WO2000072674A1 - Formulation antiparasitaire solide à concentration élevée - Google Patents

Formulation antiparasitaire solide à concentration élevée Download PDF

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Publication number
WO2000072674A1
WO2000072674A1 PCT/JP2000/003376 JP0003376W WO0072674A1 WO 2000072674 A1 WO2000072674 A1 WO 2000072674A1 JP 0003376 W JP0003376 W JP 0003376W WO 0072674 A1 WO0072674 A1 WO 0072674A1
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Prior art keywords
concentration
agricultural chemical
water
molecular weight
solid preparation
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PCT/JP2000/003376
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English (en)
Japanese (ja)
Inventor
Kinji Tanizawa
Masakazu Tomioka
Tsuyoshi Hirata
Hiroshi Sabi
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Sankyo Company, Limited
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Publication of WO2000072674A1 publication Critical patent/WO2000072674A1/fr

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    • 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

Definitions

  • the present invention provides a suspension (slurry) containing a high concentration of a pesticidal active ingredient by blending a polyalkylene glycol-type nonionic surfactant containing a block of ethylene dalicol and propylene dalicol in the molecule.
  • High-concentration pesticide solid preparation obtained by wet-grinding and kneading and granulating the obtained suspension, a method for producing and using the same, and dispersing the high-concentration pesticide solid preparation into a water-soluble film or sheet. And a method for using the same.
  • pesticides have been formulated in various dosage forms, for example, powders, wettable powders, emulsions and granules, and sprayed on the water surface, soil and plants for the convenience of use.
  • the flowable agent for dusting without dispersion the flowable agent for paddy fields that can be processed without using a machine, and the so-called 1 kg granule that increases the active ingredient content in granules to reduce the amount of spraying as a formulation
  • dosage forms such as granular wettable powders with little dusting have come to be used frequently.
  • a solid agricultural chemical formulation is packaged in a water-soluble film, and this package can be processed simply by throwing from a ridge without entering a paddy field.
  • paddy field pesticide preparations JP-A-3-173802
  • JP-A-3-173802 paddy field pesticide preparations
  • Examples of such preparations for throwing into paddy fields include: (1) a large effervescent tablet directly thrown into a paddy field (Japanese Patent Laid-Open No. 6-170503); and (2) a small effervescent tablet is divided into water-soluble films. Wrapped in a paddy and thrown into a paddy field (Japanese Patent Laid-Open No. Hei 5-33991)
  • a water-soluble carrier such as potassium chloride is granulated together with a water-soluble film-forming polymer, and the pesticidal active ingredient is contained in the granulated water-soluble film.
  • Japanese Unexamined Patent Publication No. Hei 5-782807 4Agrochemical solid preparation prepared to float and spread on the water surface is packaged in a water-soluble film and thrown into a paddy field (JP-A-6-336) (Patent Document 4; Japanese Patent Application Laid-Open No. 5-339103), and an oil preparation having water surface spreading property is packed in a water-soluble container and thrown into a paddy field.
  • the production of the pesticide for rice paddy throwing into paddy fields involves a process of packaging in small sachets, which tends to increase production costs.To reduce costs, make a high-content formulation and treat it in unit area. It is necessary to reduce the number of sachets and the number of sachets to be thrown. For this reason, it is necessary to wet-pulverize the suspension with the highest possible content, but the wet-grinding using a conventionally known surfactant has never been able to grind a satisfactory content.
  • the present inventors can wet-pulverize a pesticidal active ingredient at a concentration as high as possible in a suspended state, and particularly produce a pesticide preparation for throwing into paddy fields.
  • a thorough study was conducted in search of a pulverization aid that would not adversely affect the spreadability of the formulation on the water surface when thrown into a paddy field.
  • a polyalkylene glycol type nonionic surfactant containing ethylene glycol and propylene glycol in the form of a block in the molecule, a suspension containing a high concentration of the pesticide active ingredient can be obtained.
  • Suspension liquid can be pulverized with low viscosity without gelling, and it does not adversely affect the water surface spreader contained in paddy rice throwing pesticide prepared by kneading and granulating the obtained pulverized suspension.
  • the present inventors have found that the paddy field pesticide preparation exhibits good spreadability, and completed the present invention.
  • the present invention
  • a suspension containing a high concentration of pesticidally active ingredients was obtained by blending a polyalkylene glycol-type nonionic surfactant containing a block of ethylene glycol and propylene dalicol in the molecule, and was obtained by wet grinding. By mixing and granulating the suspension High concentration pesticide solid preparation obtained,
  • a suspension containing a high concentration of pesticidally active ingredients is obtained by blending a polyalkylene glycol-type nonionic surfactant containing a block of ethylene dalicol and propylene dalicol in the molecule, and wet-pulverizing the suspension.
  • a method for producing the high-concentration agricultural chemical solid preparation which comprises kneading and granulating the suspension.
  • Paddy field pesticide formulation in which the high-concentration pesticide solid formulation is packaged in a water-soluble film or sheet,
  • a polyalkylene dalicol-type nonionic surfactant containing ethylene dalicol and propylene glycol in a molecule in a molecule includes, for example, higher alcohols, alkylphenols, fatty acids, higher aliphatic amines or Ethylene oxide (hereinafter referred to as E0) and propylene oxide (hereinafter referred to as P0) are added to the hydroxyl group, carboxyl group, amino group or amide group of fatty acid amides in the molecule.
  • the hydroxyl group at the terminal to which E0 or P0 is added may be a hydroxyl group, or may be a suitable alcohol (such as The alcohol may be, for example, a linear or branched unsaturated or saturated aliphatic alcohol having 1 to 18 carbon atoms, Suitably, it is a straight-chain or branched-chain saturated aliphatic alcohol or oleyl alcohol having 6 to 12 carbon atoms, or may form an ether, or an organic acid (the organic acid is For example, it may be a linear or branched unsaturated or saturated fatty acid having 1 to 18 carbon atoms, preferably a linear or branched saturated fatty acid having 6 to 12 carbon atoms.
  • the terminal When there are a plurality of hydroxyl groups, each hydroxyl group may optionally form an ether bond or an ester bond.
  • the polyalkylene glycol type nonionic surfactant 1 containing ethylene glycol and propylene glycol in a block in the molecule of the present invention preferably has the following formula:
  • R 1 represents a hydrogen atom, a higher alcohol residue, an alkyl phenol residue, an aryl fuynol residue, a fatty acid residue, a higher aliphatic amide residue or a fatty acid amide residue
  • xl, x 2, X 3 and X 4 each independently represent an integer of 4 or more and 900 or less
  • yl, y 2, y 3 and y 4 each independently represent an integer of 16 or more and 130 or less (preferably Is an integer of 16 or more and 70 or less.)
  • the higher alcohol residue is a straight or branched chain having 4 to 18 carbon atoms.
  • a branched alcohol residue for example, a butyl alcohol residue, a hexyl alcohol residue, an ethylhexyl alcohol residue, a lauryl alcohol residue or an oleyl alcohol residue; It is an alcohol residue or a radical alcohol residue.
  • the alkylphenol residue is a phenol residue in which the same or different 1 to 3 linear or branched alkyl groups having 3 to 9 carbon atoms are bonded, for example, tributylphenol
  • the residue may be a methylhexylphenol residue or a nonylphenol residue, and is preferably a noylphenol residue.
  • the arylphenol residue has 1 to 3 styryl groups bonded thereto, and 1 or 2 identical or different linear or branched alkyl groups having 1 to 4 carbon atoms bonded thereto. And may be, for example, a monostyrylphenol residue, a distyrylphenol residue, a tristyrylphenol residue or a distyrylcresol residue, preferably a tristyrylphenol residue. .
  • the fatty acid residue is a saturated or unsaturated fatty acid residue having 2 to 18 carbon atoms, for example, an acetic acid residue, a butyric acid residue, a lauric acid residue or an oleic acid residue. It is preferably a lauric acid residue.
  • the higher aliphatic amine residue is a saturated or unsaturated aliphatic amine residue having 4 to 18 carbon atoms, for example, hexylamine residue, ethylhexylamine residue, laurylamine residue. Or a oleylamine residue, preferably a lauramine or oleylamine residue.
  • the fatty acid amide residue is a saturated or unsaturated fatty acid amide residue having 4 to 18 carbon atoms, such as a butyric acid amide residue, a lauric acid amide residue, or oleic acid. It may be an amide residue, preferably a lauric acid amide residue.
  • the compounds (1) and (2) are those in which R 1 is a hydrogen atom and are nonionic surfactants called a pluronic type, and the compounds (3) and (4) are called a tetronic type Nonionic surfactant.
  • R 1 is a hydrogen atom and are nonionic surfactants called a pluronic type
  • the compounds (3) and (4) are called a tetronic type Nonionic surfactant.
  • the relationship between the compounds (1) and (2) and the compounds (3) and (4) is such that the addition positions of E0 and P0 are reversed.
  • These compounds are surfactants commonly used as auxiliaries for pesticides, have low toxicity, are less harmful, have less environmental impact, It has features such as being less affected by pH.
  • R 1 is preferably a hydrogen atom.
  • the polyalkylene dalicol type nonionic surfactant containing ethylene dalicol and propylene dalicol in the molecule used in the present invention in a block shape is more preferably a polyalkylene glycol type nonionic surfactant.
  • the molecular weight of the propylene dalicol portion (P0 added portion) is 2000 to 400, and the molecular weight of the ethylene dalicol portion (E0 added portion) with respect to the molecular weight of the propylene dalicol portion (P0 added portion) It is a polyalkylene glycol type nonionic surfactant having a ratio of 0.05 to 10 times, and even more preferably, the molecular weight of the propylene glycol portion of the polyalkylene glycol type nonionic surfactant is 25.
  • the ratio of the molecular weight of the ethylene glycol moiety to the molecular weight of the propylene glycol moiety is 0.000 to 350.
  • the compound (1) is 1 to 4 times, and R 1 is a hydrogen atom.
  • R 1 is a hydrogen atom.
  • the molecular weight of the propylene dalicol moiety is 2700 to 3200, and the propylene glycol moiety is The ratio of the molecular weight of the ethylene glycol moiety to the molecular weight of
  • the above molecular weight may represent not only the molecular weight of one molecule but also the average molecular weight of a plurality of molecules.
  • the viscosity of the suspension does not increase even if the concentration of the pesticidal active ingredient is high, and a considerably high concentration suspension is used as described below.
  • the suspension can be wet-pulverized, and the resulting suspension can be kneaded and granulated to produce a high content of granules.
  • these surfactants are added to granules that float and spread on the water surface, they only have a small degree of hindrance to the action of the water surface spread agent used at the same time. It can be blended with paddy field throwing pesticide formulations that are packaged in water-soluble films.
  • the above-mentioned nonionic surfactant is suspended in water together with the active ingredient of the pesticidal active ingredient, and further, if necessary, together with a grinding aid such as a dispersing agent or a wetting agent. It can be crushed in the same way.
  • the wet pulverizer used for such wet pulverization is generally a pulverizer used for wet pulverization of pesticides, for example, an attrition mill such as an attritor; a vertical mill such as an apex mill, a dyno mill, and a sand mill. It can be a horizontal bead mill; a hammer mill such as a wet atomizer; or a colloid mill, preferably an atrition mill or a bead mill.
  • an attrition mill such as an attritor
  • a vertical mill such as an apex mill, a dyno mill, and a sand mill. It can be a horizontal bead mill; a hammer mill such as a wet atomizer; or a colloid mill, preferably an atrition mill or a bead mill.
  • the pesticidal active ingredient used in the present invention is generally used as a pesticide, and is not particularly limited as long as the drug substance is solid at room temperature.
  • ordinary pesticides, fungicides, herbicides, or plant regulators Preferably, a fungicide or a herbicide, more preferably, a herbicide.
  • the stability to water is not extremely poor, and the solubility in water is high. No or melting point higher than 30 ° C.
  • insecticides used in the present invention include, for example, trichlorfon, monocrotophos, acephate, canolevofuran, bensnorepap, buprofezin, methorne canoleb, propoxure, imidacloprid, acetamiprid, milbemectin, carbaryl, chlorfluaz Ron, dimethylvinphos or pyrimidifen, preferably buprofezin, imidacloprid, acetamiprid, milbemectin or pyrimidifen.
  • the fungicides used in the present invention include, for example, fusalide, iprodione, probenazole, isoprothiolane, tricyclazole, pyroquilon, carpropamide, oliburite, azoxystrobin and 7-fluoro-1,2,5. , 6-Tetrahydro-14H-pyrro [3.2.1-j] Quinoline-141-one and other blast agents; diclomedin, flutolanyl, mepronil, tifluzamide, flametopyr, 2- (4-phenol) Orophenyl) 1- (1H-1,2,4-1triazole-11-yl) -13-Trimethylsilylpropan-12-ol, peniculon, etc.
  • fungicides such as clofphthalam, benomyl, metalaxyl, maneb, zineb, thiadiazine, thiuram, polycarbamate, capyatan, TPN, thiophanatemethyl, vinclozolin, fluazinam, PCNB, triazine, chlorothaloninole and carboxin,
  • it is fusalide, probenazole, isoprothiolane, carpropamide, olibulite, azoxystrobin, diclomedin, flutranil, tifluzamide, flametopyr or techmouth phthalam.
  • herbicides used in the present invention include, for example, pyrazolate, benzofenap, birazoxifen, pyribuchicarp, bromobutide, mefenacet, bensnoreflon-methinole, chronolenitrofen, clometoxifene, dimelon, bifenoxazirazone, naprooxadizone, naprooxadizone, naprooxadizone Pirate, dichopyr, imazos noreflon, quinoclamin, MCPA, 2, 4-D, MCPB, kink mouth rack, bilazosulfuron monoethinole, pentoxazone, teni / claw, cumino ⁇ , sinosnoreflon, simetrin, Sihalofop-Butinore, Etobenzad, Cahuens Tronoré, Ethoxysnoreflon, Azimsn
  • a non-cropland herbicide preferably pyrazolate, benzofenap, virazoxyfe , Piribuchikalp, Bromobutide, Mefenacet, Bensnoleflon-Methinole, Daimron, Oxazianoreginore, Imazosnolefin, Birazosnolefron-etinole, Pentoxazone, Cafuenstronole, Inethoxysulfuron, Inethoxysulfuron Oxadiclomephone, NBA061 or Benzovisik.
  • the plant regulator used in the present invention includes, for example, Inabenfide, Parkou Butorazo Or Nikonazol.
  • wet grinding of a high-concentration suspension is a wet grinding of a suspension having a concentration of an agricultural chemical active ingredient that exceeds the limit of the concentration that can be ground using an ordinary surfactant.
  • the concentration of the pesticidal active ingredient in the suspension to be wet-pulverized varies depending on, for example, the physical properties of the pesticidal active ingredient and the presence and type of grinding aids such as dispersants and wetting agents. 0% by mass, the higher is more efficient.
  • the wet pulverization of the present invention is 80 mass depending on the combination of the pesticidally active ingredient and the nonionic surfactant used. / 0 than are possible grinding of high concentration suspensions, for example, it is possible to grind the suspension Nigoeki is 8 5 wt% pesticide active ingredient, in this case, of course agrochemical active ingredient is 3 0 Grinding of the suspension, which is 880% by weight, is also possible.
  • the concentration of the pesticidal active ingredient in the suspension that can be wet-pulverized differs depending on the type of pesticidal active ingredient.
  • the conventional method requires that the pesticide content be in the suspension.
  • the content is at most 60 to 65%
  • the use of diclomedine is at most 50%
  • the use of pyrimidiphene is at most 45%
  • the wet-millable pesticide of the present invention is The maximum concentration of active ingredient in suspension is 85% for virazolate, 70% for diclomedine and 65% for pyrimidifen, as described below.
  • dispersant used in the wet milling examples include lignin sulfonate, (alkyl) naphthalene sulfonate and its condensate, phenol sulfonate and its condensate, styrene sulfonate condensate, maleic acid and styrene Salts of condensates with sulfonic acid, salts of carboxylic acid condensates such as acrylic acid and maleic acid, polyacrylic acid salts, salts of acrylic acid and maleic acid copolymers, maleic anhydride and methyl vinyl ether
  • Nonionic surfactants with common ethylene oxides such as copolymer salts, alkyl benzene sulfonates, dialkyl resulfosuccinates, lauryl sulfate salts, polyoxyethylene alkylaryl ether sulfates Sulfuric acid ester, polyoxyethylene alkyl aryl ether phosphate
  • the mixing amount of the above-mentioned dispersant or the above-mentioned dispersant and the wetting agent is usually 0.01 to 30% by mass in the suspension at the time of wet pulverization, and preferably 0.03 to 30% by mass.
  • the content is preferably from 10 to 10% by mass, more preferably from 0.1 to 5% by mass.
  • the pesticide preparation of the present invention when the high-concentration pesticide solid preparation of the present invention is subjected to so-called frame spraying or sprinkling treatment, and when the pesticide formulation for paddy field injection of the present invention is spouted or cast, the pesticide preparation is locally dispersed in the paddy field. It is necessary to spread the granules on the water surface with the power of the water surface spreader to exert the effect on the entire paddy field.However, if a large amount of the above dispersant is used, the water surface The spreading agent and the above-mentioned dispersant may antagonize. Therefore, as the dispersant used in the present invention, it is necessary to select and use a surfactant that does not antagonize the water surface spreader and the like.
  • the high-concentration pesticidal solid preparation of the present invention has a force S that can add other auxiliaries and liquid active ingredients, etc., as needed, during wet pulverization of the pesticidal active ingredient. It is necessary to select and use components that do not antagonize.
  • the suspension obtained by wet-grinding the solid pesticidal active ingredient thus obtained is, for example, an appropriate bulking agent, binder, disintegrant / dispersant, wetting agent, granulation improver, stabilizer, efficacy enhancer, drug It is mixed with a harm reducing agent, a floating agent, a water surface spreader, and other dry-ground active pesticide active ingredients, and if necessary, kneaded by adding water.
  • Wet granulation can be performed using a granulator.
  • these extenders, binders, disintegration agents *, dispersants, wetting agents, granulation improvers, stabilizers, potency enhancers, safeners, suspending agents and other active ingredients of agricultural chemicals do not compete with each other.
  • the extender used in the present invention is not particularly limited as long as it is generally used as a carrier for agricultural chemicals.
  • fine particles of mineral substances such as clay, calcium carbonate, diatomaceous earth, amorphous silicon dioxide, talc and bentonite
  • Plant powders such as starch, wood flour, ogatazu, coffee bean powder, tub flour, cellulose powder, microcrystalline cellulose, rice husk powder, rice bran, bran and coconut husk powder
  • water-soluble water such as urea, potassium chloride, ammonium sulfate and borate
  • a water-soluble saccharide such as sugar, lactose and glucose, and is preferably a mineral fine powder or a vegetable powder.
  • the amount of the extender used varies depending on the type and amount of the other auxiliaries, but is usually 0.1 to 80 mass in the high-concentration agricultural solid preparation. /. And preferably 1 to 50% by mass.
  • the high-concentration pesticide solid preparation of the present invention can contain a binder for imparting hardness to the preparation when the high-concentration pesticide solid preparation is prepared by granulating a powder material.
  • the binder used depends on whether the high-concentration pesticide solid preparation should disintegrate in water or not, but if it is preferable to disintegrate, for example, dextrin having a relatively low molecular weight can be used.
  • Polyvinylpyrrolidone salts of polyacrylic acid or salts of carboxymethylcellulose, polyvinyl alcohol, ligninsulfonic acid salts with relatively low molecular weight and low testability, water-soluble polymer substances such as gum arabic or bentonite Etc., preferably a low molecular weight dextrin, a low molecular weight carboxymethyl cellulose salt, a lignin sulfonic acid salt, or a bentonite, preferably a non-disintegrating one.
  • examples include starch; water-soluble starch, dextrin, pregelatinized starch, and various other starches.
  • a conductor or a relatively high molecular weight polyvinylpyrrolidone, a salt of polyacrylic acid, a salt of carboxymethylcellulose or polyvinyl alcohol, preferably a water-soluble starch, dextrin, pregelatinized starch or other starch derivative. is there.
  • the amount of the binder to be used varies depending on the composition of the formulation, the granulation method, the size of the granules, and the like, but it is usually 0.1 to 30% by mass in the high-concentration solid agricultural chemical formulation. Is 0.5 to 20% by mass.
  • the high-concentration agricultural chemical solid preparation of the present invention can contain a disintegrating / dispersing agent for disintegrating the particles in water and suspending / dispersing the active ingredient in water.
  • Disintegration agent used Is often, preferably, an anionic surfactant.
  • the disintegrating and dispersing agents used can be common, and these disintegrating and dispersing agents are often useful as wetting agents.
  • the disintegrating and dispersing agents and wetting agents are not limited to these, and nonionic, cationic or zwitterionic surfactants may be suitable.
  • starch carboxymethylcellulose, carboxymethylated starch and their salts, crosslinked products of polybutylpyrrolidone, microcrystalline cellulose, superabsorbent resins and the like having a property of absorbing water and expanding can be used as a disintegrant.
  • the amount of the disintegrant or wetting agent is usually a high concentration agrochemical solid formulation, 0. 0 1-3 0 weight 0 /. It is preferably from 0.3 to 20% by mass, and more preferably from 0.05 to 10% by mass.
  • a granulation enhancer can be used to improve the granulation of the high-concentration agricultural chemical solid preparation.
  • the granulating agent used may be a surfactant generally used as a granulating agent in pesticide granules or a material having a viscosity that imparts plasticity to the composition.
  • Nonionic surfactants such as aryl ethers, polyoxyethylene alkyl esters, and polyoxyethylene aryl aryl ethers; sodium salts of dialkyl sulfosuccinates, and sodium salts of alkyl benzene sulfonic acid Anionic surfactants; mineral fines such as bentonite; starch derivatives such as dextrins and arsenic starch; natural gums such as gum arabic; cellulose derivatives such as sodium salt of carboxymethylcellulose; And water-soluble, such as sodium salt of polyacrylic acid It can be a synthetic polymer, preferably an anionic surfactant or bentonite.
  • the amount of the granulation enhancer to be used varies depending on the type of the granulation enhancer and the kind and amount of other auxiliaries. % By mass, and preferably 0.05 to 20% by mass. /. And more preferably 0.1 to 10% by mass.
  • the high-concentration agricultural chemical solid preparation of the present invention can contain a stabilizer, if necessary, for stabilization of the pesticidal active ingredient or physical stability in the high-concentration agricultural chemical solid preparation.
  • Stabilizers used include, for example, pH regulators, antioxidants, light stabilizers and solid acid There may be a body base activity remover.
  • the amount of the stabilizer to be used is usually 0.01 to 5% by mass, and preferably 0.01 to 2% by mass, in the high-concentration solid agricultural chemical formulation. /. It is.
  • the high-concentration agricultural chemical solid preparation of the present invention may contain an efficacy enhancer such as, for example, piperonyl butoxide, as necessary, in order to maximize the efficacy of the agricultural chemical active ingredient.
  • an efficacy enhancer such as, for example, piperonyl butoxide
  • the high-concentration agricultural chemical solid preparation of the present invention can contain a safener if necessary.
  • the compounding amount of the potency enhancer or safener used depends on the type and amount of the pesticidal active ingredient.
  • the amount is usually 0.1 to 10 times the amount of the pesticidal active ingredient, and preferably 0 to 10 times. 5 to 5 times the amount.
  • the high-concentration pesticide solid preparation of the present invention may be used as it is or may be formed into a paddy throw-in preparation, and may be locally treated without uniformly treating the pesticide throughout the paddy field, for example, in a frame treatment, a spout treatment, and a throw-in treatment described below.
  • a water-floating agent can be included to spread the solid formulation on the surface of the water and spread the active agricultural chemical throughout the paddy field.
  • the water-floating agent used is, for example, mineral substances such as foamed shirasu, foamed perlite, foamed pumice and calcined vermiculite; plant materials such as konolek, wood flour and cellulose; foamed synthetic resins such as styrofoam; Synthetic resin powder such as; plastic hollow body (for example, Matsumoto Microsphere F30E); synthetic resin granule; or a mixture thereof, preferably cork, wood powder, and foamed silica.
  • the amount of the water-floating agent used depends on, for example, the type and formulation of the water-floating agent and the particle size of the solid product, but may be any amount sufficient to allow the high-concentration pesticide solid product to float on the water surface.
  • a high concentration agrochemical solid formulation 0.0 1-9 0 wt% Deari, preferably, a 0.1 to 7 0 wt%, more preferably, 0.5 to 6 0 mass 0 It is.
  • the high-concentration agricultural chemical solid preparation of the present invention can contain a water surface spreader to improve the spread of the high-concentration agricultural chemical solid preparation on the water surface.
  • water surface spreader examples include (co) polymers of carboxylic acids such as acrylic acid and maleic acid, acrylic acid, and maleic acid.
  • Polycarboxylic acid-type polysoaps such as sodium, potassium, ammonium and other polymer salts obtained by copolymerizing styrene snorenoic acid, vinyl groups, etc.
  • potassium sodium stearate Stones such as dialkyl sodium snolefosuccinate, sodium dodecylbenzenesulfonate, sodium laurinoleate, perfluoroalkylcarboxylate, ⁇ -olefinsulfonic acid salt, ⁇ -sulfofatty acid salt, oleyl
  • anionic surfactants such as salts of methyl tauride; polyoxyethylene alkyl aryl ethers, polyoxyethylene aryl aryl ethers, polyoxyethylene alkynole esters, alkyl esters of sonolebitan Alkylene oxide like
  • Nonionic surfactants of the type added with silicone various nonionic surfactants such as silicone surfactants and acetylene surfactants; these nonionic surfactants are esters of phosphoric acid or sulfuric acid, and in some cases, Surfactants neutralizing them with a suitable solvent; surfactants containing a fluorine atom in the molecular
  • acetylene-based surfactants, silicone-based surfactants, and surfactants containing a fluorine atom in the molecular structure are particularly good as water surface spreaders.
  • a general surfactant is used in combination, the water surface spreadability often decreases, and it is desirable that the amount of the surfactant be kept to a minimum.
  • the polyalkylene dalycol type nonionic surfactants containing ethylene glycol and propylene glycol in the molecule of the present invention in a block form are not limited to these water surface spreading. It has the characteristic that it has no adverse effect on the vehicle.
  • the amount of the water surface spreader used is, for example, the type and content of the pesticidal active ingredient, the type and content of the water surface spreader and the formulation and formulation of the other components, such as the type and amount. Usually, it is 0.01 to 10% by mass, and preferably 0.1 to 5% by mass in the high-concentration agricultural chemical solid preparation. /. And more preferably 0.2 to 3 mass. /. It is.
  • the high-concentration agricultural chemical solid preparation of the present invention can be prepared by the following method.
  • the high-concentration agricultural chemical solid preparation of the present invention can be obtained by kneading and granulating a high-concentration suspension of an agricultural chemical active ingredient that has been wet-pulverized by the above-mentioned method together with other auxiliaries.
  • the granulator used can be, for example, an extrusion granulator such as a side-pressing, pre-pressing or basket type, a mixing granulator, a tumbling granulator, a fluidized-bed granulator and a spray dryer. If foam contains shirasu or foamed perlite, pressurizing them strongly may collapse the balloon and reduce buoyancy.If cork is contained, pressurizing the foam will reduce buoyancy. Therefore, a granulator that does not require strong pressure or shearing force is preferred.
  • the obtained wet granules are subjected to, for example, drying, sizing, and sieving steps to obtain target granules.
  • the granule obtained is too large, drying of the granules becomes difficult.
  • the granule is The surface of the water is susceptible to the effects of the wind. If the particles are hydratable, if the particles are too large, the dispersion of the active pesticide in water will be slow.If the particles are too fine, the workability for dispensing will deteriorate. It is usually from 0.1 to 5 mm, preferably from 0.3 to 3 mm, and more preferably from 0.5 to 2 mm, as it may cause dusting during use. .
  • the shape of the particles is not particularly limited, and may be, for example, a columnar shape, a spherical shape, and an irregular shape.
  • the apparent specific gravity of the high-concentration pesticide solid preparation of the present invention is usually 0.000 when the high-concentration pesticide solid preparation is a water-floating granule in terms of ease of handling, productivity, and ease of floating on the water surface. It is from 0.5 to 0.50, preferably from 0.2 to 0.45, and more preferably from 0.25 to 0.40.
  • the high-concentration pesticide solid preparation of the present invention may be dissolved in a solvent or an emulsifier if necessary to prepare a concentrated preservative.
  • a mix can be prepared and absorbed into the granules obtained by the above method to produce the mixture.
  • the concentrated premix can optionally contain, for example, a water surface spreader, a stabilizer, an emulsifier, a dispersant, a wetting agent, and a solvent.
  • the pesticidal active ingredient is absorbed together with other auxiliaries into a carrier having a high oil-absorbing property, such as amorphous synthetic silica, diatomaceous earth, calcium silicate, a highly oil-absorbing resin and a highly oil-absorbing dextrin, or If a solid solution is formed with a resin, chemical substance or other solid pesticide active ingredient that is compatible with the ingredient, and this is crushed, it can be handled in the same manner as a solid pesticide active ingredient.
  • a carrier having a high oil-absorbing property such as amorphous synthetic silica, diatomaceous earth, calcium silicate, a highly oil-absorbing resin and a highly oil-absorbing dextrin, or If a solid solution is formed with a resin, chemical substance or other solid pesticide active ingredient that is compatible with the ingredient, and this is crushed, it can be handled in the same manner as a solid pesticide active ingredient.
  • the high-concentration pesticidal solid preparation of the present invention provides a solid pesticidal active ingredient when a solid pesticidal active ingredient and a liquid pesticidal active ingredient, a liquid pesticidal active ingredient, or a low-melting pesticidal active ingredient are used simultaneously.
  • the ingredients and other pesticidal active ingredients are ground together to prepare a so-called suspension emulsion, which is mixed and kneaded with other raw materials in the same manner as the above-mentioned suspension of the solid raw material, and granulated. It is possible to manufacture.
  • the high-concentration agricultural chemical solid preparation of the present invention is produced by an absorption method
  • the previously prepared granules are charged into the above-mentioned stirring mixer, and the liquid or liquefied agricultural chemical active ingredient or a concentrated premix thereof is mixed with stirring.
  • a method of absorbing is common.
  • the premix can optionally contain, for example, a water surface spreader, a solvent, an emulsifier, and a stabilizer.
  • the high-concentration agricultural chemical solid preparation of the present invention may contain a solvent, if necessary, to dilute the liquid drug substance or to make the low-melting drug substance liquid.
  • the solvents used are soluble in the drug substance, do not affect the stability of the drug substance, have a high boiling point, low toxicity and low flammability, and include, for example, paraffinic, aromatic and High-boiling solvents such as naphthenes; fatty acids obtained from various animal and vegetable oils such as oleic acid, maleic acid, fumaric acid and coconut oil used as plasticizers; esters such as phthalic acid, adipic acid and phosphoric acid; And vegetable oils such as rapeseed oil; or animal oils such as whale oil and sardine oil.
  • the solvent used is preferably liquid paraffin or low molecular weight polybutene.
  • the amount of solvent used depends on the type and physical properties of the pesticidal active ingredient, but should be as small as possible as long as it does not affect the stability over time or physical properties of the solid preparation. For 1 part, the amount is 0.1 to 50 parts, preferably 0.2 to 10 parts.
  • the high-concentration pesticidal solid preparation of the present invention can contain an emulsifier for emulsifying the pesticidal active ingredient in water, and such an emulsifier can be used in the same manner as selecting an emulsifier for an emulsion. Can be selected and used according to the type and physical properties.
  • the emulsifier used is different from a usual emulsifier and does not artificially stir when a pesticidal solid preparation is used. Therefore, the emulsifier preferably has a self-emulsifying property as much as possible and performs fine emulsification.
  • the amount of the emulsifier to be used is usually 0.01 to 10 parts with respect to 1 part of the liquid to be emulsified consisting of the liquid pesticidal active ingredient or the pesticidal active ingredient diluted or dissolved in a solvent. There are 0.03 to 3 parts.
  • the high-concentration pesticide solid preparation of the present invention is manufactured by the coating method
  • previously prepared grain nuclei are charged into a stirring mixer, and if necessary, a liquid binder is added to wet the surface of the grain nuclei.
  • a concentrated premix of the pesticidal active ingredient is added, and the mixture is further stirred and mixed to coat the surface of the grain nucleus with the pesticidal active ingredient.
  • the stirring mixer used can be, for example, a Nauta mixer, a ribbon blender, a rotary blender or a V-type mixer, preferably a low-speed mixer with less crushing of particles.
  • the high-concentration pesticide solid preparation of the present invention is manufactured using the granulation method, the coating method, and the absorption method, the necessary steps among the steps of granulation, coating, and absorption are performed at one time. It may be carried out in two or more stages as necessary.For example, a part of the active pesticide is kneaded and granulated to obtain a floating granule, and the remaining pesticide is effective.
  • the water-spreading agent may be coated or absorbed on the surface of the buoyant granules prepared by the granulation method, and the coating method and the absorption method may be applied to the same formulation. You may.
  • the high-concentration agricultural chemical solid preparation of the present invention can be used as follows.
  • the high-concentration agricultural chemical solid preparation of the present invention can be, for example, a granule, a granular wettable powder or a fine granule, and is preferably a granule or a granular wettable powder.
  • the high-concentration pesticide of the present invention When using the high-concentration pesticide solid formulation of the present invention as a paddy field pesticide, the high-concentration pesticide of the present invention
  • pesticide solid preparations When pesticide solid preparations are granules, they can be evenly sprayed into the paddy field from the ridge without using a machine or using a spraying machine, as in the case of general granules.
  • the high-concentration agricultural chemical solid preparation of the present invention can be subjected to a transfer treatment (frame treatment) from a ridge to a paddy field, a pouring treatment along with an inflow of irrigation water from a water mouth portion of a paddy field (water mouth treatment), or an appropriate water solubility. Separate into films and throw the resulting packages into paddy fields from the ridge.
  • the high-concentration pesticide solid preparation of the present invention is a water-dispersible granule
  • the water-dispersible granule is diluted with a small amount of water at the time of use to prepare a suspension.
  • pesticides can be sprayed by, for example, uniform spraying in a paddy field, frame treatment, water mouth treatment, and air spraying using a helicopter or the like.
  • the high-concentration pesticide solid preparation of the present invention is used as a pesticide other than for paddy fields
  • the high-concentration pesticide solid preparation of the present invention when used as a pesticide other than for paddy fields, when the high-concentration pesticide solid preparation of the present invention is granules, the granules can be uniformly dispersed in the same manner as general granules. It can be used as a high-concentration small amount of sprayable granules for labor-saving spraying.
  • the high-concentration agricultural chemical solid preparation of the present invention is a water-dispersible granule
  • the water-dispersible granule is diluted with water at the time of use to prepare a suspension, and the suspension is prepared in the same manner as the flowable.
  • the water-soluble film is a film that dissolves or disperses in water and has spreadability.
  • the raw material of the film may be, for example, polyvinyl alcohol or a derivative thereof, a pullulan film or a polyethylene oxide or a derivative thereof, and is preferably spreadable water-soluble paper, and more preferably, a polyvinyl alcohol or a derivative thereof.
  • Film or sheet (hereinafter abbreviated as PVA film).
  • the PVA film was formed into a film or a sheet of polyvinyl alcohol having a degree of polymerization of 500 to 200 and a saponification degree of 80 to 98% together with a small amount of a plasticizer and a stabilizer. And films or sheets containing a small amount of a copolymer such as carboxylic acid and sulfonic acid in the polymer.
  • a water-soluble film must have high mechanical strength and cold-resistance strength and be water-soluble. In that sense, the degree of polymerization of the raw material polyvinyl alcohol is too high or the saponification degree is low. If it is too high, it will be difficult to dissolve in cold water.
  • the thickness of the water-soluble film depends on the strength of the film and the dissolution time, but is usually 20 to 80 m, preferably 30 to 50 m.
  • the end of the water-soluble film may be sealed with glue, but there is a problem in workability, and the glued portion may be difficult to dissolve.
  • a material that can be heat-sealed is preferable.
  • the weight of the sachet for throwing into a paddy field is usually 10 to 200 g per pack, preferably 20 to 100 g, more preferably 25 to 100 g. ⁇ 60 g. With this weight, even a child, woman or elderly person can easily throw the sachet into a target point within 15m. If the package is heavier than this, it will be difficult to throw it in and it will not be easy to process it over a large area.If the package is smaller than this, the package will reach the target point due to the wind. It becomes difficult to do.
  • the solid pesticidal formulation floating on the water surface of the present invention spreads widely on the water surface and the active ingredient of the pesticide diffuses over a wide range, it is not necessary to forcibly throw the pesticide far away in a paddy field of normal size. Throwing it into the water two to three meters away is sufficient.
  • the number of packages to be thrown into the paddy field is too large, the throwing requires labor and labor is not saved, and it is economically disadvantageous. If the number is too small, the spread of the solid pesticide formulation that floats on the water surface is not sufficient. There is a possibility that the number will be sufficient. Usually, the number is 1 to 30 and preferably 2 to 20 per 10 a of the paddy field.
  • the exterior of the package for throwing into a paddy field is, for example, paper, resin, a bag or box or bottle made of metal, wood, etc., which is made by attaching aluminum foil or depositing aluminum foil or silica to these.
  • it is a bag made of paper, resin, or those obtained by laminating aluminum foil on these or by depositing aluminum or silica.
  • the water-floating pesticidal solid preparation of the present invention when it is a granular wettable powder or granules for uniform application, or when it is not packaged in a water-soluble film, even when it is subjected to a frame treatment or a mouth opening treatment, the above-mentioned packaging is used.
  • Package in the same bag, box or bottle as the package.
  • the solid water-floating pesticide solid formulation of the present invention is stable over time in terms of physical properties with respect to moisture absorption, and therefore does not require attention to moisture absorption as compared to formulations containing a foaming agent. However, the water-soluble film will break if exposed to water. It is desirable to use a finished exterior.
  • a pyrazolate slurry was prepared by mixing the pyrazolate drug substance, Surfinol TGE, NE291Pg, pull mouth nick P103 and water.
  • a mixture of pyrazolate drug substance (70.0%), Surfynol TGE (0.5%), surfactant (0.4%) selected from Table 2 below, and water (29.1%) is mixed with a virazolose slurry.
  • 3 kg of the above slurry was added to a vessel of an atritor MA1 NS-X type (manufactured by Mitsui Mining Co., Ltd.) filled with 17 kg of a 3/16 inch steel ball, and pulverized at 200 rpm for 1 hour. After pulverization, the slurry was discharged from the attritor, and the weight of the slurry that could be taken out by natural discharge was measured to determine the yield relative to the charged amount, which was defined as the discharge rate. The viscosity of the obtained slurry was measured with a B-type viscometer. Table 2 shows the results. Table 2
  • Example 1 an attempt was made to obtain a 1 kg granule in the same manner as in Example 1, except that the slurry used was changed to 31.2 parts of the slurry described in Test Example 1 as Experiment No. 6.
  • the slurry was added to the powder mixture and kneaded, the granules extruded from the screen adhered to each other to form large lumps, did not flow in the fluidized bed dryer, and produced satisfactory granules. I could't get it.
  • the amount of granules calculated from the amount of virazolate required per 10 a is larger than 1 kg, and that 1 kg of pyrazolate cannot be produced.
  • Paddy field throw-in pesticide formulation manufactured using wet-milled slurry containing Pull Mouth Nick P 103
  • Cork powder (0.2-0.5 mm division, 13.36 parts), bentonite powder (6.0 parts), cellogen 5A (8.0 parts), Surfynol 104S (3.0 parts) And ta Mol PP (manufactured by BAS F, sodium salt of a condensate of phenol sulfonic acid, 3.0 parts) was mixed in a kneader, and then a slurry (84. 5 parts), Toxanone GR31A (5.0 parts) and kneading water (small amount) are added and kneaded, and 1.2 mm using Twin Dome Gran (Fuji Baudal Co., Ltd., extrusion granulator). And extruded through a screen.
  • BAS F sodium salt of a condensate of phenol sulfonic acid
  • the obtained granules were dried using a fluidized-bed dryer at 70 ° C., and sized with 2 mm and 0.5 mm sieves to obtain granules.
  • the resulting granules are water spreadability of floating granules in a c-obtained granules Haiseron C one 200 containing 63% Birazoreto (Nichigo Film Co., Ltd., PVA film, thickness 40 m)
  • Birazoreto Nigo Film Co., Ltd., PVA film, thickness 40 m
  • This formulation is a paddy field pesticide formulation that processes 10 packs per 10 a.
  • Throw-in pesticide formulation for paddy field which was manufactured using wet-milled slurry without blending with Pull-out Nick P 103
  • Example 2 in order to obtain granules having a pyrazolate content of 63%, 104 parts of the slurry was required in place of the slurry described in Test Example 1 as Experiment No. 6 in Test Example 1, and the kneading water was required. The granulation was difficult due to too much, and therefore, the desired agricultural chemical for throwing in paddy fields could not be obtained.
  • the content of granules that could be obtained using this slurry was limited to 47.3%.
  • the pesticide formulation for paddy field injection of this example is also economical in terms of raw material cost, packaging cost, fare, etc. It is also disadvantageous in terms of portability and labor.
  • Granular wettable powder manufactured using a slurry obtained by wet-milling with the blend of Pull Mouth Nick P 103
  • Test Example 1 was prepared by mixing Neogen Powder (made by Daiichi Kogyo Seiyaku Co., Ltd., sodium dodecylbenzenesulfonate, 2.0 parts) and dried potato starch (Matsuya Chemical Co., Ltd., 18.42 parts). Then, the slurry (79.53 parts) described as Experiment No. 5 and kneading water (small amount) were added and kneaded.
  • the mixture was granulated with a 0.7 mm screen using a basket type granulator (L-15 type, manufactured by Kikusui Seisakusho Co., Ltd.), and then dried in a blow dryer set at 70 ° C.
  • the obtained granules were sieved with a lmm to 0.3 mm sieve to obtain a granular wettable powder containing 63% of virazolate.
  • This drug can be used in the same manner as flowables, by diluting 300 g per 10a into a small amount of water.
  • Example 3 When the slurry used in Example 3 was changed to the slurry described in Experiment No. 6 in Test Example 1, the kneading water became too large, and a granular wettable powder having an active ingredient content of 52.5% at the maximum was used. However, it was not possible to obtain the desired granular wettable powder.
  • Example 3 In order to obtain the same amount of active ingredient as in Example 3 using the water dispersible granules, it was necessary to treat 360 g of the granules per 10 a. Compared with 300 g of the granular wettable powder of Example 3 having the same active ingredient, the granular wettable powder of this example is disadvantageous in terms of economy and convenience in use.
  • Nipsi NA (10.0 parts), Kaolin (6.85 parts), Vanirex N (8.0 parts) and Neogen Powder (2.0 parts) are mixed in a speed box, and then further The obtained slurry (1000.0 parts) was added, mixed and granulated. After the obtained granules were dried in a blow dryer at 70 ° C., a 0.2 to 0.7 mm section was sieved to obtain a granular wettable powder containing 70% of diclomedin. This wettable powder in granular form can be diluted with a small amount of water and used as a flying agent for aerial application.
  • Example 4 In the wet pulverization of Example 4, the mixture except for Evan u103 was tried to be wet pulverized in the same manner as in Example 4, but the viscosity of the slurry containing 70% of diclomedine was increased, and pulverization was impossible. Therefore, the desired granular wettable powder could not be obtained.
  • Example 4 Granulation was carried out in the same manner as in Example 4 using this 50% diclomedin slurry, whereby a granular wettable powder containing 35% diclomedine was obtained.
  • Table 3 shows a composition comparison between Example 4 and Comparative Example 4. “One” in the table indicates that no component was added. Table 3
  • composition of wettable powder in granules Ingredient Example Content in Example 4 Content in Comparative Example 4 Slurry Monguard original substance 70.7 parts 50.5 parts
  • Nipseal N A 10.0 parts 100 parts Kaolin 6.85 parts 43 49 parts Nilex N 8.0 parts 80 parts Neogen powder 2.0 parts 20 parts
  • Granulated hydrated pyrimidifen drug substance (99.5%, 65.33 ⁇ , Epane u102 (1.0 parts), Newcol 291) prepared by using wet-milled slurry containing Evan u102 PG (manufactured by Nippon Emulsifier Co., Ltd., sodium salt of dialkyl sulfosuccinate, 0.8 part) and water (32.87 parts) are mixed, and Dynomill KDL type (600 ml, continuous vessel, 480 ml, 1 mm diameter) Filled with glass beads, wet-pulverized using a rotation speed of 3000 rpm and a supply speed of 200 m1Z) to obtain a slurry containing 65% of pyrimidifen.Nipsil NA (18.0 parts), Tamol PP (8.0 parts), neogen powder (2.0 parts), AMICOL No.
  • Example 5 In the wet pulverization of Example 5, the mixture excluding Evan u102 was subjected to wet pulverization in the same manner as in Example 5, but the viscosity of the slurry containing 65% of pyrimidifen was increased, so that pulverization was impossible. Therefore, the desired granular wettable powder was not obtained.
  • Example 5 In order to wet-pulverize the mixture except for epan u 102, it is necessary to reduce the amount of the pyrimidifune bulk material to 45.23 parts and increase the amount of water to 53.97 parts as compared with Example 5. Yes, millable pyrimidifen concentration was limited to 45%. Granulation was carried out in the same manner as in Example 5 using this 45% slurry of pyrimidifen, and a granular wettable powder containing 35% of pyrimidifen was obtained. Table 4 shows a composition comparison between Example 5 and Comparative Example 5. “One” in the table indicates that no component was added. Table 4
  • composition of granulated wettable powder Ingredients Content in Example 5 Content in Comparative Example 5 Slurry Pyrimidifen drug substance 65.33 parts 45.23 parts
  • the present invention it has become possible to produce a solid preparation containing a high concentration of a solid agricultural chemical active ingredient finely pulverized by wet pulverization. As a result, it was possible to reduce the weight of pesticide formulations, and it was possible to save labor and costs in terms of production and transportation. In terms of distribution and use, it is easy to handle and greatly contributes to the development of agriculture.

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Abstract

L'invention concerne une formulation antiparasitaire solide à concentration élevée, obtenue par pulvérisation par voie humide d'une suspension qui contient un principe actif antiparasitaire à concentration élevée, lequel est mélangé à un tensioactif de type non ionique de polyalkylèneglycol renfermant de l'éthylèneglycol et du propylèneglycol sous la forme d'une molécule de type bloc. La suspension ainsi obtenue est ensuite destinée à être malaxée et granulée.
PCT/JP2000/003376 1999-05-27 2000-05-26 Formulation antiparasitaire solide à concentration élevée WO2000072674A1 (fr)

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JP11/148116 1999-05-27
JP14811699 1999-05-27

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WO2000072674A1 true WO2000072674A1 (fr) 2000-12-07

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04297403A (ja) * 1991-03-06 1992-10-21 Ishihara Sangyo Kaisha Ltd 水田除草用錠剤またはカプセル
JPH0517303A (ja) * 1991-07-09 1993-01-26 Nissan Chem Ind Ltd 水田用除草粒剤
JPH0570304A (ja) * 1991-09-11 1993-03-23 Ishihara Sangyo Kaisha Ltd 水田害虫防除用錠剤またはカプセル
JPH05310516A (ja) * 1992-04-30 1993-11-22 Sds Biotech Kk 水田施用固状除草剤
JPH0648902A (ja) * 1992-07-22 1994-02-22 Mikasa Kagaku Kogyo Kk 省力散布型水田用農薬
JPH1149601A (ja) * 1997-08-08 1999-02-23 Hodogaya Chem Co Ltd 大粒子の水性懸濁製剤を水田に直接散布する除草方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04297403A (ja) * 1991-03-06 1992-10-21 Ishihara Sangyo Kaisha Ltd 水田除草用錠剤またはカプセル
JPH0517303A (ja) * 1991-07-09 1993-01-26 Nissan Chem Ind Ltd 水田用除草粒剤
JPH0570304A (ja) * 1991-09-11 1993-03-23 Ishihara Sangyo Kaisha Ltd 水田害虫防除用錠剤またはカプセル
JPH05310516A (ja) * 1992-04-30 1993-11-22 Sds Biotech Kk 水田施用固状除草剤
JPH0648902A (ja) * 1992-07-22 1994-02-22 Mikasa Kagaku Kogyo Kk 省力散布型水田用農薬
JPH1149601A (ja) * 1997-08-08 1999-02-23 Hodogaya Chem Co Ltd 大粒子の水性懸濁製剤を水田に直接散布する除草方法

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