alloxydim, isouron, isoxaben,ammonium imazaquin, imazapyr, imazosulfuron, esprocarb,ethidimuron, etobenzanid, disodium endothal, oxadiazon,orthobencarb, karbutilate, quizalofop-ethyl, quinclorac,ammonium glyphosate, isopropylamine glyphosate, trimesiumglyphosate, glufosinate, chlomethoxynil, chlorphthalim,cyanazin, diquat, dithiopyr, siduron, cinsulfuron,cyhalofop-butyl, diphenamid, dimethametryn, simetryn,dimepiperate, cinmethylin, sethoxydim, terbacil, daimuron,dazomet, thiazafluron, tetrapion, thenylchlor,tebuthiuron, triclopyr, trifluralin, naproanilide, napropamide, nicosulfuron, paraquat, halosulfuron-methyl,bialaphos, picloram, bifenox, piperophos, pyrazoxyfen,pyrazosulfuron-ethyl, pyrazolynate, pyridate,pyributicarb, fenoxaprop-ethyl, phenothiol, phenmedipham,butachlor, butamifos, flazasulfuron, fluazifop,pretilachlor, prodiamine, propyzamide, bromacil,prometryn, bromobutide, hexazinone, beslogine,bensulfuron-methyl, benzofenap, bentazone, sodiumbentazone, thiobencarb, pendimethalin, benfuresate,methyldymron, metsulfuron-methyl, metolachlor, metribuzin,mefenacet, molinate, linuron, linuron, lenacil, sodiumchloride, cafenstrole, pyriminobac-methyl, azimsulfron,diflufenican, sodium bispyribac, cyclosulfamuron,triaziflam, pentoxazone, isopropylamine MDBA, clethodim,ethoxysulfuron, ammonium imazamox, desmedipham,pyraflufen-ethyl and indanofan.
    [0022] Plant growth regulators may, for example, be 1-naphthylacetamide,4-CPA, MCPB, ancymidol, inabenfide,indole butyric acid, uniconazole P, ethychlozate,ethephon, oxyethylene docosanol, oxine sulfate,cloxyfonac, chlormequat, chlorella extract, cholinechloride, dichlorprop, dikegulac, gibberelline, decylalcohol, pacrobutrazol, paraffin, piperonyl butoxide,flurprimidol, prohexadione-calcium, benzylaminopurine,pendimethalin, forchlorfenuron, hydradicholine maleate,hydrazide maleate, mepiquat chloride, mefluidide, wax andcalcium peroxide, but not restricted to these.
    [0023] The concentration of such pesticidal activeingredients in the granular composition is notparticularly limited. However, it is usually preferablyat most 85 wt%, particularly preferably from about 0.1 to75 wt%, more preferably from about 1 to 50 wt%, from theviewpoint of the granulation properties and bioactivities.
    [0024] In the present invention, the highly pure quartzpowder means one whereby the diffraction peaks obtainedby powder X-ray diffraction have the three strong X-raypowder diffraction values of quartz (Science Chronology,vol. 72, 1999, published on November 30, 1998, p. 731,compiled by National Astronomical Observatory, publishedby Maruzen Co., Ltd.). It is not required that nodiffraction peak other than the diffraction peaks ofquartz, is observed. However, the peak intensity ratioof (the maximum peak intensity among diffraction peaks ofother than quartz)/(the maximum peak intensity among thediffraction peaks of quartz) is not more than 0.1. It isparticularly preferably a highly pure quartz powderhaving no diffraction peak attributable to kaolinite,halloysite, pyrophyllite observed. The highly purequartz powder of the present invention preferably has avolume median diameter of from 2 to 15 µm, morepreferably from 2.5 to 10 µm. Specifically, it may, forexample, be jyunkei clay, tokuhun clay, ohira clay, ohiraDL under clay or ohira DL clay, tradename of NeoraitoKosan K.K., ohira clay, ohira DL under clay or ohira DL clay, tradename of Miyaki kogyo K.K., or ohira clay,ohira DL under clay or ohira DL clay, tradename of NipponTaika Genryo K.K.
    [0025] In the present invention, the content of the highlypure quartz powder in the granular composition maysuitably be changed depending upon the concentration ofthe active ingredient in the formulation. It is usuallyfrom 5 to 95 wt%. With a view to improving thegranulation properties, it is more preferred to add it inan amount of from about 15 to 95 wt%.
    [0026] As the surfactant to be used in the presentinvention, any of a nonionic surfactant, a cationicsurfactant and an anionic surfactant which are commonlyused in granules or granular wettable powders, may beemployed. Such surfactants may be used alone or incombination as a mixture of two or more of them. Thecontent of such surfactants in the granular compositionis usually from 0.01 to 25 wt%. Especially, with a viewto improving the granulation properties or improving thedisintegration dispersibility in water in the case of agranular wettable powder, the content is more preferablyfrom 0.1 to 15 wt%.
    [0027] The nonionic surfactant may be any nonionicsurfactant such as a polyoxyethylene alkyl ether, apolyoxyethylene alkyl phenyl ether, a polyoxyethylenepolyoxypropylene ether, a polyoxyethylene alkyl ester, apolyoxyethylene sorbitan alkyl ester, a polyoxyethylene polyoxypropylene block copolymer, a sorbitan alkyl esteror a higher fatty acid alkanolamide. Such nonionicsurfactants may be used alone or in combination as amixture of two or more of them.
    [0028] The cationic surfactant may be any one such as analkylamine salt or a quaternary ammonium salt. Suchcationic surfactants may be used alone or in combinationas a mixture of two or more of them.
    [0029] The anionic surfactant may, for example, be anaphthalenesulfonic acid polycondensate, analkenylsulfonate, a naphthalenesulfonate, a formalincondensate of a naphthalenesulfonate, a formalincondensate of an alkylnaphthalenesulfonate, a ligninsulfonate, an alkylallylsulfonate, an alkylallylsulfonate sulfate, a polystyrene sulfonate, apolycarboxylate, a polyoxyethylenealkyl ether sulfate, apolyoxyethylenealkylallyl ether sulfate, analkylsulfosuccinate, an alkyl sulfate, an alkyl ethersulfonate, or a higher fatty acid alkali salt. Suchanionic surfactants may be used alone or in combinationas a mixture of two or more of them.
    [0030] As the surfactant to be used in the presentinvention, among the above mentioned, an anionicsurfactant is preferred, and particularly, an alkylsulfate, an alkylsulfosuccinate or a polycarboxylate ispreferred.
    [0031] The composition of the present invention may further contain a binder such as carboxymethylcellulose,polyvinyl alcohol, polyvinylpyrrolidone, dextrin, starchor α-modified starch, a physical property-improvingagent such as sodium tripolyphosphate, an arginate or apolyacrylate and, if necessary, other adjuvants such as awater soluble polymer, a solvent, an absorptive finepowder, a binder, a pulverization assistant, adecomposition-preventing agent, a colorant, a defoamingagent, an effect-improving agent, a perfume or a builder.
    [0032] The composition of the present invention may containa carrier for formulation, such as a mineral carrierother than the highly pure quartz powder, a water-solublecarrier or a vegetable carrier. The mineral carrier may,for example, be diatomaceous earth, talc, clay, calciumcarbonate, acid clay, attapulgite, zeolite, sericite,sepiolite or calcium silicate. The water-soluble carriermay, for example, be ammonium sulfate, urea, dextrin,lactose, fructose, sucrose glucose, sodium chloride,Glaubers salt, sodium carbonate, sodium bicarbonate,maleic acid, citric acid, fumaric acid, malic acid orpolyethylene glycol having an average molecular weight offrom 6000 to 20000. The vegetable carrier may, forexample, be wheat flour, wood powder, starch, bran, soyflour or a pulverized product of fiber plant. Thecontent of such a carrier in the composition of thepresent invention is usually from 0.1 to 90 wt%,preferably from 0.5 to 75 wt%.
    [0033] The composition of the present invention can beproduced, for example, by the following method, but theproduction method is not limited thereto. Namely, to apesticidal active ingredient, a binder, a physicalproperty-improving agent, and the component-stabilizer,etc. are added, and if necessary, pulverized by e.g. animpact pulverizer, whereupon a highly pure quartz powderand, if necessary, a mineral powder other than the highlypure quartz powder, are mixed, water is added, and themixture is kneaded and then granulated usually by anextrusion granulator employing a screen for a particlesize of from 0.1 to 5 mm, preferably from 0.2 to 2 mm,and the granulated product is dried and sieved by asuitable screen for a predetermined grain size, to obtainthe composition of the present invention.
    [0034] Further, it is also possible that to a proper amountof water, a pesticidal active ingredient, a surfactantand if necessary, other components such as a carrier, areadded in necessary amounts, followed by pulverization bymeans of a wet type pulverizer such as a ball mill, aDyno-mill or a sand grinder. To the obtained aqueoussuspension, other components such as a surfactant, acarrier, etc., may be mixed in a suitable amount, as thecase requires, to obtain a kneaded product which can begranulated by an extrusion granulator.
    [0035] The composition of the present invention thusobtained has merits such that (1) it is excellent in the granulation properties by an extrusion granulation methodirrespective of the content, the type and the nature ofthe pesticidal active ingredient, (2) while the decreasein the granulation ability is problematic in many casesparticularly with a granular wettable powder having arelatively small screen pore size, the composition of thepresent invention is excellent in the granulationproperties irrespective of the screen pore diameter ofthe extrusion granulator, (3) it is excellent in thegranulation properties and has a wide margin for theaddition of water to facilitate the grain size adjustment,(4) the surface of the granulated product is smooth, thusminimizing powdering due to abrasion of the grains to oneanother, and (5) in the case of a granular wettablepowder, it is excellent in the disintegrationdispersibility in water. Thus, it can widely be employedas a pesticide such as a fungicide, an insecticide, aherbicide or a plant growth regulator. EXAMPLES
    [0036] Now, the present invention will be described infurther detail with reference to Examples, ComparativeExamples and Test Examples of the present invention.However, the present invention is by no means restrictedthereto. Further, "parts" means "parts by weight".
    [0037] Further, kneading in Examples and ComparativeExamples was carried out by a desk top twin screw kneader(manufactured by IKEDARIKA Inc.), and extrusion granulation was carried out by RG-5M (extrusiongranulator, manufactured by Kikusui Seisakusho Ltd.).Further, the highly pure quartz powder used in Examples 1to 11 was one corresponding to such that the diffractionpeaks obtained by powder X-ray diffraction have threestrong X-ray powder diffraction values of quartz(disclosed in the above-mentioned Science Chronology,compiled by National Astronomical Observatory, and thediffraction peak intensity ratio of (the maximum peakintensity among diffraction peaks of other thanquartz)/(the maximum peak intensity among the diffractionpeaks of quartz) was not more than 0.1. Further, nodiffraction peak attributable to kaolinite, halloysite,pyrophyllite, was observed. EXAMPLE 1
    [0038] 4 Parts of BPMC heated and melted at 60°C andadsorbed on 5 parts of white carbon, 3.5 parts of cartaphydrochloride, 2 parts of polyvinyl alcohol and 85.5parts of a highly pure quartz powder (volume mediandiameter: 7.2 µm) were pulverized by an impact pulverizerand then put into a desk top twin screw kneader(manufactured by IKEDARIKA Inc.), and about 15% ofdistilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui SeisakushoLtd.) having a screen with a pore size of 1.0 mm mounted.After drying at 60°C, the grain size was adjusted by a screen of from 12 to 24 mesh to obtain a granule. EXAMPLE 2
    [0039] 4 Parts of BPMC heated and melted at 60°C andadsorbed on 5 parts of white carbon, 3.5 parts of cartaphydrochloride, 0.5 part of sodium alkylsulfate (NewCalgen WG-6, tradename of Takemoto Oil & Fat Co., Ltd.),2 parts of polyvinyl alcohol and 85 parts of a highlypure quartz powder (volume median diameter: 7.2 µm) werepulverized by an impact pulverizer and then put into adesk top twin screw kneader (manufactured by IKEDARIKAInc.), and about 15% of distilled water was added,followed by kneading for 5 minutes and then bygranulation by means of an extrusion granulator (RG-5M,manufactured by Kikusui Seisakusho Ltd.) having a screenhaving a pore diameter of 1.2 mm mounted. After dryingat 60°C, the grain size was adjusted by a screen of from12 to 24 mesh to obtain a granule. EXAMPLE 3
    [0040] 16 Parts of BPMC heated and melted at 60°C andadsorbed on 15 parts of white carbon, 14 parts of cartaphydrochloride, 2 parts of α-modified starch and 53 partsof a highly pure quartz powder (volume median diameter:7.2 µm) were pulverized by an impact pulverizer and then,put into a desk top twin screw kneader (manufactured byIKEDARIKA Inc.), and about 20% of distilled water wasadded, followed by kneading for 5 minutes and then bygranulation by means of an extrusion granulator (RG-5M, manufactured by Kikusui Seisakusho Ltd.) having a screenhaving a pore size of 1.0 mm mounted. After drying at60°C, the grain size was adjusted by a screen of from 12to 24 mesh to obtain a granule. EXAMPLE 4
    [0041] 16 Parts of BPMC heated and melted at 60°C andadsorbed on 15 parts of white carbon, 14 parts of cartaphydrochloride, 2 parts of α-modified starch and 53 partsof a highly pure quartz powder (volume median diameter:7.2 µm) were pulverized by an impact pulverizer and then,put into a desk top twin screw kneader (manufactured byIKEDARIKA Inc.), and about 20% of distilled watercontaining 0.5 part of sodium dioctylsulfosuccinate, wasadded, followed by kneading for 5 minutes and then bygranulation by means of an extrusion granulator (RG-5M,manufactured by Kikusui Seisakusho Ltd.) having a screenhaving a pore size of 1.2 mm mounted. After drying at60°C, the grain size was adjusted by a screen of from 12to 24 mesh to obtain a granule. EXAMPLE 5
    [0042] 3 Parts of PHC, 1.5 parts of carboxymethylcellulose,2 parts of white carbon and 93.5 parts of a highly purequartz powder (volume median diameter: 8.8 µm) werepulverized by an impact pulverizer and then put into adesk top twin screw kneader (manufactured by IKEDARIKAInc.), and about 15% of distilled water was added,followed by kneading for 5 minutes and then by granulation by means of an extrusion granulator (RG-5M,manufactured by Kikusui Seisakusho Ltd.) having a screenhaving a pore size of 1.0 mm mounted. After drying at60°C, the grain size was adjusted by a screen of from 12to 24 mesh to obtain a granule. EXAMPLE 6
    [0043] 4 Parts of cartap hydrochloride, 1.5 parts ofcarboxymethylcellulose, 5 parts of diatomaceous earth and89.5 parts of a highly pure quartz powder (volume mediandiameter: 8.8 µm) were pulverized by an impact pulverizerand then put into a desk top twin screw kneader(manufactured by IKEDARIKA Inc.), and about 15% ofdistilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui SeisakushoLtd.) having a screen having a pore size of 0.8 mmmounted. After drying at 60°C, the grain size wasadjusted by a screen of from 12 to 24 mesh to obtain agranule. EXAMPLE 7
    [0044] 96.2 Parts of mepronil and 3.8 parts of white carbonwere uniformly mixed and then finely pulverized by a Jet-O-mizerto obtain a mepronil premix. 78 Parts of thismepronil premix, 2 parts of sodium alkylsulfate (NewCalgen WG-6, tradename of Takemoto Oil & Fat Co., Ltd.),6 parts of sodium alkylnaphthalenesulfonate (New CalgenWG-1, tradename of Takemoto Oil & Fat Co., Ltd.), 3 parts of calcium lignin sulfonate and 11 parts of a highly purequartz powder (volume median diameter: 5.5 µm) werepulverized by an impact pulverizer and then put into adesk top twin screw kneader (manufactured by IKEDARIKAInc.), and about 15% of distilled water was added,followed by kneading for 5 minutes and then bygranulation by means of an extrusion granulator (RG-5M,manufactured by Kikusui Seisakusho Ltd.) having a screenhaving a pore size of 0.6 mm mounted. After drying at50°C, the grain size was adjusted by a screen of from 16to 48 mesh to obtain a granular wettable powder. EXAMPLE 8
    [0045] 94.4 Parts of mepanipyrim and 5.6 parts of whitecarbon were uniformly mixed and then finely pulverized bya Jet-O-mizer to obtain a mepanipyrim premix. 53 Partsof this mepanipyrim premix, 2 parts of sodiumalkylsulfate (New Calgen WG-6, tradename of Takemoto Oil& Fat Co., Ltd.), 5 parts of sodiumalkylnaphthalenesulfonate (New Calgen WG-1, tradename ofTakemoto Oil & Fat Co., Ltd.), 2 parts of calcium ligninsulfonate and 38 parts of a highly pure quartz powder(volume median diameter: 5.5 µm) were pulverized by animpact pulverizer and then put into a desk top twin screwkneader (manufactured by IKEDARIKA Inc.), and about 15%of distilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui Seisakusho Ltd.) having a screen having a pore size of 0.6 mmmounted. After drying at 50°C, the grain size wasadjusted by a screen of from 16 to 48 mesh to obtain agranular wettable powder. EXAMPLE 9
    [0046] 96.8 Parts of tricyclazole and 3.2 parts of whitecarbon were uniformly mixed and then finely pulverized bya Jet-O-mizer to obtain a tricyclazole premix. 77.5Parts of this tricyclazole premix, 2 parts of sodiumalkylsulfate (New Calgen WG-6, tradename of Takemoto Oil& Fat Co., Ltd.), 9 parts of a formalin condensate ofsodium alkylnaphthalenesulfonate (Demol MS, tradename ofKao Corporation), 5 parts of potassium chloride and 6.5parts of a highly pure quartz powder (volume mediandiameter: 5.5 µm) were pulverized by an impact pulverizerand then put into a desk top twin screw kneader(manufactured by IKEDARIKA Inc.), and about 15% ofdistilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui SeisakushoLtd.) having a screen having a pore size of 0.6 mmmounted. After drying at 50°C, the grain size wasadjusted by a screen of from 16 to 48 mesh to obtain agranular wettable powder. EXAMPLE 10
    [0047] 1 Part of prohexadione-calcium, 1 part of whitecarbon, 2 parts of sodium alkylsulfate (New Calgen WG-6, tradename of Takemoto Oil & Fat Co., Ltd.), 6 parts of apolycarboxylate (New Calgen WG-5, tradename of TakemotoOil & Fat Co., Ltd.) and 90 parts of a highly pure quartzpowder (volume median diameter: 4.1 µm) were pulverizedby an impact pulverizer and then put into a desk top twinscrew kneader (manufactured by IKEDARIKA Inc.), and about15% of distilled water was added, followed by kneadingfor 5 minutes and then by granulation by means of anextrusion granulator (RG-5M, manufactured by KikusuiSeisakusho Ltd.) having a screen having a pore size of0.6 mm mounted. After drying at 50°C, the grain size wasadjusted by a screen of from 16 to 48 mesh to obtain agranular wettable powder. EXAMPLE 11
    [0048] 5 Parts of a bispyribac-sodium, 1 part of whitecarbon, 2 parts of sodium alkylsulfate (New Calgen WG-6,tradename of Takemoto Oil & Fat Co., Ltd.), 6 parts of aformalin condensate of sodium alkylnaphthalenesulfonate(Demol MS, tradename of Kao Corporation) and 86 parts ofa high pure quartz powder (volume median diameter: 4.1µm) were pulverized by an impact pulverizer and then putinto a desk top twin screw kneader (manufactured byIKEDARIKA Inc.), and about 15% of distilled water wasadded, followed by kneading for 5 minutes and then bygranulation by means of an extrusion granulator (RG-5M,manufactured by Kikusui Seisakusho Ltd.) having a screenhaving a pore size of 0.6 mm mounted. After drying at 50°C, the grain size was adjusted by a screen of from 16to 48 mesh to obtain a granular wettable powder. COMPARATIVE EXAMPLE 1
    [0049] 4 Parts of BPMC heated and melted at 60°C andadsorbed on 5 parts of white carbon, 3.5 parts of cartaphydrochloride, 2 parts of polyvinyl alcohol and 85.5parts of a clay (volume media diameter: 7.3 µm, by thepowder X-ray diffraction, it was identified to be amixture of kaolinite, halloysite, pyrophyllite and quartz,and the diffraction peak intensity ratio of (the maximumpeak intensity among diffraction peaks of other thanquartz)/(the maximum peak intensity among the diffractionpeaks of quartz) was 0.50), were pulverized by an impactpulverizer and then put into a desk top twin screwkneader (manufactured by IKEDARIKA Inc.), and about 15%of distilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui SeisakushoLtd.) having a screen having a pore size of 1.0 mmmounted. After drying at 60°C, the grain size wasadjusted by a screen of from 12 to 24 mesh to obtain agranule. COMPARATIVE EXAMPLE 2
    [0050] 16 Parts of BPMC heated and melted at 60°C andadsorbed on 15 parts of white carbon, 14 parts of cartaphydrochloride, 2 parts of α-modified starch and 53 partsof a clay (volume media diameter: 7.3 µm, by the powder X-ray diffraction, it was identified to be a mixture ofkaolinite, halloysite, pyrophyllite and quartz, and thediffraction peak intensity ratio of (the maximum peakintensity among diffraction peaks of other thanquartz)/(the maximum peak intensity among the diffractionpeaks of quartz) was 0.50), were pulverized by an impactpulverizer and then put into a desk top twin screwkneader (manufactured by IKEDARIKA Inc.), and about 20%of distilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui SeisakushoLtd.) having a screen having a pore size of 1.0 mmmounted. After drying at 60°C, the grain size wasadjusted by a screen of from 12 to 24 mesh to obtain agranule. COMPARATIVE EXAMPLE 3
    [0051] 3 Parts of PHC, 1.5 parts of carboxymethylcellulose,2 parts white carbon and 93 parts of calcium carbonate(volume media diameter: 6.5 µm) were pulverized by animpact pulverizer and then put into a desk top twin screwkneader (manufactured by IKEDARIKA Inc.), and about 15%of distilled water containing 0.5 part of sodiumdioctylsulfosuccinate, was added, followed by kneadingfor 5 minutes and then by granulation by means of anextrusion granulator (RG-5M, manufactured by KikusuiSeisakusho Ltd.) having a screen having a pore size of1.0 mm mounted. After drying at 60°C, the grain size was adjusted by a screen of from 12 to 24 mesh to obtain agranule. COMPARATIVE EXAMPLE 4
    [0052] 4 Parts cartap hydrochloride, 1.5 parts ofcarboxymethylcellulose, 5 parts of diatomaceous earth and89.5 parts of a clay (volume media diameter: 7.3 µm, bythe powder X-ray diffraction, it was identified to be amixture of kaolinite, halloysite, pyrophyllite and quartz,and the diffraction peak intensity ratio of (the maximumpeak intensity among diffraction peaks of other thanquartz)/(the maximum peak intensity among the diffractionpeaks of quartz) was 0.50), were pulverized by an impactpulverizer and then put into a desk top twin screwkneader (manufactured by IKEDARIKA Inc.), and about 15%of distilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui SeisakushoLtd.) having a screen having a pore size of 0.8 mmmounted. After drying at 60°C, the grain size wasadjusted by a screen of from 12 to 24 mesh to obtain agranule. COMPARATIVE EXAMPLE 5
    [0053] 96.2 Parts of mepronil and 3.8 parts of white carbonwere uniformly mixed and then finely pulverized by a Jet-O-mizerto obtain a mepronil premix. 78 Parts of thismepronil premix, 2 parts of sodium alkylsulfate (NewCalgen WG-6, tradename of Takemoto Oil & Fat Co., Ltd.), 6 parts of sodium alkylnaphthalenesulfonate (New CalgenWG-1, tradename of Takemoto Oil & Fat Co., Ltd.), 3 partsof calcium lignin sulfonate and 11 parts of a clay(volume median diameter: 7.3 µm) by the powder X-raydiffraction, it was identified to be a mixture ofkaolinite, halloysite, pyrophyllite and quartz, and thediffraction peak intensity ratio of (the maximum peakintensity among diffraction peaks of other thanquartz)/(the maximum peak intensity among the diffractionpeaks of quartz) was 0.50) were pulverized by an impactpulverizer and then put into a desk top twin screwkneader (manufactured by IKEDARIKA Inc.), and about 15%of distilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui SeisakushoLtd.) having a screen haying a pore size of 0.6 mmmounted. After drying at 50°C, the grain size wasadjusted by a screen of from 16 to 48 mesh to obtain agranular wettable powder. COMPARATIVE EXAMPLE 6
    [0054] 94.4 Parts of mepanipyrim and 5.6 parts of whitecarbon were uniformly mixed and then finely pulverized bya Jet-O-mizer to obtain a mepanipyrim premix. 53 Partsof this mepanipyrim premix, 2 parts of sodiumalkylsulfate (New Calgen WG-6, tradename of Takemoto Oil& Fat Co., Ltd.), 5 parts of sodiumalkylnaphthalenesulfonate (New Calgen WG-1, tradename of Takemoto Oil & Fat Co., Ltd.), 2 parts of calcium ligninsulfonate and 37 parts of calcium carbonate (volumemedian diameter: 6.5 µm) were pulverized by an impactpulverizer and then put into a desk top twin screwkneader (manufactured by IKEDARIKA Inc.), and about 15%of distilled water containing 1 part of sodiumdioctylsulfosuccinate was added, followed by kneading for5 minutes and then by granulation by means of anextrusion granulator (RG-5M, manufactured by KikusuiSeisakusho Ltd.) having a screen having a pore size of0.6 mm mounted. After drying at 50°C, the grain size wasadjusted by a screen of from 16 to 48 mesh to obtain agranular wettable powder. COMPARATIVE EXAMPLE 7
    [0055] 96.8 Parts of tricyclazole and 3.2 parts of whitecarbon were uniformly mixed and then finely pulverized bya Jet-O-mizer to obtain a tricyclazole premix. 77.5Parts of this tricyclazole premix, 2 parts of sodiumalkylsulfate (New Calgen WG-6, tradename of Takemoto Oil& Fat Co., Ltd.), 9 parts of a formalin condensate ofsodium alkylnaphthalenesulfonate (Demol MS, tradename ofKao Corporation), 5 parts of potassium chloride and 6.5parts of a clay (volume median diameter: 4.5 µm, by thepowder X-ray diffraction, it was identified to be amixture of kaolinite, halloysite, pyrophyllite and quartz,and the diffraction peak intensity ratio of (the maximumpeak intensity among diffraction peaks of other than quartz)/(the maximum peak intensity among the diffractionpeaks of quartz) was 0.50) were pulverized by an impactpulverizer and then put into a desk top twin screwkneader (manufactured by IKEDARIKA Inc.), and about 15%of distilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui SeisakushoLtd.) having a screen having a pore size of 0.6 mmmounted. After drying at 50°C, the grain size wasadjusted by a screen of from 16 to 48 mesh to obtain agranular wettable powder. COMPARATIVE EXAMPLE 8
    [0056] 1 Part of prohexadione-calcium, 1 part of whitecarbon, 2 parts of sodium alkylsulfate (New Calgen WG-6,tradename of Takemoto Oil & Fat Co., Ltd.), 6 parts of apolycarboxylate (New Calgen WG-5, tradename of TakemotoOil & Fat Co., Ltd.) and 90 parts of calcium carbonate(volume median diameter: 6.5 µm) were pulverized by animpact pulverizer and then put into a desk top twin screwkneader (manufactured by IKEDARIKA Inc.), and about 15%of distilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui SeisakushoLtd.) having a screen having a pore size of 0.6 mmmounted. After drying at 50°C, the grain size wasadjusted by a screen of from 16 to 48 mesh to obtain agranular wettable powder. COMPARATIVE EXAMPLE 9
    [0057] 1 Part of prohexadione-calcium, 1 part of whitecarbon, 2 parts of sodium alkylsulfate (New Calgen WG-6,tradename of Takemoto Oil & Fat Co., Ltd.), 6 parts of apolycarboxylate (New Calgen WG-5, tradename of TakemotoOil & Fat Co., Ltd.) and 90 parts of a clay (volumemedian diameter: 2.2 µm) by the powder X-ray diffraction,it was identified to be a mixture of kaolinite,halloysite, pyrophyllite and quartz, and the diffractionpeak intensity ratio of (the maximum peak intensity amongdiffraction peaks of other than quartz)/(the maximum peakintensity among the diffraction peaks of quartz) was 0.17were pulverized by an impact pulverizer and then put intoa desk top twin screw kneader (manufactured by IKEDARIKAInc.), and about 15% of distilled water was added,followed by kneading for 5 minutes and then bygranulation by means of an extrusion granulator (RG-5M,manufactured by Kikusui Seisakusho Ltd.) having a screenhaving a pore size of 0.6 mm mounted. After drying at50°C, the grain size was adjusted by a screen of from 16to 48 mesh to obtain a granular wettable powder. COMPARATIVE EXAMPLE 10
    [0058] 1 Part of prohexadione-calcium, 1 part of whitecarbon, 2 parts of sodium alkylsulfate (New Calgen WG-6,tradename of Takemoto Oil & Fat Co., Ltd.), 6 parts of apolycarboxylate (New Calgen WG-5, tradename of TakemotoOil & Fat Co., Ltd.) and 90 parts of a clay (volume median diameter: 17.4 µm) by the powder X-ray diffraction,it was identified to be a mixture of kaolinite,halloysite, pyrophyllite and quartz, and the diffractionpeak intensity ratio of (the maximum peak intensity amongdiffraction peaks of other than quartz)/(the maximum peakintensity among the diffraction peaks of quartz) was 0.50were pulverized by an impact pulverizer and then put intoa desk top twin screw kneader (manufactured by IKEDARIKAInc.), and about 15% of distilled water was added,followed by kneading for 5 minutes and then bygranulation by means of an extrusion granulator (RG-5M,manufactured by Kikusui Seisakusho Ltd.) having a screenhaving a pore size of 0.6 mm mounted. After drying at50°C, the grain size was adjusted by a screen of from 16to 48 mesh to obtain a granular wettable powder. COMPARATIVE EXAMPLE 11
    [0059] 5 Parts of a bispyribac-sodium, 1 part of whitecarbon, 2 parts of sodium alkylsulfate (New Calgen WG-6,tradename of Takemoto Oil & Fat Co., Ltd.), 6 parts of aformalin condensate of sodium alkylnaphthalenesulfonate(Demol MS, tradename of Kao Corporation) and 86 parts ofa clay (volume median diameter: 4.5 µm), by the powder X-raydiffraction, it was identified to be a mixture ofkaolinite, halloysite, pyrophyllite and quartz, and thediffraction peak intensity ratio of (the maximum peakintensity among diffraction peaks of other thanquartz)/(the maximum peak intensity among the diffraction peaks of quartz) was 0.50) were pulverized by an impactpulverizer and then put into a desk top twin screwkneader (manufactured by IKEDARIKA Inc.), and about 15%of distilled water was added, followed by kneading for 5minutes and then by granulation by means of an extrusiongranulator (RG-5M, manufactured by Kikusui SeisakushoLtd.) having a screen having a pore size of 0.6 mmmounted. After drying at 50°C, the grain size wasadjusted by a screen of from 16 to 48 mesh to obtain agranular wettable powder. TEST EXAMPLE 1
    [0060] About 500 g of a kneaded product obtained by thedesk top twin screw kneader (manufactured by IKEDARIKAInc.) in accordance with each Example or ComparativeExample, was subjected to granulation operation for 4minutes by means of an extrusion granulator RG-5M(manufactured by Kikusui Seisakusho Ltd.), whereby theweight of granules granulated in 2 minutes were measured,and the granulation property was evaluated by the weightof granules per 1 minute. Tested pesticide Weight of granules (g/min) Tested pesticide Weight of granules (g/min) Example 1 78 Comparative Example 1 48 Example 2 86 Comparative Example 2 41 Example 3 73 Comparative Example 3 50 Example 4 83 Comparative Example 4 47 Example 5 106 Comparative Example 5 28 Example 6 96 Comparative Example 6 33 Example 7 65 Comparative Example 7 29 Example 8 77 Comparative Example 8 38 Example 9 67 Comparative Example 9 19 Example 10 89 Comparative Example 10 10 Example 11 88 Comparative Example 11 35 TEST EXAMPLE 2
    [0061] With respect to a sample immediately after thepreparation of the formulation obtained in each Exampleor Comparative Example, the disintegration dispersibilityin water and suspensibility were measured by thefollowing methods. In a constant temperature water tankof 25°C, a 250 ml cylinder having a stopper andcontaining 125 ml of three degree hard water, was set.250 mg of each granular wettable powder was put into thecylinder, and falling/restoring of the cylinder wasrepeated once every 2 seconds, and the number offalling/restoring times until the granular wettable powder became completely disintegrated and dispersed, wastaken as the disintegration dispersibility in water.Then, this cylinder was left to stand still in a constanttemperature water tank of 25°C, and upon expiration of 15minutes, 25 ml was sampled from the center portion of thecylinder, whereupon water was evaporated, and then thepesticidal active ingredient was analyzed by highperformance liquid chromatography, and the suspensibilitywas obtained.
    [0062] The suspensibility is obtained by the followingformula.Suspensibility (%)=[(B × 10)/A] × 100 A: The amount of the active ingredient in theinitial sample (the sample immediately after thepreparation) B: The amount of the active ingredient in thesampled liquid. Tested pesticide Disintegration dispersibility in water (times) Suspensibility (%) Example 7 5 98.6 Example 8 5 99.1 Example 9 4 97.3 Example 10 5 92.4 Comparative Example 5 9 81.7 Comparative Example 6 10 83.7 Comparative Example 7 9 85.1 Comparative Example 8 10 80.2
    [0063] With the granular composition of the presentinvention, the granulation properties can be improvedwithout being affected by the content, type or nature ofthe pesticidal active ingredient or by the prescribedgrain size of the granular composition.
    权利要求:
    Claims (10)
    [1] A granular composition which comprises a pesticidalactive ingredient and a highly pure quartz powder asessential components and which is obtained by anextrusion granulation method.
    [2] The granular composition according to Claim 1,wherein the highly pure quartz powder has a volume mediandiameter of from 2 to 15 µm and a purity such that in theX-ray diffraction, (the maximum peak intensity amongdiffraction peaks of other than quartz)/(the maximum peakintensity among the diffraction peaks of quartz) is notmore than 0.1.
    [3] The granular composition according to Claim 1 or 2,wherein the pesticidal active ingredient is in an amountof from 0.1 to 75 wt% and the highly pure quartz powderis in an amount of from 5 to 95 wt%, in the granularcomposition.
    [4] The granular composition according to Claim 1, 2 or3, which further contains a surfactant.
    [5] The granular composition according to Claim 4,wherein the surfactant is an anionic surfactant.
    [6] The granular composition according to Claim 4 or 5,wherein the surfactant is at least one surfactantselected from the group consisting of alkyl sulfates,alkyl sulfosuccinates and polycarboxylates.
    [7] The granular composition according to any one ofClaims 1 to 6, wherein the granular composition has a grain diameter of from 0.1 to 5 mm.
    [8] The granular composition according to any one ofClaims 1 to 7, wherein the granular composition is apesticidal granule.
    [9] The granular composition according to any one ofClaims 1 to 7, wherein the granular composition is apesticidal water dispersible granule.
    [10] A process for producing the granular composition asdefined in Claim 1, which comprises blending a pesticidalactive ingredient and a highly pure quartz powder asessential components, and granulation by an extrusiongranulation method.
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    同族专利:
    公开号 | 公开日
    CN1258977C|2006-06-14|
    BR0209115B1|2013-12-03|
    BR0209115A|2004-07-13|
    EP1382244A4|2004-05-19|
    JP2002322003A|2002-11-08|
    WO2002087324A1|2002-11-07|
    JP4707254B2|2011-06-22|
    DE60225262T2|2008-06-19|
    DE60225262D1|2008-04-10|
    US20050100562A1|2005-05-12|
    AT387089T|2008-03-15|
    KR20040015119A|2004-02-18|
    KR100831028B1|2008-05-21|
    IL158501D0|2004-05-12|
    EP1382244B1|2008-02-27|
    CN1505476A|2004-06-16|
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    JP2001125190A|JP4707254B2|2001-04-24|2001-04-24|Granular composition and method for producing the same|
    JP2001125190||2001-04-24||
    PCT/JP2002/003556|WO2002087324A1|2001-04-24|2002-04-09|Granular compositions and process for producing the same|
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