WO2010023863A1 - Granular wettable powder - Google Patents

Granular wettable powder Download PDF

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Publication number
WO2010023863A1
WO2010023863A1 PCT/JP2009/004055 JP2009004055W WO2010023863A1 WO 2010023863 A1 WO2010023863 A1 WO 2010023863A1 JP 2009004055 W JP2009004055 W JP 2009004055W WO 2010023863 A1 WO2010023863 A1 WO 2010023863A1
Authority
WO
WIPO (PCT)
Prior art keywords
wettable powder
white carbon
active ingredient
water
melting point
Prior art date
Application number
PCT/JP2009/004055
Other languages
French (fr)
Japanese (ja)
Inventor
中村喜朗
岡田恵理子
Original Assignee
日本曹達株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本曹達株式会社 filed Critical 日本曹達株式会社
Priority to JP2010526528A priority Critical patent/JP5285074B2/en
Priority to KR1020117004131A priority patent/KR101303548B1/en
Priority to CN200980133210.5A priority patent/CN102131388B/en
Publication of WO2010023863A1 publication Critical patent/WO2010023863A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A01N25/14—Powders or granules wettable
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof

Definitions

  • the present invention relates to a granular wettable powder which is excellent in disintegration and dispersibility in water even after being stored at high temperature.
  • Granule wettable powders are increasing in demand because of their ease of use, safety, and space saving during transportation. Has been done.
  • Granule wettable powders are usually obtained by adding and mixing auxiliary agents such as wetting agents, dispersants, binders, and bulking agents to the active ingredients of agricultural chemicals (agrochemical ingredients) and granulating them into granules. can get.
  • Granule wettable powder is usually used after diluting and suspending with water about 10 to 10,000 times.
  • Granule wettable powders are required to disintegrate and disperse quickly after being added to water, and various proposals have been made to improve disintegration and dispersibility. If it is inferior in disintegration or dispersibility, the active ingredients of agricultural chemicals are separated in water, causing uneven spraying, which may cause phytotoxicity to crops.
  • Non-patent Document 1 a method of mixing the agrochemical active ingredient with a large amount of an inactive substance to prepare a formulation and a method of adsorbing a solution of the agrochemical active ingredient on a carrier to prepare the formulation.
  • an agrochemical active ingredient that is liquid at normal temperature, a saccharide, a fired product of wet-process silica, a granule hydrate obtained by mixing and granulating bentonite and an anionic surfactant (Patent Document 1), melting point 70 A granulated wettable powder obtained by granulating a baked product of a wet process silica and an anionic surfactant to an agrochemical active ingredient at a temperature of °C or less, and further adding a solvent and a water-soluble carrier has been proposed (patent) Reference 2).
  • the granule wettable powders proposed in these show good disintegration and dispersibility when put into water immediately after granulation or after low-temperature storage. However, after being exposed to high temperatures for a long time, such as when stored in a warehouse without temperature control equipment, disintegration and dispersibility will decrease, causing the active ingredients of agricultural chemicals to separate in water, resulting in dispersion unevenness. was there.
  • Granule hydration obtained by granulating a mixture of an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less, an N-acylamino acid salt as a dispersant, and an adsorbent as an improved disintegration and dispersibility An agent has been proposed (Patent Document 3). However, since there are countries that regulate the use of N-acylamino acid salts, the granule dispersant cannot be used in the regulated countries.
  • An object of the present invention is a granule wettable powder containing an agrochemical active ingredient having a melting point or a softening point of 70 ° C. or less, which is excellent in disintegration and dispersibility in water and suppressed phytotoxicity even after being stored at a high temperature. Is to provide.
  • the inventor obtained a premix preparation by mixing an active ingredient of agricultural chemicals having a melting point or softening point of 70 ° C. or less and acidic white carbon, and then the premix preparation and the base By mixing and granulating a reactive white carbon, a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less, it is excellent in disintegration and dispersibility in water and has no phytotoxicity even after storage at high temperature. It has been found that an inhibited granular wettable powder is obtained. The present invention has been completed by further studies based on this finding.
  • the present invention is a granular wettable powder containing an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less, acidic white carbon, basic white carbon, a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less.
  • the saccharide is preferably at least one selected from the group consisting of glucose, sorbitol, lactose, sucrose and maltose.
  • the said pesticidal active ingredient is iminotadine albesylate.
  • the present invention also provides a premix preparation by mixing an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less and acidic white carbon, the premix preparation, basic white carbon, and a polycarboxylic acid surfactant. And a saccharide having a molecular weight of 400 or less, and granulating the resulting mixture.
  • the granule wettable powder of the present invention is excellent in disintegration and dispersibility in water even after being stored at high temperature. That is, disintegration and dispersibility do not deteriorate even after being exposed to a high temperature for a long time due to storage in a warehouse without temperature control equipment. Moreover, since it is excellent in the disintegration property and dispersibility in water, an agricultural chemical active ingredient is hard to isolate
  • the granule wettable powder of the present invention is suitable as an agricultural and horticultural agricultural chemical.
  • the granule wettable powder of the present invention contains an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less, acidic white carbon, basic white carbon, a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less. is there.
  • the agrochemical active ingredient used for the granule wettable powder of the present invention has a melting point or softening point of 70 ° C. or less.
  • compounds generally used as agrochemicals such as bactericides, insecticides, acaricides, plant growth regulators, herbicides, fungicides, fungicides, fungicides, and algaecides can be used. . These compounds can be used alone or in admixture of two or more.
  • agrochemical active ingredient having a melting point of 70 ° C. or less for example, 2- (1,2-dimethylpropylamino) -4-ethylamino-6-methylthio-1,3,5-triazine (generic name: dimetamethrin, melting point: 65 ° C), S, S-dimethyl-2- (difluoromethyl) -4-isobutyl-6- (trifluoromethyl) -3,5-pyridinedicarbothionate (generic name: dithiopyr, melting point: 65 ° C), 2 , 3-Dihydro-3,3-dimethylbenzofuran-5-ylethanesulfonate (generic name: benfrate, melting point: 32-35 ° C.), butyl (R) -2- [4- (4-cyano-2-fluoro Phenoxy) phenoxy] propionate (generic name: cihalohop butyl, melting point: 50 ° C
  • active agricultural chemicals that are liquid at room temperature
  • active agricultural chemicals include, for example, 2-chloro-2 ′, 6′-diethyl-N- (2-propoxyethyl) -acetanilide (generic name: pretilachlor), S-benzyl-N— ( 1,2-dimethylpropyl) -N-ethylthiocarbamate (generic name: Esprocarb).
  • an agrochemical active ingredient having a softening point of 70 ° C.
  • 1,1′-iminodi octamethylene
  • diguanidinium tris alkylbenzenesulfonate
  • iminoctadine albecyl salt softening point: 55 to 60 ° C.
  • Etc aric name: iminoctadine albecyl salt, softening point: 55 to 60 ° C.
  • iminotadine albesylate is suitable for the granular wettable powder of the present invention.
  • the granule wettable powder of the present invention may contain an agrochemical active ingredient having a melting point and a softening point exceeding 70 ° C.
  • an agrochemical active ingredient compounds generally used as agrochemicals such as bactericides, insecticides, acaricides, plant growth regulators, herbicides, fungicides, fungicides, fungicides, and algaecides can be used. . These compounds can be used alone or in admixture of two or more.
  • Pesticide active ingredients having a melting point and softening point exceeding 70 ° C. include, for example, 2-isopropylphenyl-N-methylcarbamate (generic name: MIPC, melting point: 88-93 ° C.), 3,5-xylyl-N-methyl Carbamate (generic name: XMC, melting point: 99-100 ° C.), 3- (4-tert-butyl-2-ethoxyphenyl) -2- (2,6-difluorophenyl) -4,5-dihydrooxazole (general Name: etoxazole, melting point: 101-102 ° C.), O-3-tert-butylphenyl-6-methoxy-2-pyridyl (methyl) thiocarbamate (generic name: pyributicalbu, melting point: 85.7-86.2 ° C.) ), 5- (2,4-dichlorophenoxy) -2-nitromethylbenzoate (generic name: biphenox
  • bis (dimethylthiocarbamoyl) disulfide (generic name: thiuram, melting point: 155 ⁇ 156 ° C.), N- (2,3-dichloro-4-hydroxyphenyl) -1-methylcyclohexanecarboxamide (generic name: phenhexamide, melting point: 153 ° C.), zinc ion coordinated Manganese ethylene bisdithiocarbamate (Generic name: mancozeb, melting point: 192 ° C.
  • the active ingredient of agricultural chemicals having a melting point or softening point of 70 ° C. or less is 0.1 to 50% by mass with respect to the entire granular wettable powder.
  • the amount of the pesticidal active ingredient whose melting point or softening point exceeds 70 ° C. is usually 10% by mass or less, preferably 5% by mass or less, based on the entire pesticidal active ingredient.
  • the acidic white carbon used in the granular wettable powder of the present invention has a pH of usually 6 to 7, preferably 6 to 7.5 in a 1% suspension of amorphous silicon dioxide powder.
  • Acidic white carbon has an average particle diameter d 50 determined by laser diffraction of usually 1 to 500 ⁇ m, preferably 10 to 100 ⁇ m. The particle size can be adjusted by pulverization or the like.
  • Examples of commercial products of acidic white carbon include Carplex # 80 (trade name / manufactured by DSL Japan), Carplex XR (trade name / manufactured by DSL Japan), Carplex FPS-3 (trade name / DSL Japan) ), Carplex CS-8 (trade name / manufactured by DSL Japan), nip seal NS-K (trade name / manufactured by Nippon Silica Industry), nip seal NS-KR (trade name / manufactured by Japan Silica Industry), Toxeal NSK (Trade name / manufactured by Tokuyama Corporation), Tokuseal P (trade name / manufactured by Tokuyama Corporation), and the like.
  • the amount of acidic white carbon is usually 1 to 50% by mass, preferably 10 to 30% by mass, based on the whole granulated wettable powder.
  • the basic white carbon used in the granular wettable powder of the present invention has a pH of usually 8 to 14, preferably 9 to 13, more preferably 10 to 12 in a 1% suspension of amorphous silicon dioxide powder. Is.
  • the basic white carbon has an average particle diameter d 50 determined by laser diffraction of usually 2 to 100 ⁇ m, preferably 5 to 20 ⁇ m. The particle size can be adjusted by pulverization or the like.
  • Examples of basic white carbon commercial products include Carplex # 100 (trade name / manufactured by DSL Japan), Carplex # 1120 (trade name / manufactured by DSL Japan), and Toxeal AL-1 (trade name / Tokuyama).
  • Nip seal NA (trade name / manufactured by Nippon Silica Industry Co., Ltd.)
  • nip seal G300 trade name / manufactured by Japan Silica Industry Co., Ltd.
  • DUROSIL (trade name / manufactured by DSL Japan)
  • EXTRUSIL trade name / manufactured by DSL Japan
  • the amount of basic white carbon is preferably from 0.1 to 50% by mass, more preferably from 1 to 20% by mass, based on the whole granulated wettable powder.
  • the polycarboxylic acid surfactant used in the granule wettable powder of the present invention is a polymer surfactant mainly having carboxylic acid as a structural unit.
  • the polymeric surfactant preferably has a molecular weight of 1,000 to 50,000.
  • Examples of the polycarboxylic acid surfactant include (1) a polymer of an ethylenically unsaturated monocarboxylic acid, and (2) a copolymer of an ethylenically unsaturated monocarboxylic acid and an ethylenically unsaturated dicarboxylic acid or an anhydride thereof.
  • Examples of the ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
  • Examples of the ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
  • Examples of the alkene having 2 to 6 carbon atoms include ethylene, propene, butylene, isobutylene, diisobutylene and the like.
  • Examples of the aromatic vinyl compound include styrene, ⁇ -methyl styrene, vinyl toluene, p-methyl styrene and the like.
  • polycarboxylic acid surfactant examples include polyacrylic acid, a copolymer of acrylic acid and maleic acid, a copolymer of isobutylene and maleic anhydride, a copolymer of acrylic acid and itaconic acid, Examples thereof include a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid and styrene, a copolymer of maleic acid and diisobutylene, and salts thereof.
  • the salt examples include alkali metal salts such as lithium, sodium, and potassium; alkaline earth metal salts such as calcium and magnesium; amine salts such as monomethylamine, monoethylamine, and dimethylamine, and ammonium salts. .
  • Isoban 600SF35 (trade name / manufactured by Kuraray Co., Ltd.) as a salt of isobutylene and maleic anhydride copolymer
  • Toxanone GR31A (trade name / manufactured by Sanyo Kasei Co., Ltd.) as a salt of isobutylene and maleic anhydride copolymer
  • Boise 530 (trade name / manufactured by Kao Corporation);
  • Boise 532A (trade name / manufactured by Kao Corporation) as ammonium polyacrylate;
  • Boise 520 (trade name / manufactured by Kao Corporation) as a salt of a copolymer of acrylic acid and maleic acid or Boise 521 (trade name / manufactured by Kao);
  • Neucargen WG-5 (trade name / manufactured by Takemoto Yushi), S-SMA3000 (trade name / manufactured by ARCO CHEMICAL), S- SMA1000 (trade name / ARCO CHEMICAL), S-SMA1440H (
  • the amount of the polycarboxylic acid-based surfactant is not particularly limited, but is usually 0.5 to 10% by mass, preferably 1 to 7% by mass, based on the whole granulated wettable powder.
  • saccharide used in the granular wettable powder of the present invention examples include monosaccharides and disaccharides having a molecular weight of 400 or less, and derivatives thereof.
  • Preferable examples include glucose, galactose, mannose, fructose, maltose, sorbitol, lactose, sucrose, mannitol, and more preferable examples include glucose, sorbitol, lactose, sucrose, maltose.
  • These saccharides can be used singly or in combination of two or more.
  • the amount of the saccharide having a molecular weight of 400 or less is not particularly limited, but is usually 1 to 15% by mass, preferably 2 to 10% by mass with respect to the whole granulated wettable powder.
  • the granule wettable powder of the present invention can further contain a wetting agent, a bulking agent, and a binder other than those described above, if necessary. In that case, it is preferable to maintain the blending ratio of the above components within the above range.
  • wetting agent examples include sodium alkyl naphthalene sulfonate, sodium alkyl sulfate, sodium alkyl benzene sulfonate, sodium alkyl sulfosuccinate, polyoxyethylene alkyl aryl ether, and the like.
  • extender examples include mica, calcium carbonate, kaolin clay, clay, bentonite, diatomaceous earth, zeolite, attapulgite, acid clay, talc, magnesium carbonate, titanium dioxide, ammonium sulfate, sodium sulfate, urea, and the like.
  • binder examples include carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, dextrin, and soluble starch.
  • the shape of the granular wettable powder of the present invention varies depending on the preparation means and conditions, etc., but is usually indeterminate, cubic, rectangular parallelepiped, triangular pyramid, conical, cylindrical, spherical, dumbbell-shaped, elliptical, It is egg-shaped, convex lens-shaped, concave lens-shaped, plate-shaped or the like. Of these, amorphous, cylindrical, spherical and elliptical are preferable. Further, the size of the granule wettable powder is preferably 0.1 to 5 mm at the maximum length portion.
  • the particle size of the granular wettable powder of the present invention is preferably in the range of 50 ⁇ m to 2000 ⁇ m, for example, and more preferably in the range of 100 ⁇ m to 800 ⁇ m.
  • these particle sizes do not require that all granules have a particle size within these ranges, and the particle size of a granule that occupies the maximum of the total particle size distribution (so-called mode diameter) is within these ranges. I just need it.
  • mode diameter the particle size of a required particle size can be obtained by classification.
  • the granule wettable powder of the present invention is publicly known using an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less, acidic white carbon, basic white carbon, a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less. It can manufacture by the method of.
  • active ingredients for agricultural chemicals having a melting point or softening point of 70 ° C. or lower acidic white carbon, basic white carbon, polycarboxylic acid surfactants and saccharides having a molecular weight of 400 or lower, and wetting agents added as necessary ( Dialkylsulfosuccinate, etc.), extenders and binders can be produced by adding a solvent (water, alcohol, etc.), if necessary, mixing at once, extruding granulation, and drying. Furthermore, after the drying, sizing and the like can be performed.
  • the pesticidal active ingredient when the pesticidal active ingredient is liquid at room temperature, the ingredients other than the pesticidal active ingredient are extruded and granulated in the same manner as described above to obtain granules, and the pesticidal active ingredient is absorbed into the granules. can do.
  • a premix preparation is obtained by mixing an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less and acidic white carbon, and the premix preparation and basic white carbon are mixed.
  • a production method including mixing a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less and granulating the resulting mixture is suitable. After granulation, it can be further dried, pulverized and classified as necessary.
  • Premix (premix) process An agrochemical active ingredient having a melting point or softening point of 70 ° C. or less and acidic white carbon are mixed. Thereby a premix formulation is obtained.
  • a mixer such as a ribbon mixer, a nauta mixer or a mixing granulator can be used.
  • the active ingredient of the agrochemical may be used as it is for mixing with the active white carbon, or the active ingredient may be dissolved in a solvent to form a solution and used for mixing with the acidic white carbon.
  • Examples of the solvent for dissolving the active ingredient of agricultural chemicals include alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons, fatty acid esters, phthalic acid esters, vegetable oils, and the like.
  • the pesticide active ingredient When the pesticide active ingredient is provided in a liquid (when the active ingredient of the pesticide active ingredient is a liquid or in the case of a solution as described above), the pesticide active ingredient is easily adsorbed on the acidic white carbon. Moreover, in mixing with an agrochemical active ingredient and acidic white carbon, it can aggregate and make it a lump. In addition, you may remove a solvent by means, such as heating and pressure reduction, after mixing an agrochemical active ingredient and acidic white carbon.
  • the mixture obtained by mixing the pesticidal active ingredient and acidic white carbon is pulverized as necessary.
  • the pulverizing means is not particularly limited, and examples thereof include dry pulverizers such as a pin mill, a hammer mill, a ball mill, and a jet mill.
  • the mixing means is not particularly limited, and can be appropriately selected from those listed as used in the premix step.
  • an agrochemical active ingredient can be further added.
  • the agrochemical active ingredient added in this mixing may be the same as or different from that added during the premixing.
  • the mixture may be pulverized as necessary.
  • the pulverizing means is not particularly limited, and can be appropriately selected from those listed as used in the premix step.
  • kneading can be performed while adding water and moistening.
  • Known methods and means can be used for the method of adding water. For example, there are methods such as dripping, jetting, or spraying.
  • a kneader can be used for kneading. Examples of the kneader include a Nauter mixer, a ribbon mixer, a Henschel mixer, and a kneader. Of these, a kneader is preferable.
  • the water added during kneading is not particularly limited.
  • purified water such as tap water, industrial water, distilled water, ion exchange resin treated water, reverse osmosis membrane (RO) treated water and ultrafiltration membrane (UF) treated water
  • natural water such as ground water, flooded water, river lake water Water
  • the amount of water added during kneading is usually 3 to 70% by weight, preferably 5 to 60% by weight, based on the mixture.
  • the kneading time varies depending on the production scale and the type of the kneader, but is preferably 3 minutes to 60 minutes, more preferably 5 minutes to 20 minutes.
  • the obtained kneaded material is granulated.
  • the granulator include a basket type granulator; an extrusion granulator such as a horizontal extruder, a twin dome gran, a single dome gran and a pelletizer; and a compression granulator such as a roller compactor. Of these, an extrusion granulator is preferred.
  • the extrusion particle size varies depending on the raw materials used and / or the amount of added water, but is preferably 0.2 to 2.0 mm, more preferably 0.5 to 1.2 mm.
  • the granulated product obtained by the above-mentioned method can be used as it is as the granule wettable powder of the present invention, but if necessary, it is dried, sized or classified and used as the granule wettable powder of the present invention. Can be used.
  • the drying process is not particularly limited as long as it can remove the water added in the kneading process and the like and the composition does not undergo a chemical change.
  • the drying temperature and drying time vary depending on the amount of water added and the apparatus used, but can usually be room temperature to 100 ° C., preferably 40 ° C. to 90 ° C., usually 2 minutes to 3 hours, preferably It can be 10 minutes to 1 hour.
  • Examples of the dryer include an aeration band dryer, a stirring dryer, a fluidized bed dryer, a vibration dryer, and a bed dryer.
  • the particle sizer is not particularly limited as long as an appropriate particle size can be obtained.
  • screw type extruders such as meat chopper (manufactured by Hiraga Kogaku Co., Ltd.) and Dome Gran (manufactured by Fuji Powdal Co., Ltd.), vertical crushers such as Rotoplex (manufactured by Hosokawa Micron Corporation), roll granulators ( Crushing type crushers such as Nippon Granulator Co., Ltd., Malmerizer, Pin Mill, etc. can be mentioned.
  • Classifier is not particularly limited. Examples thereof include a gyro shifter and an electromagnetic vibration type sieving machine.
  • the granule wettable powder of the present invention can be applied to crops, soil, and the like with a sprayer after being poured into water and dispersed and diluted.
  • the dilution ratio in water varies depending on the type, content and application purpose of the active ingredient of the agrochemical in the granular wettable powder, but is usually 10 to 10,000 times, preferably 50 to 8000 times, more preferably 500 to 4000 times. is there.
  • the water used for dilution / suspension is not particularly limited, and may be either soft water or hard water.
  • purified water such as tap water, industrial water, distilled water, ion exchange resin treated water, reverse osmosis membrane (RO) treated water and ultrafiltration membrane (UF) treated water
  • natural water such as ground water, flooded water, river lake water Water
  • the granule wettable powder of the present invention can be a container or package that can be used with normal granules or wettable powder, such as aluminum bags, paper bags, paper packs, and plastic bottles.
  • normal granules or wettable powder such as aluminum bags, paper bags, paper packs, and plastic bottles.
  • a paper bag, a plastic bag, a plastic bottle or the like with an aluminum bag or an interior coated with aluminum is preferable.
  • by filling the bag packed in the water-soluble pack into a bag that prevents moisture absorption it is possible to prevent moisture absorption during storage, improve safety, and handleability during dilution.
  • Example 1 50 parts by mass of iminotadine albecyl salt (softening point: 60 ° C.) was dissolved in 50 parts by mass of methanol. This solution was mixed with 50 parts by mass of acidic white carbon (trade name “Carplex XR” manufactured by Shionogi & Co., Ltd.), heated at 50 ° C. to distill off methanol. The obtained powdery mixture was pulverized using a jet mill (trade name “Supersonic Jet Mill PJM” manufactured by Nippon Pneumatic Industry Co., Ltd.), and granules containing 50% iminoctadine albecyl salt (premix preparation) )
  • Siflufenamide (general name / manufactured by Nippon Soda Co., Ltd .; melting point: about 62 ° C.) 3.4 parts by mass, 40 parts by mass of the premix preparation, basic white carbon (trade name “Carplex # 1120” manufactured by DSL Japan) 10 parts by mass, 25 parts by mass of sodium polycarboxylate (trade name “New Calgen WG-5” manufactured by Takemoto Yushi), 5 parts by mass of sorbitol, sodium dioctylsulfosuccinate (trade name “New Calgen EX-70 manufactured by Takemoto Yushi” 3 parts by mass (containing 30% sodium benzoate) and 13.6 parts by mass of potassium chloride were mixed and pulverized with an air pulverizer (trade name “Ulmax” manufactured by Nisso Engineering Co., Ltd.).
  • Example 1 The same operation as in Example 1 except that basic white carbon (trade name “Carplex # 1120” manufactured by DSL Japan) was replaced with acidic white carbon (trade name “Carplex # 80” manufactured by DSL Japan). To obtain a granulated wettable powder.
  • Example 2 Except for changing the amount of sorbitol to 0 parts by mass and the amount of potassium chloride to 18.6 parts by mass, the same operation as in Example 1 was performed to obtain a granular wettable powder.
  • Comparative Example 3 The same operation as Comparative Example 2 except that basic white carbon (trade name “Carplex # 1120” manufactured by DSL Japan) was replaced with acidic white carbon (trade name “Carplex # 80” manufactured by DSL Japan). To obtain a granulated wettable powder.
  • the granule wettable powder obtained in Examples and Comparative Examples was evaluated by the following method. The results are shown in Table 1. (Evaluation of self-dispersibility) When 100 mL of water is added, 100 mL of 3 degree hard water based on the pesticide process inspection method is added to a test tube whose distance from the water surface to the bottom is about 180 mm and the spatial volume is 30 mL. Then, the state until the granule wettable powder sinks to the bottom was observed, and judged according to the following criteria. ⁇ : Disintegration started before the granular wettable powder reached the bottom of the test tube. X: It did not disintegrate at all until the granule wettable powder reached the bottom of the test tube.
  • ⁇ indicates that there is self-dispersibility, and ⁇ indicates that there is no self-dispersibility.
  • O to X represent cases where the particles generally have self-dispersibility but some of the granules do not have self-dispersibility.
  • X to ⁇ represent cases where some of the granules have no self-dispersibility but have self-dispersibility.
  • the conventional granule dispersant has self-dispersibility and is excellent in disintegration and dispersibility in water.
  • the self-dispersibility is lost and the disintegration and dispersibility are reduced.
  • the granule dispersant of the present invention maintains its self-dispersibility even after high-temperature storage, and the degradation of disintegration and dispersibility is small.
  • the granule wettable powder of the present invention is suitable as an agricultural and horticultural agricultural chemical because its disintegration and dispersibility do not decrease even after storage at high temperatures.

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Abstract

Disclosed are a granular wettable powder that contains an agrochemical active ingredient with a melting point or softening point of 70ºC or lower, acidic white carbon, basic white carbon, a polycarboxylic acid-based surfactant, and a saccharide with a molecular weight of 400 or less, and a method for manufacture thereof. The granular wettable powder has superior disintegration and dispersibility in water, and crop injury is suppressed, even after storage at high temperatures.

Description

顆粒水和剤Granule wettable powder
　本発明は、高温下で保管した後においても、水中での崩壊性および分散性に優れる顆粒水和剤に関する。
　本願は、２００８年８月２６日に、日本に出願された特願２００８－２１６７４５号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a granular wettable powder which is excellent in disintegration and dispersibility in water even after being stored at high temperature.
This application claims priority on August 26, 2008 based on Japanese Patent Application No. 2008-216745 filed in Japan, the contents of which are incorporated herein by reference.
　農薬製剤において、顆粒水和剤は、使用時の簡便性、安全性および輸送時の省スペース性に優れるため、需要が高まっており、さまざまな農薬有効成分を配合した顆粒水和剤の開発検討が行われている。
　顆粒水和剤は、通常、農薬有効成分（農薬原体）に、湿潤剤、分散剤、結合剤、増量剤などの補助剤を添加・混合して、それを顆粒状に造粒することによって得られる。
　顆粒水和剤は、通常、水で１０～１００００倍程度に希釈・懸濁して用いられる。顆粒水和剤は、水に投入後、速やかに崩壊・分散することが要求されており、崩壊性および分散性を向上させるための種々の提案がなされている。崩壊性または分散性に劣ると、水中にて農薬有効成分が分離し、散布ムラを生じさせ、それが原因となって作物に薬害を与えるおそれがある。 In agrochemical formulations, granule wettable powders are increasing in demand because of their ease of use, safety, and space saving during transportation. Has been done.
Granule wettable powders are usually obtained by adding and mixing auxiliary agents such as wetting agents, dispersants, binders, and bulking agents to the active ingredients of agricultural chemicals (agrochemical ingredients) and granulating them into granules. can get.
Granule wettable powder is usually used after diluting and suspending with water about 10 to 10,000 times. Granule wettable powders are required to disintegrate and disperse quickly after being added to water, and various proposals have been made to improve disintegration and dispersibility. If it is inferior in disintegration or dispersibility, the active ingredients of agricultural chemicals are separated in water, causing uneven spraying, which may cause phytotoxicity to crops.
　常温で液体の農薬有効成分や低融点の農薬有効成分そのままでは造粒性に難がある。そこで、該農薬有効成分を多量の不活性物質と混合して製剤化する方法や該農薬有効成分の溶液を担体に吸着させて製剤化する方法が提案されている（非特許文献１）。
　また、常温で液体の農薬有効成分、糖類、湿式法シリカの焼成品、ベントナイトおよびアニオン性界面活性剤を混合し造粒することにより得られた顆粒水和物（特許文献１）や、融点７０℃以下の農薬有効成分に湿式法シリカの焼成品およびアニオン性界面活性剤を加え、さらに溶媒および水溶性担体を加えて造粒することにより得られた顆粒水和剤が提案されている（特許文献２）。 The agronomic active ingredient that is liquid at room temperature or the agrochemical active ingredient having a low melting point is difficult to granulate. Therefore, a method of mixing the agrochemical active ingredient with a large amount of an inactive substance to prepare a formulation and a method of adsorbing a solution of the agrochemical active ingredient on a carrier to prepare the formulation (Non-patent Document 1) have been proposed.
In addition, an agrochemical active ingredient that is liquid at normal temperature, a saccharide, a fired product of wet-process silica, a granule hydrate obtained by mixing and granulating bentonite and an anionic surfactant (Patent Document 1), melting point 70 A granulated wettable powder obtained by granulating a baked product of a wet process silica and an anionic surfactant to an agrochemical active ingredient at a temperature of ℃ or less, and further adding a solvent and a water-soluble carrier has been proposed (patent) Reference 2).
　これらに提案された顆粒水和剤は、造粒直後または低温保管後において水に投入した場合には良好な崩壊性および分散性を示す。しかしながら、温度調整設備の無い倉庫で保管したことなどによって長時間高温にさらされた後においては、崩壊性および分散性が低下し、水中にて農薬有効成分が分離し、散布ムラを生じさせることがあった。
　崩壊性および分散性を改良したものとして、融点または軟化点が７０℃以下の農薬有効成分と分散剤としてのＮ－アシルアミノ酸塩と吸着担体との混合物を造粒することにより得られる顆粒水和剤が提案されている（特許文献３）。ところが、Ｎ－アシルアミノ酸塩の使用を規制している国があるので、該規制国では前記顆粒分散剤を使用できない。 The granule wettable powders proposed in these show good disintegration and dispersibility when put into water immediately after granulation or after low-temperature storage. However, after being exposed to high temperatures for a long time, such as when stored in a warehouse without temperature control equipment, disintegration and dispersibility will decrease, causing the active ingredients of agricultural chemicals to separate in water, resulting in dispersion unevenness. was there.
Granule hydration obtained by granulating a mixture of an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less, an N-acylamino acid salt as a dispersant, and an adsorbent as an improved disintegration and dispersibility An agent has been proposed (Patent Document 3). However, since there are countries that regulate the use of N-acylamino acid salts, the granule dispersant cannot be used in the regulated countries.
特開２００７－３９４４０号公報JP 2007-39440 A 特開平３－１６３００６号公報JP-A-3-163006 特開２００５－１０４９５９号公報JP 2005-104959 A
　本発明の目的は、高温下で保管した後においても、水中での崩壊性および分散性に優れ且つ薬害が抑制された、融点または軟化点が７０℃以下の農薬有効成分を含む顆粒水和剤を提供することにある。 An object of the present invention is a granule wettable powder containing an agrochemical active ingredient having a melting point or a softening point of 70 ° C. or less, which is excellent in disintegration and dispersibility in water and suppressed phytotoxicity even after being stored at a high temperature. Is to provide.
　本発明者は上記課題を解決するために種々検討した結果、融点または軟化点が７０℃以下の農薬有効成分と酸性ホワイトカーボンとを混合してプレミックス製剤を得、次いで該プレミックス製剤と塩基性ホワイトカーボンとポリカルボン酸系界面活性剤と分子量が４００以下の糖類とを混合・造粒することによって、高温下で保管した後においても、水中での崩壊性および分散性に優れ且つ薬害が抑制された顆粒水和剤が得られることを見出した。本発明はこの知見に基づいてさらに検討を加えて完成するに至ったものである。 As a result of various studies to solve the above problems, the inventor obtained a premix preparation by mixing an active ingredient of agricultural chemicals having a melting point or softening point of 70 ° C. or less and acidic white carbon, and then the premix preparation and the base By mixing and granulating a reactive white carbon, a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less, it is excellent in disintegration and dispersibility in water and has no phytotoxicity even after storage at high temperature. It has been found that an inhibited granular wettable powder is obtained. The present invention has been completed by further studies based on this finding.
　すなわち、本発明は、融点または軟化点が７０℃以下の農薬有効成分、酸性ホワイトカーボン、塩基性ホワイトカーボン、ポリカルボン酸系界面活性剤および分子量が４００以下の糖類を含有する顆粒水和剤である。
　本発明の顆粒水和剤では、前記糖類がグルコース、ソルビトール、ラクトース、シュークロースおよびマルトースからなる群から選ばれる少なくとも一種のものであることが好ましい。また、前記農薬有効成分がイミノクタジンアルベシル酸塩であることが好ましい。 That is, the present invention is a granular wettable powder containing an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less, acidic white carbon, basic white carbon, a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less. is there.
In the granular wettable powder of the present invention, the saccharide is preferably at least one selected from the group consisting of glucose, sorbitol, lactose, sucrose and maltose. Moreover, it is preferable that the said pesticidal active ingredient is iminotadine albesylate.
　また、本発明は、融点または軟化点が７０℃以下の農薬有効成分と酸性ホワイトカーボンとを混合してプレミックス製剤を得、該プレミックス製剤と塩基性ホワイトカーボンとポリカルボン酸系界面活性剤と分子量が４００以下の糖類とを混合し、得られた混合物を造粒することを含む、顆粒水和剤の製造方法である。 The present invention also provides a premix preparation by mixing an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less and acidic white carbon, the premix preparation, basic white carbon, and a polycarboxylic acid surfactant. And a saccharide having a molecular weight of 400 or less, and granulating the resulting mixture.
　本発明の顆粒水和剤は、高温下で保管した後においても、水中での崩壊性および分散性に優れている。すなわち、温度調整設備の無い倉庫で保管したことなどによって、長時間高温にさらされた後においても、崩壊性および分散性が低下しない。また、水中での崩壊性および分散性に優れているので、水中にて農薬有効成分が分離し難く、散布ムラが抑制される。その結果、薬害が生じ難くなる。本発明の顆粒水和剤は、農園芸用の農薬として好適である。 The granule wettable powder of the present invention is excellent in disintegration and dispersibility in water even after being stored at high temperature. That is, disintegration and dispersibility do not deteriorate even after being exposed to a high temperature for a long time due to storage in a warehouse without temperature control equipment. Moreover, since it is excellent in the disintegration property and dispersibility in water, an agricultural chemical active ingredient is hard to isolate | separate in water, and dispersion | spreading unevenness is suppressed. As a result, chemical damage is less likely to occur. The granule wettable powder of the present invention is suitable as an agricultural and horticultural agricultural chemical.
　本発明の顆粒水和剤は、融点または軟化点が７０℃以下の農薬有効成分、酸性ホワイトカーボン、塩基性ホワイトカーボン、ポリカルボン酸系界面活性剤および分子量が４００以下の糖類を含有するものである。 The granule wettable powder of the present invention contains an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less, acidic white carbon, basic white carbon, a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less. is there.
［農薬有効成分］
　本発明の顆粒水和剤に用いる農薬有効成分は、融点または軟化点が７０℃以下のものである。該農薬有効成分は、殺菌剤、殺虫剤、殺ダニ剤、植物生長調節剤、除草剤、殺そ剤、防菌剤、防かび剤、防藻剤などの一般に農薬として使用される化合物を使用できる。これらの化合物は単独でまたは２種以上を混合して使用できる。 [Agrochemical active ingredients]
The agrochemical active ingredient used for the granule wettable powder of the present invention has a melting point or softening point of 70 ° C. or less. As the agrochemical active ingredient, compounds generally used as agrochemicals such as bactericides, insecticides, acaricides, plant growth regulators, herbicides, fungicides, fungicides, fungicides, and algaecides can be used. . These compounds can be used alone or in admixture of two or more.
　融点７０℃以下の農薬有効成分としては、例えば、２－（１，２－ジメチルプロピルアミノ）－４－エチルアミノ－６－メチルチオ－１，３，５－トリアジン（一般名：ジメタメトリン、融点：６５℃）、Ｓ，Ｓ－ジメチル－２－（ジフルオロメチル）－４－イソブチル－６－（トリフルオロメチル）－３，５－ピリジンジカルボチオナート（一般名：ジチオピル、融点：６５℃）、２，３－ジヒドロ－３，３－ジメチルベンゾフラン－５－イルエタンスルホナート（一般名：ベンフレセート、融点：３２～３５℃）、ブチル（Ｒ）－２－［４－（４－シアノ－２－フルオロフェノキシ）フェノキシ］プロピオナート（一般名：シハロホップブチル、融点：５０℃）、Ｓ－１－メチル－１－フェニルエチルピペリジン－１－カルボチオアート（一般名：ジメピペレート、融点：３８．８～３９．３℃）などが挙げられる。また、常温で液体の農薬有効成分としては、例えば、２－クロロ－２’，６’－ジエチル－Ｎ－（２－プロポキシエチル）－アセトアニリド（一般名：プレチラクロール）、Ｓ－ベンジル－Ｎ－（１，２－ジメチルプロピル）－Ｎ－エチルチオカルバマート（一般名：エスプロカルブ）などが挙げられる。
　軟化点７０℃以下の農薬有効成分としては、例えば、１，１’－イミノジ（オクタメチレン）ジグアニジニウム・トリス（アルキルベンゼンスルホナート）（一般名：イミノクタジンアルベシル酸塩、軟化点：５５～６０℃）などが挙げられる。
　これらのうち、イミノクタジンアルベシル酸塩が、本発明の顆粒水和剤に好適である。 As an agrochemical active ingredient having a melting point of 70 ° C. or less, for example, 2- (1,2-dimethylpropylamino) -4-ethylamino-6-methylthio-1,3,5-triazine (generic name: dimetamethrin, melting point: 65 ° C), S, S-dimethyl-2- (difluoromethyl) -4-isobutyl-6- (trifluoromethyl) -3,5-pyridinedicarbothionate (generic name: dithiopyr, melting point: 65 ° C), 2 , 3-Dihydro-3,3-dimethylbenzofuran-5-ylethanesulfonate (generic name: benfrate, melting point: 32-35 ° C.), butyl (R) -2- [4- (4-cyano-2-fluoro Phenoxy) phenoxy] propionate (generic name: cihalohop butyl, melting point: 50 ° C.), S-1-methyl-1-phenylethylpiperidine-1-carbothioate Common name: dimepiperate, mp: 38.8 ~ 39.3 ° C.), and the like. Examples of active agricultural chemicals that are liquid at room temperature include, for example, 2-chloro-2 ′, 6′-diethyl-N- (2-propoxyethyl) -acetanilide (generic name: pretilachlor), S-benzyl-N— ( 1,2-dimethylpropyl) -N-ethylthiocarbamate (generic name: Esprocarb).
As an agrochemical active ingredient having a softening point of 70 ° C. or lower, for example, 1,1′-iminodi (octamethylene) diguanidinium tris (alkylbenzenesulfonate) (generic name: iminoctadine albecyl salt, softening point: 55 to 60 ° C.) Etc.
Of these, iminotadine albesylate is suitable for the granular wettable powder of the present invention.
　本発明の顆粒水和剤は、融点および軟化点が７０℃を超える農薬有効成分を含有していても構わない。該農薬有効成分は、殺菌剤、殺虫剤、殺ダニ剤、植物生長調節剤、除草剤、殺そ剤、防菌剤、防かび剤、防藻剤などの一般に農薬として使用される化合物を使用できる。これらの化合物は単独でまたは２種以上を混合して使用できる。 The granule wettable powder of the present invention may contain an agrochemical active ingredient having a melting point and a softening point exceeding 70 ° C. As the agrochemical active ingredient, compounds generally used as agrochemicals such as bactericides, insecticides, acaricides, plant growth regulators, herbicides, fungicides, fungicides, fungicides, and algaecides can be used. . These compounds can be used alone or in admixture of two or more.
　融点および軟化点が７０℃を超える農薬有効成分としては、例えば、２－イソプロピルフェニル－Ｎ－メチルカルバマート（一般名：ＭＩＰＣ、融点：８８～９３℃）、３，５－キシリル－Ｎ－メチルカルバマート（一般名：ＸＭＣ、融点：９９～１００℃）、３－（４－ｔｅｒｔ－ブチル－２－エトキシフェニル）－２－（２，６－ジフルオロフェニル）－４，５－ジヒドロオキサゾール（一般名：エトキサゾール、融点：１０１～１０２℃）、Ｏ－３－ｔｅｒｔ－ブチルフェニル－６－メトキシ－２－ピリジル（メチル）チオカルバマート（ 一般名：ピリブチカルブ、融点：８５．７～８６．２℃）、５－（２，４－ジクロロフェノキシ）－２－ニトロメチルベンゾアート（一般名：ビフェノックス、融点：８４～８６℃）、１－（α，α－ジメチルベンジル）－３－（パラトリル）尿素（一般名：ダイムロン、融点：２０３℃）、Ｎ，Ｎ－ジエチル－３－メシチルスルホニル－１Ｈ－１，２，４－トリアゾール－１－カルボキサミド（一般名：カフェンストロール、融点：１１４～１１６℃）、メチル－α－（４，６－ジメトキシピリミジン－２－イル）カルバモイルスルファモイル］－ｏ－トルアート（一般名：ベンスルフロンメチル、融点：１８５～１８８℃）、２－ブロモ－Ｎ－（α，α－ジメチルベンジル）－３，３－ジメチルブタナミド（一般名：ブロモブチド、融点：１８０．１℃）、１－（２－クロロイミダゾ［１，２－ａ］ピリジン－３－イルスルホニル）－３－（４，６－ジメトキシピリジン－２－イル）尿素（一般名：イマゾスルフロン、融点：１８３～１８４℃）、１－｛［Ｏ－（シクロプロピルカルボニル）フェニル］スルファモイル｝－３（４，６－ジメトキシ－２－ピリミジニル）－尿素（一般名：シクロスルファムロン、融点：１４９．６～１５３．２℃）、メチル（Ｅ）－２－メトキシイミノ［α－（ｏ－トリルオキシ）ｏ－トリル］アセタート（一般名：クレソキシムメチル、融点：１０１．６～１０２．５℃）、メチル（Ｅ）－２－［２－｛６－（２－シアノフェノキシ）ピリミジン－４－イルオキシ｝フェニル］－３－メトキシアクリラート（一般名：アゾキシストロビン、融点：１１６℃）、５－〔〔２－アミノ－５－Ｏ－（アミノカルボニル）－２－デオキシ－Ｌ－キシロニル〕アミノ〕－１，５－ジデオキシ－１－〔３，４－ジヒドロ－５－（ヒドロキシメチル）－２，４－ジオキソ－１（２Ｈ）－ピリミジル〕－β－Ｄ－アロフラヌロニック酸（一般名：ポリオキシン、融点：１６０℃以上）、ビス（ジメチルチオカルバモイル）ジスルフィド（一般名：チウラム、融点：１５５～１５６℃）、Ｎ－（２，３－ジクロロ－４－ヒドロキシフェニル）－１－メチルシクロヘキサンカルボキサミド（一般名：フェンヘキサミド、融点：１５３℃）、亜鉛イオン配位マンガニーズエチレンビスジチオカルバマート（一般名：マンコゼブ、融点：１９２℃以上）、３－（３，５－ジクロロフェニル）－Ｎ－イソプロピル－２，４－ジオキソイミダゾリジン－１－カルボキサミド（一般名：イプロジオン、融点：１３４℃）、３’－イソプロポキシ－２－メチルベンズアニリド（一般名：メプロニル、融点：９２～９３℃）、（１ＲＳ，２ＳＲ，５ＳＲ；１ＲＳ，２ＳＲ，５ＳＲ）－２－（４－クロロベンジル）－５－イソプロピル－１－（１Ｈ－１，２，４－トリアゾール－１－イルメチル）シクロペンタノール（一般名：イプコナゾール、融点：９１～１１９℃）などが挙げられる。 Pesticide active ingredients having a melting point and softening point exceeding 70 ° C. include, for example, 2-isopropylphenyl-N-methylcarbamate (generic name: MIPC, melting point: 88-93 ° C.), 3,5-xylyl-N-methyl Carbamate (generic name: XMC, melting point: 99-100 ° C.), 3- (4-tert-butyl-2-ethoxyphenyl) -2- (2,6-difluorophenyl) -4,5-dihydrooxazole (general Name: etoxazole, melting point: 101-102 ° C.), O-3-tert-butylphenyl-6-methoxy-2-pyridyl (methyl) thiocarbamate (generic name: pyributicalbu, melting point: 85.7-86.2 ° C.) ), 5- (2,4-dichlorophenoxy) -2-nitromethylbenzoate (generic name: biphenox, melting point: 84-86 ° C.), 1- (α , Α-dimethylbenzyl) -3- (paratolyl) urea (generic name: Daimlon, melting point: 203 ° C.), N, N-diethyl-3-mesitylsulfonyl-1H-1,2,4-triazole-1-carboxamide (Generic name: caffeentrol, melting point: 114-116 ° C.), methyl-α- (4,6-dimethoxypyrimidin-2-yl) carbamoylsulfamoyl] -o-toluate (generic name: bensulfuron methyl, melting point: 185 ˜188 ° C.), 2-bromo-N- (α, α-dimethylbenzyl) -3,3-dimethylbutanamide (generic name: bromobutide, melting point: 180.1 ° C.), 1- (2-chloroimidazo [1 , 2-a] pyridin-3-ylsulfonyl) -3- (4,6-dimethoxypyridin-2-yl) urea (generic name: imazosulfuron, melting point: 183) 184 ° C.), 1-{[O- (cyclopropylcarbonyl) phenyl] sulfamoyl} -3 (4,6-dimethoxy-2-pyrimidinyl) -urea (generic name: cyclosulfamlone, melting point: 149.6 to 153) 2 ° C), methyl (E) -2-methoxyimino [α- (o-tolyloxy) o-tolyl] acetate (generic name: cresoxime methyl, melting point: 101.6-102.5 ° C), methyl (E)- 2- [2- {6- (2-cyanophenoxy) pyrimidin-4-yloxy} phenyl] -3-methoxyacrylate (generic name: azoxystrobin, melting point: 116 ° C.), 5-[[2-amino -5-O- (aminocarbonyl) -2-deoxy-L-xylonyl] amino] -1,5-dideoxy-1- [3,4-dihydro-5- (hydroxymethyl) -2 4-dioxo-1 (2H) -pyrimidyl] -β-D-alofurauronic acid (generic name: polyoxin, melting point: 160 ° C. or higher), bis (dimethylthiocarbamoyl) disulfide (generic name: thiuram, melting point: 155 ˜156 ° C.), N- (2,3-dichloro-4-hydroxyphenyl) -1-methylcyclohexanecarboxamide (generic name: phenhexamide, melting point: 153 ° C.), zinc ion coordinated Manganese ethylene bisdithiocarbamate (Generic name: mancozeb, melting point: 192 ° C. or higher), 3- (3,5-dichlorophenyl) -N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide (generic name: iprodione, melting point: 134 ° C.) 3'-isopropoxy-2-methylbenzanilide (generic name: mepronil, melting point: 92-93) ° C), (1RS, 2SR, 5SR; 1RS, 2SR, 5SR) -2- (4-chlorobenzyl) -5-isopropyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (Generic name: ipconazole, melting point: 91-119 ° C.).
　本発明の顆粒水和剤では、融点または軟化点が７０℃以下の農薬有効成分が、顆粒水和剤全体に対して、０．１～５０質量％であることが好ましい。
　融点または軟化点が７０℃を超える農薬有効成分の量は、農薬有効成分全体に対して、通常１０質量％以下、好ましくは５質量％以下である。 In the granular wettable powder of the present invention, it is preferable that the active ingredient of agricultural chemicals having a melting point or softening point of 70 ° C. or less is 0.1 to 50% by mass with respect to the entire granular wettable powder.
The amount of the pesticidal active ingredient whose melting point or softening point exceeds 70 ° C. is usually 10% by mass or less, preferably 5% by mass or less, based on the entire pesticidal active ingredient.
［酸性ホワイトカーボン］
　本発明の顆粒水和剤に用いる酸性ホワイトカーボンは、非晶質二酸化ケイ素粉末のうち、１％懸濁液においてｐＨが通常６～７、好ましくは６～７．５のものである。酸性ホワイトカーボンは、レーザー回折で求めた平均粒径ｄ50が、通常１～５００μｍ、好ましくは１０～１００μｍである。なお、粒径は粉砕などによって調整できる。 [Acid white carbon]
The acidic white carbon used in the granular wettable powder of the present invention has a pH of usually 6 to 7, preferably 6 to 7.5 in a 1% suspension of amorphous silicon dioxide powder. Acidic white carbon has an average particle diameter d 50 determined by laser diffraction of usually 1 to 500 μm, preferably 10 to 100 μm. The particle size can be adjusted by pulverization or the like.
　酸性ホワイトカーボンの市販品の例としては、カープレックス＃８０（商品名／ＤＳＬジャパン社製）、カープレックスＸＲ（商品名／ＤＳＬジャパン社製）、カープレックスＦＰＳ－３（商品名／ＤＳＬジャパン社製）、カープレックスＣＳ－８（商品名／ＤＳＬジャパン社製）、ニップシールＮＳ－Ｋ（商品名／日本シリカ工業社製）、ニップシールＮＳ－ＫＲ（商品名／日本シリカ工業社製）、トクシールＮＳＫ（商品名／トクヤマ社製）、トクシールＰ（商品名／トクヤマ社製）などを挙げることができる。
　酸性ホワイトカーボンの量は、顆粒水和剤全体に対して、通常１～５０質量％、好ましくは、１０～３０質量％である。 Examples of commercial products of acidic white carbon include Carplex # 80 (trade name / manufactured by DSL Japan), Carplex XR (trade name / manufactured by DSL Japan), Carplex FPS-3 (trade name / DSL Japan) ), Carplex CS-8 (trade name / manufactured by DSL Japan), nip seal NS-K (trade name / manufactured by Nippon Silica Industry), nip seal NS-KR (trade name / manufactured by Japan Silica Industry), Toxeal NSK (Trade name / manufactured by Tokuyama Corporation), Tokuseal P (trade name / manufactured by Tokuyama Corporation), and the like.
The amount of acidic white carbon is usually 1 to 50% by mass, preferably 10 to 30% by mass, based on the whole granulated wettable powder.
［塩基性ホワイトカーボン］
　本発明の顆粒水和剤に用いる塩基性ホワイトカーボンは、非晶質二酸化ケイ素粉末のうち、１％懸濁液においてｐＨが通常８～１４、好ましくは９～１３、更に好ましくは１０～１２のものである。該塩基性ホワイトカーボンは、レーザー回折で求めた平均粒径ｄ50が、通常２～１００μｍ、好ましくは５～２０μｍである。なお、粒径は粉砕などによって調整できる。 [Basic white carbon]
The basic white carbon used in the granular wettable powder of the present invention has a pH of usually 8 to 14, preferably 9 to 13, more preferably 10 to 12 in a 1% suspension of amorphous silicon dioxide powder. Is. The basic white carbon has an average particle diameter d 50 determined by laser diffraction of usually 2 to 100 μm, preferably 5 to 20 μm. The particle size can be adjusted by pulverization or the like.
　塩基性ホワイトカーボンの市販品の例としては、カープレックス＃１００（商品名／ＤＳＬジャパン社製）、カープレックス＃１１２０（商品名／ＤＳＬジャパン社製）、トクシールＡＬ－１（商品名／トクヤマ社製）、ニップシールＮＡ（商品名／日本シリカ工業社製）、ニップシールＧ３００（商品名／日本シリカ工業社製）、ＤＵＲＯＳＩＬ（商品名／ＤＳＬジャパン社製）、ＥＸＴＲＵＳＩＬ（商品名／ＤＳＬジャパン社製）などを挙げることができる。
　塩基性ホワイトカーボンの量は、顆粒水和剤全体に対して、０．１～５０質量％であることが好ましく、１～２０質量％であることがさらに好ましい。 Examples of basic white carbon commercial products include Carplex # 100 (trade name / manufactured by DSL Japan), Carplex # 1120 (trade name / manufactured by DSL Japan), and Toxeal AL-1 (trade name / Tokuyama). Nip seal NA (trade name / manufactured by Nippon Silica Industry Co., Ltd.), nip seal G300 (trade name / manufactured by Japan Silica Industry Co., Ltd.), DUROSIL (trade name / manufactured by DSL Japan), EXTRUSIL (trade name / manufactured by DSL Japan) And so on.
The amount of basic white carbon is preferably from 0.1 to 50% by mass, more preferably from 1 to 20% by mass, based on the whole granulated wettable powder.
［ポリカルボン酸系界面活性剤］
　本発明の顆粒水和剤に用いるポリカルボン酸系界面活性剤は、カルボン酸を構造単位として主に有する高分子界面活性剤である。該高分子界面活性剤は分子量が好ましくは１，０００～５０，０００である。ポリカルボン酸系界面活性剤としては、例えば（１）エチレン性不飽和モノカルボン酸の重合体、（２）エチレン性不飽和モノカルボン酸とエチレン性不飽和ジカルボン酸もしくはその無水物との共重合体、（３）エチレン性不飽和モノカルボン酸またはエチレン性不飽和ジカルボン酸もしくはその無水物と炭素数２～６のアルケンとの共重合体、（４）エチレン性不飽和モノカルボン酸またはエチレン性不飽和ジカルボン酸もしくはその無水物と芳香族ビニル化合物との共重合体およびこれらの塩などが挙げられる。 [Polycarboxylic acid surfactant]
The polycarboxylic acid surfactant used in the granule wettable powder of the present invention is a polymer surfactant mainly having carboxylic acid as a structural unit. The polymeric surfactant preferably has a molecular weight of 1,000 to 50,000. Examples of the polycarboxylic acid surfactant include (1) a polymer of an ethylenically unsaturated monocarboxylic acid, and (2) a copolymer of an ethylenically unsaturated monocarboxylic acid and an ethylenically unsaturated dicarboxylic acid or an anhydride thereof. (3) Copolymer of ethylenically unsaturated monocarboxylic acid or ethylenically unsaturated dicarboxylic acid or anhydride thereof and alkene having 2 to 6 carbon atoms, (4) ethylenically unsaturated monocarboxylic acid or ethylenic Examples thereof include copolymers of unsaturated dicarboxylic acids or anhydrides thereof and aromatic vinyl compounds, and salts thereof.
　エチレン性不飽和モノカルボン酸としては、アクリル酸、メタクリル酸、クロトン酸などが挙げられる。
　エチレン性不飽和ジカルボン酸としては、マレイン酸、フマル酸、イタコン酸などが挙げられる。
　炭素数２～６のアルケンとしては、エチレン、プロペン、ブチレン、イソブチレン、ジイソブチレンなどが挙げられる。
　芳香族ビニル化合物としては、スチレン、α－メチルスチレン、ビニルトルエン、ｐ－メチルスチレンなどが挙げられる。 Examples of the ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
Examples of the ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
Examples of the alkene having 2 to 6 carbon atoms include ethylene, propene, butylene, isobutylene, diisobutylene and the like.
Examples of the aromatic vinyl compound include styrene, α-methyl styrene, vinyl toluene, p-methyl styrene and the like.
　ポリカルボン酸系界面活性剤の具体例としては、ポリアクリル酸、アクリル酸とマレイン酸との共重合体、イソブチレンと無水マレイン酸との共重合体、アクリル酸とイタコン酸との共重合体、メタクリル酸とイタコン酸との共重合体、マレイン酸とスチレンとの共重合体、マレイン酸とジイソブチレンとの共重合体およびそれらの塩などが挙げられる。なお、塩としては、例えばリチウム、ナトリウム、カリウムなどのアルカリ金属の塩；カルシウム、マグネシウムなどのアルカリ土類金属の塩；モノメチルアミン、モノエチルアミン、ジメチルアミンなどのアミン塩およびアンモニウム塩などが挙げられる。 Specific examples of the polycarboxylic acid surfactant include polyacrylic acid, a copolymer of acrylic acid and maleic acid, a copolymer of isobutylene and maleic anhydride, a copolymer of acrylic acid and itaconic acid, Examples thereof include a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid and styrene, a copolymer of maleic acid and diisobutylene, and salts thereof. Examples of the salt include alkali metal salts such as lithium, sodium, and potassium; alkaline earth metal salts such as calcium and magnesium; amine salts such as monomethylamine, monoethylamine, and dimethylamine, and ammonium salts. .
　イソブチレンと無水マレイン酸共重合体の塩としてイソバン６００ＳＦ３５（商品名／クラレ社製）；イソブチレンと無水マレイン酸共重合体の塩としてトキサノンＧＲ３１Ａ（商品名／三洋化成社製）；ポリアクリル酸塩としてボイズ５３０（商品名／花王社製）；ポリアクリル酸アンモニウムとしてボイズ５３２Ａ（商品名／花王社製）；アクリル酸とマレイン酸の共重合体の塩としてボイズ５２０（商品名／花王社製）またはボイズ５２１（商品名／花王社製）；マレイン酸とアルケンの共重合体としてニューカルゲンＷＧ－５（商品名／竹本油脂社製）、Ｓ－ＳＭＡ３０００（商品名／ＡＲＣＯ ＣＨＥＭＩＣＡＬ社製）、Ｓ－ＳＭＡ１０００（商品名／ＡＲＣＯ ＣＨＥＭＩＣＡＬ社製）、Ｓ－ＳＭＡ１４４０Ｈ（商品名／ＡＲＣＯ ＣＨＥＭＩＣＡＬ社製）、ポリスターＯＭＰ（商品名／日本油脂社製）、ポリスターＯＭＡ（商品名／日本油脂社製）、ポリスターＳＭＸ（商品名／日本油脂社製）、ポリスターＳＭ－１０１５（商品名／日本油脂社製）、ポリスターＡ－１０６０（商品名／日本油脂社製）、ソカランＣＰ－５（商品名／ＢＡＳＦ社製）、ソカランＣＰ－７（商品名／ＢＡＳＦ社製）、ソカランＣＰ－９（商品名／ＢＡＳＦ社製）、ソカランＣＰ－１０（商品名／ＢＡＳＦ社製）、ＧＥＲＯＰＯＮ Ｔ／３６（商品名／ローヌプーラン社製）、ＧＥＲＯＰＯＮ ＴＡ／７２（商品名／ローヌプーラン社製）、ＧＥＲＯＰＯＮ ＳＣ／２１３（商品名／ローヌプーラン社製）、またはＳｏｒｐｏｌ－７２４８（商品名／東邦化学社製）などが挙げられる。 Isoban 600SF35 (trade name / manufactured by Kuraray Co., Ltd.) as a salt of isobutylene and maleic anhydride copolymer; Toxanone GR31A (trade name / manufactured by Sanyo Kasei Co., Ltd.) as a salt of isobutylene and maleic anhydride copolymer; Boise 530 (trade name / manufactured by Kao Corporation); Boise 532A (trade name / manufactured by Kao Corporation) as ammonium polyacrylate; Boise 520 (trade name / manufactured by Kao Corporation) as a salt of a copolymer of acrylic acid and maleic acid or Boise 521 (trade name / manufactured by Kao); Neucargen WG-5 (trade name / manufactured by Takemoto Yushi), S-SMA3000 (trade name / manufactured by ARCO CHEMICAL), S- SMA1000 (trade name / ARCO CHEMICAL), S-SMA1440H (trade name / ARC) O CHEMICAL), Polystar OMP (trade name / manufactured by NOF Corporation), POLYSTAR OMA (trade name / manufactured by NOF Corporation), Polystar SMX (trade name / manufactured by NOF Corporation), Polystar SM-1015 (trade name / Nippon Oil & Fats Co., Ltd., Polystar A-1060 (trade name / manufactured by Nippon Oil & Fats), Socaran CP-5 (trade name / manufactured by BASF), Socaran CP-7 (trade name / manufactured by BASF), Socaran CP-9 (Brand name / BASF), Socaran CP-10 (Brand / BASF), GERAPON ／ T / 36 (Brand / Rhone-Poulein), GERAPON TA / 72 (Brand name / Rhone-Poulein), GEROPON SC / 213 (trade name / Rhône-Poulenc) or Sorpol-7248 (trade name / Toho Chemical Co., Ltd.).
　ポリカルボン酸系界面活性剤の量は特に限定されないが、顆粒水和剤全体に対して、通常は０．５～１０質量％、好ましくは１～７質量％である。 The amount of the polycarboxylic acid-based surfactant is not particularly limited, but is usually 0.5 to 10% by mass, preferably 1 to 7% by mass, based on the whole granulated wettable powder.
［糖類］
　本発明の顆粒水和剤に用いられる糖類としては、分子量が４００以下の単糖類および二糖類並びにそれらの誘導体が挙げられる。好適なものとしては、グルコース、ガラクトース、マンノース、フルクトース、マルトース、ソルビトール、ラクトース、シュークロース、マンニトールが挙げられ、更に好適なものとしては、グルコース、ソルビトール、ラクトース、シュークロース、マルトースが挙げられる。これらの糖類は、一種単独でまたは二種以上を組み合わせて使用できる。 [Sugar]
Examples of the saccharide used in the granular wettable powder of the present invention include monosaccharides and disaccharides having a molecular weight of 400 or less, and derivatives thereof. Preferable examples include glucose, galactose, mannose, fructose, maltose, sorbitol, lactose, sucrose, mannitol, and more preferable examples include glucose, sorbitol, lactose, sucrose, maltose. These saccharides can be used singly or in combination of two or more.
　分子量が４００以下の糖類の量は特に限定はないが、顆粒水和剤全体に対して、通常は１～１５質量％、好ましくは２～１０質量％である。 The amount of the saccharide having a molecular weight of 400 or less is not particularly limited, but is usually 1 to 15% by mass, preferably 2 to 10% by mass with respect to the whole granulated wettable powder.
　本発明の顆粒水和剤は、必要に応じて、上記以外の湿潤剤、増量剤、結合剤をさらに含有することができる。その場合、上記の構成成分の配合割合は上記の範囲内に維持するのが好ましい。 The granule wettable powder of the present invention can further contain a wetting agent, a bulking agent, and a binder other than those described above, if necessary. In that case, it is preferable to maintain the blending ratio of the above components within the above range.
　湿潤剤としては、例えば、アルキルナフタレンスルホン酸ナトリウム、アルキル硫酸ナトリウム、アルキルベンゼンスルホン酸ナトリウム、アルキルスルホコハク酸ナトリウム、ポリオキシエチレンアルキルアリールエーテル、などが挙げられる。 Examples of the wetting agent include sodium alkyl naphthalene sulfonate, sodium alkyl sulfate, sodium alkyl benzene sulfonate, sodium alkyl sulfosuccinate, polyoxyethylene alkyl aryl ether, and the like.
　増量剤としては、例えば、雲母、炭酸カルシウム、カオリンクレー、クレー、ベントナイト、珪藻土、ゼオライト、アタパルジャイト、酸性白土、タルク、炭酸マグネシウム、二酸化チタン、硫酸アンモニウム、硫酸ナトリウム、尿素、などが挙げられる。 Examples of the extender include mica, calcium carbonate, kaolin clay, clay, bentonite, diatomaceous earth, zeolite, attapulgite, acid clay, talc, magnesium carbonate, titanium dioxide, ammonium sulfate, sodium sulfate, urea, and the like.
　結合剤としては、例えば、カルボキシメチルセルロース、ポリビニルアルコール、ポリビニルピロリドン、デキストリン、可溶性デンプン、などが挙げられる。 Examples of the binder include carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, dextrin, and soluble starch.
　本発明の顆粒水和剤の形状は、調製の手段や条件などにより変わるが、通常、不定形、立方体状、直方体状、三角錐状、円錐状、円柱状、球状、ダンベル状、楕球状、卵状、凸レンズ状、凹レンズ状、板状などである。中でも不定形、円柱状、球状および楕球状が好ましい。さらに、顆粒水和剤の大きさは、最大長部分で０．１～５mmであることが好ましい。 The shape of the granular wettable powder of the present invention varies depending on the preparation means and conditions, etc., but is usually indeterminate, cubic, rectangular parallelepiped, triangular pyramid, conical, cylindrical, spherical, dumbbell-shaped, elliptical, It is egg-shaped, convex lens-shaped, concave lens-shaped, plate-shaped or the like. Of these, amorphous, cylindrical, spherical and elliptical are preferable. Further, the size of the granule wettable powder is preferably 0.1 to 5 mm at the maximum length portion.
　本発明の顆粒水和剤の粒径は、例えば５０μｍ～２０００μｍの範囲が好ましく、１００μｍ～８００μｍの範囲がより好ましい。但し、これらの粒径は、全顆粒がこれらの範囲内の粒径であることが必要ではなく、全粒度分布のうち最大を占める顆粒の粒径（いわゆる、モード径）がこれらの範囲内であればよい。また、分級によって必要な粒径の顆粒のみを得ることができる。 The particle size of the granular wettable powder of the present invention is preferably in the range of 50 μm to 2000 μm, for example, and more preferably in the range of 100 μm to 800 μm. However, these particle sizes do not require that all granules have a particle size within these ranges, and the particle size of a granule that occupies the maximum of the total particle size distribution (so-called mode diameter) is within these ranges. I just need it. Moreover, only the granule of a required particle size can be obtained by classification.
［顆粒水和剤の製造方法］
　本発明の顆粒水和剤は、融点または軟化点が７０℃以下の農薬有効成分、酸性ホワイトカーボン、塩基性ホワイトカーボン、ポリカルボン酸系界面活性剤および分子量が４００以下の糖類を用いて、公知の方法によって製造することができる。 [Production method of granule wettable powder]
The granule wettable powder of the present invention is publicly known using an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less, acidic white carbon, basic white carbon, a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less. It can manufacture by the method of.
　例えば、融点または軟化点が７０℃以下の農薬有効成分、酸性ホワイトカーボン、塩基性ホワイトカーボン、ポリカルボン酸系界面活性剤および分子量が４００以下の糖類、並びに必要に応じて添加される湿潤剤（ジアルキルスルホコハク酸塩など）、増量剤および結合剤を、必要に応じて溶媒（水、アルコールなど）を添加して、一括で混合し、押出造粒し、乾燥することによって製造することができる。さらに乾燥後に解砕などの整粒を行うことができる。
　また、農薬有効成分が常温で液状の場合には、農薬有効成分を除く成分を上記と同様に押出造粒して粒剤を得、該粒剤に液状の農薬有効成分を吸収させることによって製造することができる。 For example, active ingredients for agricultural chemicals having a melting point or softening point of 70 ° C. or lower, acidic white carbon, basic white carbon, polycarboxylic acid surfactants and saccharides having a molecular weight of 400 or lower, and wetting agents added as necessary ( Dialkylsulfosuccinate, etc.), extenders and binders can be produced by adding a solvent (water, alcohol, etc.), if necessary, mixing at once, extruding granulation, and drying. Furthermore, after the drying, sizing and the like can be performed.
In addition, when the pesticidal active ingredient is liquid at room temperature, the ingredients other than the pesticidal active ingredient are extruded and granulated in the same manner as described above to obtain granules, and the pesticidal active ingredient is absorbed into the granules. can do.
　本発明の顆粒水和剤を得る方法としては、融点または軟化点が７０℃以下の農薬有効成分と酸性ホワイトカーボンとを混合してプレミックス製剤を得、該プレミックス製剤と塩基性ホワイトカーボンとポリカルボン酸系界面活性剤と分子量が４００以下の糖類とを混合し、得られた混合物を造粒することを含む、製法が好適である。造粒後、さらに必要に応じて乾燥、粉砕、分級することができる。 As a method for obtaining the granule wettable powder of the present invention, a premix preparation is obtained by mixing an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less and acidic white carbon, and the premix preparation and basic white carbon are mixed. A production method including mixing a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less and granulating the resulting mixture is suitable. After granulation, it can be further dried, pulverized and classified as necessary.
（プレミックス（予混合）工程）
　融点または軟化点が７０℃以下の農薬有効成分と酸性ホワイトカーボンとを混合する。それによってプレミックス製剤を得る。
　農薬有効成分と酸性ホワイトカーボンとの混合には、例えば、リボンミキサー、ナウタミキサー、混合造粒機などの混合機を用いることができる。
　農薬有効成分は、原体そのままを酸性ホワイトカーボンとの混合に供してもよいが、原体を溶媒に溶解させて溶液にし該溶液で酸性ホワイトカーボンとの混合に供してもよい。
　農薬有効成分を溶解させるための溶媒としては、メタノール、エタノールなどのアルコール類；アセトン、メチルエチルケトンなどのケトン類；芳香族系炭化水素、脂肪酸エステル類、フタル酸エステル類、植物油、などが挙げられる。 (Premix (premix) process)
An agrochemical active ingredient having a melting point or softening point of 70 ° C. or less and acidic white carbon are mixed. Thereby a premix formulation is obtained.
For mixing the agrochemical active ingredient and the acidic white carbon, for example, a mixer such as a ribbon mixer, a nauta mixer or a mixing granulator can be used.
The active ingredient of the agrochemical may be used as it is for mixing with the active white carbon, or the active ingredient may be dissolved in a solvent to form a solution and used for mixing with the acidic white carbon.
Examples of the solvent for dissolving the active ingredient of agricultural chemicals include alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons, fatty acid esters, phthalic acid esters, vegetable oils, and the like.
　農薬有効成分を液で供した場合（農薬有効成分の原体が液体である場合または上記のように溶液とした場合）には、酸性ホワイトカーボンに農薬有効成分が吸着されやすい。また、農薬有効成分と酸性ホワイトカーボンとの混合において、凝集をおこさせ塊状にすることができる。
　なお、溶媒は、農薬有効成分と酸性ホワイトカーボンとの混合後に、加温や減圧などの手段によって除去してもよい。 When the pesticide active ingredient is provided in a liquid (when the active ingredient of the pesticide active ingredient is a liquid or in the case of a solution as described above), the pesticide active ingredient is easily adsorbed on the acidic white carbon. Moreover, in mixing with an agrochemical active ingredient and acidic white carbon, it can aggregate and make it a lump.
In addition, you may remove a solvent by means, such as heating and pressure reduction, after mixing an agrochemical active ingredient and acidic white carbon.
　農薬有効成分と酸性ホワイトカーボンとの混合で得られた混合物は、必要に応じて粉砕される。粉砕手段は特に制限されず、例えば、ピンミル、ハンマーミル、ボールミル、ジェットミルなどの乾式粉砕機が挙げられる。 The mixture obtained by mixing the pesticidal active ingredient and acidic white carbon is pulverized as necessary. The pulverizing means is not particularly limited, and examples thereof include dry pulverizers such as a pin mill, a hammer mill, a ball mill, and a jet mill.
（本混合工程）
　次に、プレミックス製剤に、塩基性ホワイトカーボン、ポリカルボン酸系界面活性剤および分子量が４００以下の糖類、並びに必要に応じて湿潤剤、その他の添加剤を加えて混合する。混合手段は特に限定されず、プレミックス工程で用いられるものとして挙げたものの中から適宜選択できる。本混合の際に、さらに、農薬有効成分を加えることができる。本混合で加える農薬有効成分は予混合の際に加えたものと同じものであっても、異なるものであってもよい。
　本混合後、必要に応じて混合物を粉砕してもよい。粉砕手段は特に限定されず、プレミックス工程で用いられるものとして挙げたものの中から適宜選択できる。 (This mixing process)
Next, basic white carbon, a polycarboxylic acid surfactant, a saccharide having a molecular weight of 400 or less, and a wetting agent and other additives as necessary are added to the premix preparation and mixed. The mixing means is not particularly limited, and can be appropriately selected from those listed as used in the premix step. In this mixing, an agrochemical active ingredient can be further added. The agrochemical active ingredient added in this mixing may be the same as or different from that added during the premixing.
After the main mixing, the mixture may be pulverized as necessary. The pulverizing means is not particularly limited, and can be appropriately selected from those listed as used in the premix step.
（加水混練工程）
　本混合工程後、水を加え湿らせながら混練することができる。水を加える方法は、公知の条件および手段を用いることができる。例えば、滴下、噴射、あるいは噴霧などの方法がある。混練には混練機を用いることができる。混練機としては、例えば、ナウターミキサー、リボンミキサー、ヘンシェルミキサー、ニーダーなどを挙げることができる。これらのうちニーダーが好ましい。 (Hydro-kneading process)
After this mixing step, kneading can be performed while adding water and moistening. Known methods and means can be used for the method of adding water. For example, there are methods such as dripping, jetting, or spraying. A kneader can be used for kneading. Examples of the kneader include a Nauter mixer, a ribbon mixer, a Henschel mixer, and a kneader. Of these, a kneader is preferable.
　混練において加える水は、特に制限されない。例えば、水道水、工業用水、蒸留水、イオン交換樹脂処理水、逆浸透膜（ＲＯ）処理水および限外ろ過膜（ＵＦ）処理水などの精製水、地下水、涌水、河川湖沼水などの天然水が挙げられる。混練の際に加えられる水の量は、混合物に対して、通常、３～７０重量％、好ましくは５～６０重量％である。混練時間は、製造のスケールおよび混練機の種類によって異なるが、好ましくは３分間～６０分間、より好ましくは５分間～２０分間である。 The water added during kneading is not particularly limited. For example, purified water such as tap water, industrial water, distilled water, ion exchange resin treated water, reverse osmosis membrane (RO) treated water and ultrafiltration membrane (UF) treated water, natural water such as ground water, flooded water, river lake water Water is mentioned. The amount of water added during kneading is usually 3 to 70% by weight, preferably 5 to 60% by weight, based on the mixture. The kneading time varies depending on the production scale and the type of the kneader, but is preferably 3 minutes to 60 minutes, more preferably 5 minutes to 20 minutes.
（造粒工程）
　次に、得られた混練物を造粒する。造粒機としては、例えば、バスケット式造粒機；横型押出し機、ツインドームグラン、シングルドームグラン、ペレタイザーなどの押出造粒機；ローラーコンパクターなどの圧縮造粒機などを挙げることができる。これらのうち押出造粒機が好ましい。押出粒径は、用いる原料および／または添加水分量によっても異なるが、０．２～２．０ｍｍが好ましく、０．５～１．２ｍｍがより好ましい。 (Granulation process)
Next, the obtained kneaded material is granulated. Examples of the granulator include a basket type granulator; an extrusion granulator such as a horizontal extruder, a twin dome gran, a single dome gran and a pelletizer; and a compression granulator such as a roller compactor. Of these, an extrusion granulator is preferred. The extrusion particle size varies depending on the raw materials used and / or the amount of added water, but is preferably 0.2 to 2.0 mm, more preferably 0.5 to 1.2 mm.
（乾燥整粒工程）
　上述の方法で得られた造粒物は、そのまま本発明の顆粒水和剤として用いることができるが、必要に応じて乾燥し、整粒しまたは分級して、本発明の顆粒水和剤として用いることができる。 (Dry sizing process)
The granulated product obtained by the above-mentioned method can be used as it is as the granule wettable powder of the present invention, but if necessary, it is dried, sized or classified and used as the granule wettable powder of the present invention. Can be used.
　乾燥工程は、混練工程等で添加した水分を除去でき、組成物が化学変化を起こさない限りにおいて特に制限されない。乾燥温度および乾燥時間は、添加した水の量および用いる装置によっても異なるが、通常、室温～１００℃、好ましくは４０℃～９０℃とすることができ、通常、２分間～３時間、好ましくは１０分間～１時間とすることができる。乾燥機としては、例えば、通気バンド乾燥機、撹拌乾燥機、流動層乾燥機、振動乾燥機、ベッド式乾燥機などを挙げることができる。 The drying process is not particularly limited as long as it can remove the water added in the kneading process and the like and the composition does not undergo a chemical change. The drying temperature and drying time vary depending on the amount of water added and the apparatus used, but can usually be room temperature to 100 ° C., preferably 40 ° C. to 90 ° C., usually 2 minutes to 3 hours, preferably It can be 10 minutes to 1 hour. Examples of the dryer include an aeration band dryer, a stirring dryer, a fluidized bed dryer, a vibration dryer, and a bed dryer.
　整粒機は、適当な粒径のものが得られる限りにおいて特に制限されない。例えば、ミートチョッパー（株式会社平賀工作所製）やドームグラン（不二パウダル株式会社製）などのスクリュー型押出機や、ロートプレックス（ホソカワミクロン株式会社製）などの竪型粉砕機、ロールグラニュレーター（日本グラニュレーター社製）などの架砕方式の解砕機、マルメライザー、ピンミルなどを挙げることができる。 The particle sizer is not particularly limited as long as an appropriate particle size can be obtained. For example, screw type extruders such as meat chopper (manufactured by Hiraga Kogaku Co., Ltd.) and Dome Gran (manufactured by Fuji Powdal Co., Ltd.), vertical crushers such as Rotoplex (manufactured by Hosokawa Micron Corporation), roll granulators ( Crushing type crushers such as Nippon Granulator Co., Ltd., Malmerizer, Pin Mill, etc. can be mentioned.
　分級機は特に制限されない。例えば、ジャイロシフター、電磁振動式篩別機などを挙げることができる。 Classifier is not particularly limited. Examples thereof include a gyro shifter and an electromagnetic vibration type sieving machine.
［顆粒水和剤の施用方法］
　本発明の顆粒水和剤は、水に投入し、分散希釈させた後、スプレー機などで作物や土壌などに施用することができる。水への希釈倍率は、顆粒水和剤中の農薬有効成分の種類、含有量、施用目的によって異なるが、通常は１０～１００００倍、好ましくは５０～８０００倍、より好ましくは５００～４０００倍である。
　希釈・懸濁に用いる水は、特に制限されず、軟水および硬水のいずれでもよい。例えば、水道水、工業用水、蒸留水、イオン交換樹脂処理水、逆浸透膜（ＲＯ）処理水および限外ろ過膜（ＵＦ）処理水などの精製水、地下水、涌水、河川湖沼水などの天然水が挙げられる。硬水は、例えば、ＣＩＰＡＣ（Collaborative International Pesticide Analytical Council；国際農薬分析法協議会）法で謂うCIPAC 標準水Ｄ（342ppm（Ｃａ2+：Ｍｇ2+＝４：１））を挙げることができるが、それに限定されない。 [Method of applying granule wettable powder]
The granule wettable powder of the present invention can be applied to crops, soil, and the like with a sprayer after being poured into water and dispersed and diluted. The dilution ratio in water varies depending on the type, content and application purpose of the active ingredient of the agrochemical in the granular wettable powder, but is usually 10 to 10,000 times, preferably 50 to 8000 times, more preferably 500 to 4000 times. is there.
The water used for dilution / suspension is not particularly limited, and may be either soft water or hard water. For example, purified water such as tap water, industrial water, distilled water, ion exchange resin treated water, reverse osmosis membrane (RO) treated water and ultrafiltration membrane (UF) treated water, natural water such as ground water, flooded water, river lake water Water is mentioned. Examples of hard water include CIPAC standard water D (342 ppm (Ca 2+ : Mg 2+ = 4: 1)), which is a CIPAC (Collaborative International Pesticide Analytical Council) method. It is not limited to it.
［顆粒水和剤の包装形態］
　本発明の顆粒水和剤は、アルミ袋、紙袋、紙パック、ポリボトルなど、通常の粒剤や水和剤で使用可能な容器や包装を使用することができる。保存時の吸湿を避けるためには、アルミ袋や内装がアルミコーテイングされた紙袋、ポリ袋、ポリボトルなどが好ましい。また、水溶性パックに梱包したものを、これらの吸湿を防止した袋に充填することにより、保存時の吸湿防止、安全性の向上、希釈時の取扱性を向上させることができる。 [Packaging form of granule wettable powder]
The granule wettable powder of the present invention can be a container or package that can be used with normal granules or wettable powder, such as aluminum bags, paper bags, paper packs, and plastic bottles. In order to avoid moisture absorption during storage, a paper bag, a plastic bag, a plastic bottle or the like with an aluminum bag or an interior coated with aluminum is preferable. In addition, by filling the bag packed in the water-soluble pack into a bag that prevents moisture absorption, it is possible to prevent moisture absorption during storage, improve safety, and handleability during dilution.
　以下に、実施例および比較例を示し、それによって本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, examples and comparative examples will be shown, and the present invention will be specifically described thereby, but the present invention is not limited to these examples.
（実施例１）
　イミノクタジンアルベシル酸塩（軟化点：６０℃）５０質量部をメタノール５０質量部に溶解した。この溶液を酸性ホワイトカーボン（塩野義製薬株式会社製の商品名「カープレックスＸＲ」）５０質量部と混合し、５０℃で加温してメタノールを留去した。得られた粉末状混合物をジェットミル（日本ニューマチック工業株式会社製の商品名「スーパーソニックジェットミルＰＪＭ」）を用いて粉砕して、イミノクタジンアルベシル酸塩を５０％含有する顆粒（プレミックス製剤）を得た。 Example 1
50 parts by mass of iminotadine albecyl salt (softening point: 60 ° C.) was dissolved in 50 parts by mass of methanol. This solution was mixed with 50 parts by mass of acidic white carbon (trade name “Carplex XR” manufactured by Shionogi & Co., Ltd.), heated at 50 ° C. to distill off methanol. The obtained powdery mixture was pulverized using a jet mill (trade name “Supersonic Jet Mill PJM” manufactured by Nippon Pneumatic Industry Co., Ltd.), and granules containing 50% iminoctadine albecyl salt (premix preparation) )
　シフルフェナミド（一般名／日本曹達社製；融点：約６２℃）３．４質量部、前記のプレミックス製剤４０質量部、塩基性ホワイトカーボン（ＤＳＬジャパン社製の商品名「カープレックス＃１１２０」）１０質量部、ポリカルボン酸ナトリウム（竹本油脂製の商品名「ニューカルゲンＷＧ－５」）２５質量部、ソルビトール５質量部、ジオクチルスルホサクシネートナトリウム（竹本油脂製の商品名「ニューカルゲンＥＸ－７０」（安息香酸ナトリウム３０％含有））３質量部、および塩化カリウム１３．６質量部を混合し、空気粉砕機（日曹エンジニアリング社製の商品名「ウルマックス」）で粉砕した。これに水４６．５質量部を加え、混練し、０．７ｍｍのスクリーンを用いて押出造粒し、５０℃の流動層乾燥機（ＦＲＥＵＮＤ/大川原製作所製　ＦＬＯＷ　ＣＯＡＴＥＲ　（ＦＬＯ－１））で３０分間乾燥し、次いで篩分し０．１５～０．５０ｍｍの篩に残った部分を分取して、顆粒水和剤を得た。 Siflufenamide (general name / manufactured by Nippon Soda Co., Ltd .; melting point: about 62 ° C.) 3.4 parts by mass, 40 parts by mass of the premix preparation, basic white carbon (trade name “Carplex # 1120” manufactured by DSL Japan) 10 parts by mass, 25 parts by mass of sodium polycarboxylate (trade name “New Calgen WG-5” manufactured by Takemoto Yushi), 5 parts by mass of sorbitol, sodium dioctylsulfosuccinate (trade name “New Calgen EX-70 manufactured by Takemoto Yushi” 3 parts by mass (containing 30% sodium benzoate) and 13.6 parts by mass of potassium chloride were mixed and pulverized with an air pulverizer (trade name “Ulmax” manufactured by Nisso Engineering Co., Ltd.). To this was added 46.5 parts by weight of water, kneaded, extruded and granulated using a 0.7 mm screen, and 30 with a fluidized bed dryer (FREEUND / Okawara Seisaku FLOW COATER (FLO-1)) at 50 ° C. Drying for a minute, then sieving, and separating the remaining part of the 0.15-0.50 mm sieve, a granular wettable powder was obtained.
（比較例１）
　塩基性ホワイトカーボン（ＤＳＬジャパン社製の商品名「カープレックス＃１１２０」）を酸性ホワイトカーボン（ＤＳＬジャパン社製の商品名「カープレックス＃８０」）に置き換えた以外は、実施例１と同じ操作を行い、顆粒水和剤を得た。 (Comparative Example 1)
The same operation as in Example 1 except that basic white carbon (trade name “Carplex # 1120” manufactured by DSL Japan) was replaced with acidic white carbon (trade name “Carplex # 80” manufactured by DSL Japan). To obtain a granulated wettable powder.
（比較例２）
　ソルビトールの量を０質量部、塩化カリウムの量を１８．６質量部に変えた以外は、実施例１と同じ操作を行い、顆粒水和剤を得た。 (Comparative Example 2)
Except for changing the amount of sorbitol to 0 parts by mass and the amount of potassium chloride to 18.6 parts by mass, the same operation as in Example 1 was performed to obtain a granular wettable powder.
（比較例３）
　塩基性ホワイトカーボン（ＤＳＬジャパン社製の商品名「カープレックス＃１１２０」）を酸性ホワイトカーボン（ＤＳＬジャパン社製の商品名「カープレックス＃８０」）に置き換えた以外は、比較例２と同じ操作を行い、顆粒水和剤を得た。 (Comparative Example 3)
The same operation as Comparative Example 2 except that basic white carbon (trade name “Carplex # 1120” manufactured by DSL Japan) was replaced with acidic white carbon (trade name “Carplex # 80” manufactured by DSL Japan). To obtain a granulated wettable powder.
　実施例および比較例で得られた顆粒水和剤の評価を下記の方法で行った。それらの結果を表１に示した。
（自己分散性の評価）
　１００ｍＬの水を入れると水面から底までの距離が約１８０ｍｍで空間容積が３０ｍＬとなる試験管に、農薬工程検査法に基づく３度硬水１００ｍＬを入れ、これに顆粒水和剤を静かに投入して、顆粒水和剤が底に沈むまでの状態を観察し、下記の基準にて判定した。
　○：顆粒水和剤が試験管の底に着くまでの間に崩壊が始まった。
　×：顆粒水和剤が試験管の底に着くまでの間には全く崩壊しなかった。
　○が自己分散性有りを、×が自己分散性無しを表す。○～×は、自己分散性を概ね有するが、一部の顆粒に自己分散性を有さない場合を表す。×～○は、自己分散性を概ね有さないが、一部の顆粒に自己分散性を有する場合を表す。 The granule wettable powder obtained in Examples and Comparative Examples was evaluated by the following method. The results are shown in Table 1.
(Evaluation of self-dispersibility)
When 100 mL of water is added, 100 mL of 3 degree hard water based on the pesticide process inspection method is added to a test tube whose distance from the water surface to the bottom is about 180 mm and the spatial volume is 30 mL. Then, the state until the granule wettable powder sinks to the bottom was observed, and judged according to the following criteria.
○: Disintegration started before the granular wettable powder reached the bottom of the test tube.
X: It did not disintegrate at all until the granule wettable powder reached the bottom of the test tube.
○ indicates that there is self-dispersibility, and × indicates that there is no self-dispersibility. O to X represent cases where the particles generally have self-dispersibility but some of the granules do not have self-dispersibility. X to ○ represent cases where some of the granules have no self-dispersibility but have self-dispersibility.
（崩壊性の評価）
　１００ｍＬの水を入れると水面から底までの距離が約１８０ｍｍで空間容積が３０ｍＬとなる試験管に、農薬工程検査法に基づく３度硬水１００ｍＬを入れ、これに顆粒水和剤を静かに投入した。投入から３０秒経過後、試験管を２秒に１回の割合で転倒、元に戻すの操作を繰り返し、顆粒水和物が完全に崩壊するまでの転倒回数（崩壊転倒回数という）を測定した。崩壊転倒回数が少ないほど崩壊性が良好である。 (Evaluation of disintegration)
When 100 mL of water is added, 100 mL of 3 degree hard water based on the pesticide process inspection method is added to a test tube whose distance from the water surface to the bottom is about 180 mm and the spatial volume is 30 mL, and the granule wettable powder is gently added thereto. . Thirty seconds after the addition, the test tube was tumbled once every 2 seconds, and the operation of returning the tube was repeated, and the number of falls until the granule hydrate completely disintegrated (called the number of collapses) was measured. . The smaller the number of collapse falls, the better the disintegration.
（沈降量（分散性））
　崩壊転倒回数の測定後に、更に試験管を２秒に１回の割合で転倒、元に戻すの操作を３０回繰り返した。転倒操作の繰り返し完了から３０分経過後、沈降量（ｍＬ）を測定した。沈降量が少ないほど分散性に優れる。 (Settling amount (dispersibility))
After the measurement of the number of collapses and falls, the operation of tumbling and returning the test tube at a rate of once every 2 seconds was repeated 30 times. After 30 minutes had elapsed since the completion of the overturning operation, the sedimentation amount (mL) was measured. The smaller the amount of sediment, the better the dispersibility.
（高温保管試験）
　実施例および比較例で得られた顆粒水和剤を、５４℃の恒温室に入れ、１４日間保管した。１４日間の高温保管後の顆粒水和剤について、上記と同じ方法で、自己分散性、崩壊性および沈降量の評価を行った。 (High temperature storage test)
The granule wettable powder obtained in Examples and Comparative Examples was placed in a constant temperature room at 54 ° C. and stored for 14 days. About the granule wettable powder after 14-day high temperature storage, self-dispersibility, disintegration, and the amount of sedimentation were evaluated by the same method as the above.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、製造直後においては、従来処方の顆粒分散剤でも自己分散性を有し、水中での崩壊性および分散性に優れている。しかし、高温保管後には、自己分散性が消失し、崩壊性および分散性が低下する。
　一方、本発明の顆粒分散剤は、高温保管後においても、自己分散性が維持されており、崩壊性および分散性の低下が小さい。
　本発明の顆粒水和剤は、高温下で保管した後においても、崩壊性および分散性が低下しないので、農園芸用の農薬として好適である。 As shown in Table 1, immediately after the production, the conventional granule dispersant has self-dispersibility and is excellent in disintegration and dispersibility in water. However, after high-temperature storage, the self-dispersibility is lost and the disintegration and dispersibility are reduced.
On the other hand, the granule dispersant of the present invention maintains its self-dispersibility even after high-temperature storage, and the degradation of disintegration and dispersibility is small.
The granule wettable powder of the present invention is suitable as an agricultural and horticultural agricultural chemical because its disintegration and dispersibility do not decrease even after storage at high temperatures.

Claims (4)

  1. 　融点または軟化点が７０℃以下の農薬有効成分、酸性ホワイトカーボン、塩基性ホワイトカーボン、ポリカルボン酸系界面活性剤および分子量が４００以下の糖類を含有する顆粒水和剤。 Granule wettable powder containing an agrochemical active ingredient having a melting point or softening point of 70 ° C. or less, acidic white carbon, basic white carbon, a polycarboxylic acid surfactant and a saccharide having a molecular weight of 400 or less.
  2. 　前記糖類が、グルコース、ソルビトール、ラクトース、シュークロースおよびマルトースからなる群から選ばれる少なくとも一種のものである請求項１に記載の顆粒水和剤。 The granule wettable powder according to claim 1, wherein the saccharide is at least one selected from the group consisting of glucose, sorbitol, lactose, sucrose and maltose.
  3. 　前記農薬有効成分がイミノクタジンアルベシル酸塩である請求項１または２に記載の顆粒水和剤。 The granule wettable powder according to claim 1 or 2, wherein the agrochemical active ingredient is iminoctadine albesylate.
  4. 　融点または軟化点が７０℃以下の農薬有効成分と酸性ホワイトカーボンとを混合してプレミックス製剤を得、該プレミックス製剤と塩基性ホワイトカーボンとポリカルボン酸系界面活性剤と分子量が４００以下の糖類とを混合し、得られた混合物を造粒することを含む、顆粒水和剤の製造方法。 An agrochemical active ingredient having a melting point or softening point of 70 ° C. or less and acidic white carbon are mixed to obtain a premix preparation, the premix preparation, basic white carbon, polycarboxylic acid surfactant, and a molecular weight of 400 or less. The manufacturing method of a granule wettable powder including mixing saccharides and granulating the obtained mixture.
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WO2017084946A1 (en) * 2015-11-18 2017-05-26 Basf Se High-payload granules containing a sulfosuccinate surfactant and a polycarboxylic acid

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CN105961380A (en) * 2016-05-14 2016-09-28 成都科利隆生化有限公司 Water dispersible granule and anhydrous preparation technology thereof
CN107889827A (en) * 2017-10-25 2018-04-10 江苏腾龙生物药业有限公司 A kind of 50% clothianidin wettable powder

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JP2002370903A (en) * 2001-06-13 2002-12-24 Kumiai Chem Ind Co Ltd Granular wettable powder
JP2005104959A (en) * 2003-01-23 2005-04-21 Nippon Soda Co Ltd Agricultural and horticultural water dispersible granule

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JP2014210760A (en) * 2013-04-05 2014-11-13 日産化学工業株式会社 Granular composition for agriculture
WO2017084946A1 (en) * 2015-11-18 2017-05-26 Basf Se High-payload granules containing a sulfosuccinate surfactant and a polycarboxylic acid

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