WO2023136320A1 - Liquid agrochemical composition - Google Patents

Liquid agrochemical composition Download PDF

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Publication number
WO2023136320A1
WO2023136320A1 PCT/JP2023/000772 JP2023000772W WO2023136320A1 WO 2023136320 A1 WO2023136320 A1 WO 2023136320A1 JP 2023000772 W JP2023000772 W JP 2023000772W WO 2023136320 A1 WO2023136320 A1 WO 2023136320A1
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Prior art keywords
mass
pyriproxyfen
clothianidin
organic solvent
less
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PCT/JP2023/000772
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French (fr)
Japanese (ja)
Inventor
智子 住田
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住友化学株式会社
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Publication of WO2023136320A1 publication Critical patent/WO2023136320A1/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
    • A01N25/02—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 containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides

Definitions

  • the present invention relates to a liquid pesticide composition.
  • Pyriproxyfen is known as an agrochemically active compound (see, for example, Japanese Patent Application Laid-Open No. 2006-193513 (Patent Document 1)).
  • Clothianidin is also known as another pesticide active compound (see, for example, JP-A-2003-321303 (Patent Document 2)).
  • An object of the present invention is to provide a liquid agricultural chemical composition containing pyriproxyfen and clothianidin as agricultural chemical active compounds and having excellent storage stability.
  • the present invention provides the following liquid agricultural chemical composition.
  • [1] comprising pyriproxyfen, clothianidin, a hydrophobic organic solvent, an ethylene oxide propylene oxide block copolymer, and water;
  • a liquid pesticide composition in which a liquid in which the pyriproxyfen is dissolved in the hydrophobic organic solvent is dispersed in water and the clothianidin is suspended,
  • the ethylene oxide propylene oxide block copolymer has an HLB value of 5.0 or more and 20.0 or less, a ratio (W 2 /W 1 ) of the weight W 2 of the hydrophobic organic solvent to the weight W 1 of the pyriproxyfen is 1.0 or more and 6.0 or less;
  • the ratio of the total weight W4 of the pyriproxyfen, the clothianidin, and the hydrophobic organic solvent to the weight W3 of the ethylene oxide propylene oxide block copolymer ( W4 / W3 ) is 2.0 or more and 80.0.
  • a liquid pesticide composition which is: [2] consisting essentially of pyriproxyfen, clothianidin, a hydrophobic organic solvent, an ethylene oxide propylene oxide block copolymer, a lignin sulfonate, a thickener, an antifoaming agent, an antifreeze agent, a preservative and water;
  • a liquid pesticide composition in which a liquid in which the pyriproxyfen is dissolved in the hydrophobic organic solvent is dispersed in water and the clothianidin is suspended,
  • the ethylene oxide propylene oxide block copolymer has an HLB value of 5.0 or more and 20.0 or less, a ratio (W 2 /W 1 ) of the weight W 2 of the hydrophobic organic solvent to the weight W 1 of the pyriproxyfen is 1.0 or more and 6.0 or less;
  • a liquid pesticide composition which is: [3] The liquid agricultural chemical composition according to [1] or [2], wherein the hydrophobic organic solvent contains a solvent having a density of 0.85 g/cm 3 or more and 1.20 g/cm 3 or less. [4] The liquid agricultural chemical composition according to [1], further comprising a second surfactant. [5] The liquid agricultural chemical composition according to [4], wherein the second surfactant comprises a ligninsulfonate. [6] Any one of [1] to [ 5] , wherein the ratio of the mass W5 of the clothianidin to the mass W1 of the pyriproxyfen ( W5 / W1 ) is 0.03 or more and 30 or less. 10.
  • Liquid pesticide composition according to paragraph. [7] When the total mass of the liquid agricultural chemical composition is 100% by mass, the total mass W6 of the pyriproxyfen and the clothianidin is 0.1% by mass or more and 50% by mass or less [1] The liquid agricultural chemical composition according to any one of [6].
  • the liquid agricultural chemical composition according to the present invention (hereinafter sometimes referred to as “the composition of the present invention”) contains pyriproxyfen, clothianidin, a hydrophobic organic solvent, a first surfactant, and water.
  • the composition of the present invention contains at least pyriproxyfen and clothianidin as pesticide active compounds.
  • Pyriproxyfen is a generic name for 4-phenoxyphenyl-2(2-pyridyloxy)propyl ether, and can be produced, for example, by the method described in JP-A-60-215671, and a commercially available product is used.
  • Clothianidin is a general name for 1-(2-chloro-5-thiazolylmethyl)-3-methyl-2-nitroguanidine, and can be produced, for example, by the method described in JP-A-3-157308. can also be used.
  • composition of the present invention a liquid in which pyriproxyfen is dissolved in the hydrophobic organic solvent is dispersed in water, and clothianidin is suspended.
  • the continuous phase is an aqueous phase
  • pyriproxyfen is dissolved in the hydrophobic organic solvent in a liquid state
  • clothianidin is in a solid state, respectively dispersed in the continuous phase Suspoemulsion ( suspoemulsion).
  • the content of pyriproxyfen in the composition of the present invention is usually 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the content of pyriproxyfen in the composition of the present invention is generally 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.
  • the content of clothianidin in the composition of the present invention is usually 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 2% by mass or more.
  • the content of clothianidin in the composition of the present invention is generally 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.
  • the ratio of the weight W1 of pyriproxyfen to the weight W5 of clothianidin in the composition of the present invention is usually 0.03 or more and 30 or less, preferably 0.05 or more and 20 or less. , more preferably 0.1 or more and 10 or less.
  • the total mass W6 of pyriproxyfen and clothianidin in the composition of the present invention is usually 50% by mass or less, preferably 30% by mass or less, when the total mass of the composition of the present invention is 100% by mass. , more preferably 25% by mass or less.
  • the total mass W6 of pyriproxyfen and clothianidin in the composition of the present invention is usually at least 0.1% by mass, preferably 0.5% by mass, when the total mass of the composition of the present invention is 100% by mass. % or more, more preferably 2 mass % or more.
  • a liquid in which pyriproxyfen is dissolved in a hydrophobic organic solvent is dispersed in the aqueous phase, and an agriculturally active compound other than pyriproxyfen may be dissolved or suspended in the liquid.
  • agrochemical active compounds include, for example, insecticidal active compounds, fungicidal active compounds, herbicidal active compounds, insect growth-regulating active compounds, and plant growth-regulating active compounds.
  • the composition of the present invention contains a hydrophobic organic solvent.
  • hydrophobic organic solvent refers to an organic solvent having a water solubility of 10% by mass or less at a temperature of 25°C.
  • the hydrophobic organic solvent is not particularly limited as long as it can dissolve pyriproxyfen. Also, two or more hydrophobic organic solvents may be mixed and used.
  • Hydrophobic organic solvents include, for example, alcohols such as benzyl alcohol; Esters such as ethyl acetate, benzyl acetate, benzyl benzoate; Ketones such as acetophenone and cyclohexanone; Amides such as N,N-dimethyloctanamide and N,N-dimethyldecanamide; alkylbenzenes such as toluene and xylene; alkylnaphthalenes such as methylnaphthalene and dimethylnaphthalene; and aromatic hydrocarbons such as phenylxylylethane and 1-phenyl-1-ethylphenylethane, and mixtures thereof; is mentioned.
  • alcohols such as benzyl alcohol
  • Esters such as ethyl acetate, benzyl acetate, benzyl benzoate
  • Ketones such as acetophenone and cyclohexanone
  • Amides such as N
  • Preferred hydrophobic organic solvents include aromatic compounds such as acetophenone, benzyl acetate, benzyl benzoate and aromatic hydrocarbons, more preferably aromatic hydrocarbons.
  • the hydrophobic organic solvent is preferably a solvent having a density of 0.85 g/cm 3 or more and 1.20 g/cm 3 or less, more preferably a solvent having a density of 0.89 g/cm 3 or more and 1.12 g/cm 3 or less. is. Density as used herein means density measured according to JIS K2249-3 (enacted on November 21, 2011).
  • the content of the hydrophobic organic solvent in the composition of the present invention is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more. is 50% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less.
  • the content of the hydrophobic organic solvent refers to the total mass when two or more hydrophobic organic solvents are included.
  • the content of the hydrophobic organic solvent in the composition of the present invention is preferably 30% by mass or more, more preferably 100% by mass of the total amount of the hydrophobic organic solvent. is 50% by mass or more, may be 70% by mass or more, may be 90% by mass or more, or may be 100% by mass.
  • the mass ratio (W 2 /W 1 ) of pyriproxyfen mass W 1 and hydrophobic organic solvent W 2 in the composition of the present invention is usually 1.0 or more and 6.0 or less, preferably 1.0 or more. 5.0 or less, more preferably 1.0 or more and 3.0 or less.
  • composition of the present invention may contain an organic solvent other than the hydrophobic organic solvent.
  • clothianidin is suspended in the aqueous phase, and an agriculturally active compound other than clothianidin may also be suspended.
  • agrochemical active compounds include, for example, insecticidal active compounds, fungicidal active compounds, herbicidal active compounds, insect growth-regulating active compounds, and plant growth-regulating active compounds.
  • the composition of the present invention contains a first surfactant.
  • the first surfactant is one or more components selected from the group consisting of fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, and ethylene oxide propylene oxide block copolymers.
  • the first surfactant contained in the composition of the present invention has an HLB value of 5.0 or more and 20.0 or less, preferably 10.0 or more and 19.0 or less.
  • the storage stability of the liquid agricultural chemical composition can be improved. As used herein, improving the storage stability includes suppressing aggregation and particle growth of the agricultural chemical active compound during storage at high and/or low temperatures.
  • the HLB value means the HLB value according to the Griffin method
  • the HLB value of the first surfactant is the HLB value of the surfactant when the first surfactant consists of one surfactant.
  • it means the total value obtained by multiplying the HLB value of each surfactant by the compounding ratio.
  • the first surfactant contains a surfactant with an HLB value of 12 at a blending ratio of 50% by mass and a surfactant with an HLB value of 6 at a blending ratio of 50% by mass
  • fatty acid ethylene oxide adduct (hereinafter, “ethylene oxide adduct” is also referred to as “EO adduct”) means a compound in which ethylene oxide is added to a fatty acid, and is also called polyethylene glycol fatty acid ester. .
  • Fatty acid EO adducts may be monoesters or diesters.
  • the fatty acid in the fatty acid EO adduct is usually a C10-20 fatty acid, preferably a C12-18 fatty acid.
  • Fatty acid EO adducts include, for example, monolauric acid EO adducts, monostearic acid EO adducts, and dioleic acid EO adducts.
  • the number of EO addition moles in the fatty acid EO adduct is usually 2-100, preferably 10-100.
  • the HLB value of the fatty acid EO adduct is preferably 5 or more, more preferably 7 or more, and may be 10 or more. Also, it is preferably 20 or less, more preferably 19 or less.
  • a polyhydric alcohol fatty acid ester EO adduct means a compound in which ethylene oxide is added to an ester of polyhydric alcohol and fatty acid.
  • Polyhydric alcohols are alcohols having 3 to 6 hydroxyl groups.
  • Esters of polyhydric alcohols and fatty acids are preferably glycerine fatty acid esters (eg, triglycerides such as castor oil), sorbitan fatty acid esters or sorbitol (sorbit) fatty acid esters.
  • Fatty acids in esters of polyhydric alcohols and fatty acids are usually fatty acids with 10 to 20 carbon atoms, preferably fatty acids with 12 to 18 carbon atoms.
  • Polyhydric alcohol fatty acid ester EO adducts include, for example, sorbitan monostearate EO adducts, sorbitan trioleate EO adducts, and castor oil EO adducts.
  • the number of EO addition moles in the polyhydric alcohol fatty acid ester EO adduct is usually 2-100, preferably 10-55.
  • the HLB value of the polyhydric alcohol fatty acid ester EO adduct is preferably 5 or more, more preferably 7 or more, and may be 10 or more. Also, it is preferably 20 or less, more preferably 19 or less.
  • the HLB value of the ethylene oxide propylene oxide block copolymer is preferably 5 or more, more preferably 7 or more, and may be 10 or more. Also, it is preferably 20 or less, more preferably 19 or less.
  • the average molecular weight of the ethylene oxide propylene oxide block copolymer is preferably 1500 or more, more preferably 2000 or more, and may be 2500 or more. Also, it is preferably 8,000 or less, more preferably 7,500 or less, and may be 7,000 or less.
  • the content of the first surfactant in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.7% by mass or more. Also, it is preferably 20.0% by mass or less, more preferably 10.0% by mass or less, and still more preferably 8.5% by mass or less.
  • the ratio (W 4 /W 3 ) of the total weight W 4 of the pyriproxyfen, the clothianidin and the hydrophobic organic solvent to the weight W 3 of the first surfactant is 2. It is 0 or more and 80.0 or less, preferably 2.0 or more and 70.0 or less, more preferably 2.0 or more and 60.0 or less.
  • the ratio (W 4 /W 3 ) is within the above range, the storage stability of the liquid agricultural chemical composition can be improved.
  • the ratio (W 1 /W 3 ) of the mass W 1 of the pyriproxyfen to the mass W 3 of the first surfactant is preferably 0.1 or more and 35.0 or less, It is more preferably 0.15 or more and 30.0 or less.
  • the ratio of the total mass of the mass W1 of the pyriproxyfen and the mass W2 of the hydrophobic organic solvent to the mass W3 of the first surfactant is preferably from 0.25 to 70.0, more preferably from 0.30 to 60.0.
  • the ratio of the mass W5 of the clothianidin to the mass W3 of the first surfactant is preferably 0.4 or more and 20 or less.
  • composition of the present invention may further contain another surfactant (hereinafter also referred to as "second surfactant") different from the first surfactant.
  • second surfactant is not limited as long as it is a surfactant other than fatty acid EO adduct, polyhydric alcohol fatty acid ester EO adduct, ethylene oxide propylene oxide block copolymer, nonionic surfactant, anionic surfactant. , cationic surfactants, amphoteric surfactants and mixtures thereof.
  • nonionic surfactants include polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, sucrose fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide, alkyl polyglycosides.
  • anionic surfactants include sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates include salts of naphthalenesulfonic acid or alkylnaphthalenesulfonic acid, salts of formalin condensates of naphthalenesulfonic acid or alkylnaphthalenesulfonic acid, alkylbenzenesulfonates, alkyldiphenylether disulfonates, and ⁇ -olefinsulfonic acids.
  • Sulfate ester salts include, for example, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts and polyoxyethylene alkylphenyl ether sulfate ester salts.
  • Phosphate salts include, for example, polyoxyethylene alkylaryl ether phosphate salts and polyoxyethylene tristyrylphenyl ether phosphate salts.
  • Examples of carboxylates include polycarboxylates such as fatty acid salts and polyacrylates.
  • Salts constituting anionic surfactants include alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; ammonium; organic ammonium derived from monoethanolamine, diethanolamine, triethanolamine, and the like. be done.
  • Cationic surfactants include alkylamine salts and quaternary ammonium salts.
  • Preferred second surfactants are nonionic surfactants other than the first surfactant and/or anionic surfactants. More preferred second surfactants include anionic surfactants.
  • the composition of the present invention can effectively suppress aggregation of the agricultural chemical active compound.
  • the content of the second surfactant in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and may be 1% by mass or more. , preferably 10% by mass or less, more preferably 7% by mass or less, and may be 5% by mass or less.
  • the content of the second surfactant refers to the total content when the second surfactant contains two or more surfactants.
  • the content of the second surfactant in the composition of the present invention is preferably 30% by mass or more when the total amount of the second surfactant is 100% by mass, More preferably, it is 50% by mass or more.
  • the mass ratio of the content of the first surfactant/second surfactant is preferably 0.1 or more, It may be 0.2 or more, or 0.25 or more, preferably 10 or less, 8 or less, or 6 or less.
  • the composition of the present invention contains water.
  • water examples include ion-exchanged water, distilled water, filtered water, tap water and groundwater.
  • the content of water in the composition of the present invention is usually 20% by mass or more, may be 30% by mass or more, may be 40% by mass or more, and is usually 90% by mass or less, It may be 85% by mass or less, or may be 80% by mass or less.
  • composition of the present invention may contain other formulation adjuvants as necessary.
  • formulation adjuvants include, for example, thickeners, antifoaming agents, antifreezing agents, preservatives and the like.
  • thickeners examples include polysaccharides such as xanthan gum, clays, and silicates.
  • the content of the thickening agent in the composition of the present invention is usually 0.05% by mass or more, and may be 0.1% by mass or more, and is usually 5% by mass or less and 3% by mass or less. may be
  • antifoaming agents examples include silicone antifoaming agents.
  • the content of the antifoaming agent in the composition of the present invention is usually 0.01% by mass or more, may be 0.05% by mass or more, and is usually 1% by mass or less, and 0.5% by mass. % or less.
  • Antifreeze agents include, for example, ethylene glycol, propylene glycol, urea, and glycerin.
  • the content of the antifreeze agent in the composition of the present invention is usually 1% by mass or more, may be 2% by mass or more, and is usually 10% by mass or less, and may be 8% by mass or less. good.
  • preservatives examples include isothiazolinone-based preservatives.
  • the content of the antiseptic in the composition of the present invention is usually 0.05% by mass or more, may be 0.1% by mass or more, and is usually 0.5% by mass or less, and 0.3% by mass. % by mass or less.
  • composition of the present invention has good stability when diluted with water (there is no precipitation or phase separation that can cause uneven spraying, and no precipitate that can cause nozzle clogging during the period assumed from dilution to spraying). , good dischargeability from containers, good physical stability during storage in low and/or high temperature environments (precipitation/caking over time, crystal growth/aggregation of solid particles, coalescence of oil droplets , phase separation, and color change), chemical stability (no or little degradation of clothianidin and/or pyriproxyfen over time), and good insecticidal activity.
  • composition of the present invention is prepared by using, for example, the agricultural chemical active compounds pyriproxyfen and clothianidin, a hydrophobic organic solvent, a first surfactant, water, and, if necessary, a second surfactant and formulation aids. can be manufactured.
  • the composition of the present invention can be produced, for example, by the following method.
  • Method 1 An emulsion is prepared by adding pyriproxyfen, a first surfactant, a hydrophobic organic solvent, and optionally formulation aids to water and stirring and dispersing with a stirrer such as a homogenizer.
  • the first surfactant may be added to the hydrophobic organic solvent, water, or both.
  • clothianidin, a first surfactant and/or a second surfactant, and optionally a formulation adjuvant are added to water, and pulverized and suspended by wet pulverization using media such as glass beads and zirconia beads. Suspensions are prepared by turbidity.
  • the emulsion, suspension, and, if necessary, formulation aids such as thickeners, preservatives and antifoaming agents are mixed to obtain the composition of the present invention.
  • Method 2 Clothianidin, a first surfactant and/or a second surfactant, and, if necessary, formulation aids are added to water, and pulverized and suspended by wet pulverization using media such as glass beads and zirconia beads. to prepare the suspension.
  • pyriproxyfen, a hydrophobic organic solvent, and optionally a first surfactant and optionally a second surfactant and formulation aids are added to the suspension and stirred with a stirrer such as a homogenizer. ⁇ Emulsify by dispersing.
  • formulation aids such as thickeners, preservatives and antifoaming agents are mixed as necessary to obtain the composition of the present invention.
  • An oil phase is prepared by mixing pyriproxyfen, a hydrophobic organic solvent, and optionally a first surfactant, optionally a second surfactant, and formulation aids.
  • clothianidin, a first surfactant and/or a second surfactant, and optionally formulation aids are added to water to prepare an aqueous phase.
  • the oil phase and water phase are mixed, emulsified, pulverized, and suspended simultaneously by wet pulverization using media such as glass beads and zirconia beads. to obtain the composition of the present invention.
  • Pests can be controlled by applying the composition of the present invention to plants or their growing environment. Pests that can be controlled by the composition of the present invention include, for example, whiteflies, aphids, leafhoppers, and cotton weevils.
  • compositions according to the invention are usually diluted with water to the desired application concentration to give a spray liquor.
  • 100 to 1000 L, preferably 300 to 800 L of spray solution are applied per hectare.
  • the application amount of the composition of the present invention varies depending on the type of plant, the type and frequency of occurrence of pests to be controlled, the timing of application, the application method, the place of application, weather conditions, etc., but the application amount of pyriproxyfen is 1. It is usually 55 to 250 g per hectare, and the application amount of clothianidin is usually 25 to 100 g per hectare.
  • Emulsogen EL540 castor oil EO adduct (manufactured by Clariant) (EO addition mole number 54, HLB 15) (denoted as “S31” in Tables 1 to 6)
  • ⁇ Tween 85 Sorbitan trioleic acid EO adduct (manufactured by Croda) (EO addition mole number 20, HLB 11) (denoted as “S32” in Tables 1 to 6)
  • ⁇ Atlas G-1096 Sorbitol hexaoleic acid EO adduct (manufactured by Croda) (EO addition mole number 50, HLB 11) (denoted as “S33” in Tables 1 to 6)
  • REAX910 sodium ligninsulfonate (manufactured by Ingevity) (Anionic surfactant)
  • SoprophorFLK polyoxyethylene tristyrylphenyl ether phosphate potassium salt (manufactured by Solvay) (anionic surfactant)
  • Kelzan xanthan gum (manufactured by CP Kelco) Veegum R: magnesium aluminum silicate (manufactured by Vanderbilt Minerals)
  • Antifoaming agent XIAMETER ACP-1500
  • Antifoam Compound silicone-based mixture (manufactured by Dow Corning Toray)
  • Antifreezing agent Propylene glycol: propylene glycol (manufactured by Adeka) [Preservative]
  • Proxel GXL 1,2-benzisothiazolin-3-one (manufactured by Lonza)
  • Example 1 Examination of the type of hydrophobic organic solvent> (Example 1) 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 2.60 g of REAX910, and 0.44 g of Veegum R were added to 31.37 g of ion-exchanged water and stirred and mixed to prepare an aqueous phase. To this, 3.51 g of clothianidin (99.8% purity) was added and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a clothianidin suspension.
  • a dyno mill 1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s
  • Example 2 Example 2-6
  • Example 2 to 5 were produced in the same manner as in Example 1 except that the type of hydrophobic organic solvent was changed.
  • Example 6 was prepared in the same manner as in Example 1, except that the type of hydrophobic organic solvent and the amount and type of first surfactant added were changed.
  • Example 7 Examination of the type and amount of the first surfactant> (Example 7) 8.06 g of pyriproxyfen (purity 99.3%), 16.00 g of GaroSOL 200ND and 1.00 g of Stepflow26F were mixed to form a uniform solution to prepare an oil phase. 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 2.60 g of REAX910, and 0.44 g of Veegum R were added to 38.87 g of ion-exchanged water, and the mixture was stirred and mixed to prepare an aqueous phase.
  • Example 8 was produced in the same manner as in Example 7, except that the type of hydrophobic organic solvent was changed.
  • Examples 9 to 11 were produced in the same manner as in Example 1 except that the type of hydrophobic organic solvent and the amount and type of first surfactant added were changed.
  • Example 12 Examination of the ratio (W 4 /W 3 ) etc.> (Example 12) 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 2.60 g of REAX910, and 0.44 g of Veegum R were added to 20.29 g of ion-exchanged water and stirred and mixed to prepare an aqueous phase. 2.01 g of clothianidin (purity 99.8%) was added thereto and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a clothianidin suspension.
  • a dyno mill 1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s
  • the thickener solution and the Suspoemulsion were mixed, and deionized water was added and mixed to make a total of 100.00 g, and 2.0 w/w% clothianidin and 20.0 w/w% pyriproxyfen A suspoemulsion of Example 12 containing was obtained.
  • Example 13 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 2.60 g of REAX910, and 0.44 g of Veegum R were added to 20.00 g of ion-exchanged water, and the mixture was stirred and mixed to prepare an aqueous phase. 20.05 g of clothianidin (purity 99.8%) was added thereto and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a clothianidin suspension.
  • a dyno mill 1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s
  • pyriproxyfen purity 99.3%
  • GaroSOL 200ND 2.00 g
  • Stepflow26F 1.00 g
  • the above clothianidin suspension and oil phase were mixed.
  • the resulting mixture was stirred using a polytron to obtain a suspoemulsion.
  • a thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water.
  • the thickener solution and the above suspoemulsion are mixed, ion-exchanged water is added and mixed to make a total of 100.00 g, and 20.0 w/w% clothianidin and 2.0 w/w% pyriproxyfen are mixed.
  • a suspoemulsion of Example 13 containing was obtained.
  • Example 14-17 Examples 14, 16 and 17 were produced in the same manner as in Example 12 except that the type of hydrophobic organic solvent and the amount and type of first surfactant added were changed.
  • Example 15 was prepared in the same manner as in Example 13 except that the type of hydrophobic organic solvent and the amount and type of first surfactant added were changed.
  • Example 18 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 1.00 g of REAX910, and 0.44 g of Veegum R were added to 20.00 g of ion-exchanged water, and the mixture was stirred and mixed to prepare an aqueous phase. To this, 10.03 g of clothianidin (99.8% purity) was added and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a clothianidin suspension.
  • a dyno mill 1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s
  • the thickener solution and the above suspoemulsion are mixed, and ion-exchanged water is added and mixed to make a total of 100.00 g to obtain 10.0 w/w% clothianidin and 1.0 w/w% pyriproxy.
  • a suspoemulsion of Example 18 containing fen was obtained.
  • Examples 19 to 24 Examination of the type of the first surfactant> (Examples 19-23) Examples 19 to 23 were produced in the same manner as in Example 1 except that the type of hydrophobic organic solvent and the type of first surfactant were changed.
  • Example 24 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 2.60 g of REAX910, and 0.44 g of Veegum R were added to 31.37 g of ion-exchanged water and stirred and mixed to prepare an aqueous phase. To this, 3.51 g of clothianidin (99.8% purity) was added and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a clothianidin suspension.
  • a dyno mill 1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s
  • Examples 25 to 29 Examination of types of surfactants> (Examples 25-27)
  • Examples 25 to 27 were prepared in the same manner as in Example 1 except that the type of hydrophobic organic solvent and the amount and type of first surfactant added were changed.
  • Example 28 8.06 g of pyriproxyfen (purity 99.3%) and 16.00 g of Solvesso 150ND were mixed to form a uniform solution to prepare an oil phase. 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 0.44 g of Veegum R, 2.50 g of Genapol PF40, and 2.50 g of Emulsogen EL540 were added to 31.37 g of ion-exchanged water, and stirred and mixed to prepare an aqueous phase. To this, 3.51 g of clothianidin (99.8% purity) was added and stirred and mixed, and 24.06 g of the prepared oil phase was further added and stirred and mixed.
  • XIAMETER ACP-1500 Antifoam Compound 0.44 g of Veegum R, 2.50 g of Genapol PF40, and 2.50 g of Emulsogen EL540 were added to 31.37 g of ion-exchanged water, and
  • the resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a suspo emulsion.
  • a thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water. The thickener solution and the Suspo emulsion were mixed, and ion-exchanged water was added and mixed to make a total of 100.00 g.
  • a suspoemulsion of Example 28 containing was obtained.
  • Example 29 8.06 g of pyriproxyfen (purity 99.3%) and 16.00 g of GaroSOL 200ND were mixed to form a uniform solution to prepare an oil phase. 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 0.44 g of Veegum R, 3.00 g of Stepflow26F, and 1.00 g of SoprophorFLK were added to 31.37 g of ion-exchanged water, and stirred and mixed to prepare an aqueous phase. To this, 3.51 g of clothianidin (99.8% purity) was added and stirred and mixed, and 24.06 g of the prepared oil phase was further added and stirred and mixed.
  • XIAMETER ACP-1500 Antifoam Compound 0.44 g of Veegum R, 3.00 g of Stepflow26F, and 1.00 g of SoprophorFLK were added to 31.37 g of ion-exchanged water, and stirred and mixed to prepare an
  • the resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a suspo emulsion.
  • a thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water. The thickener solution and the Suspo emulsion were mixed, and ion-exchanged water was added and mixed to make a total of 100.00 g.
  • a suspoemulsion of Example 29 containing was obtained.
  • Comparative Example 1 was prepared in the same manner as in Example 12 except that the type of hydrophobic organic solvent and the type and amount of the first surfactant were changed.
  • Comparative Example 2 Comparative Example 2 was produced in the same manner as in Example 18, except that the amount of the first surfactant added was changed.
  • Example 2 The suspoemulsion of Example 8 was diluted with ion-exchanged water so that the concentrations of clothianidin and pyriproxyfen were 1.1 ppm and 2.5 ppm, respectively, to prepare a spray liquid containing clothianidin and pyriproxyfen.
  • Adults of Bemisia tabaci were released to 3-4 leaf stage cabbage (Brassica oleracea) seedlings planted in 90 ml plastic containers filled with potting soil and allowed to lay eggs for about 24 hours.
  • the spray solution was sprayed on the seedlings using a spray gun so that the amount of the spray solution per 3 seedlings was 20 mL.
  • Prevention value (ab) / a ⁇ 100 a: Number of parasitic larvae in untreated area, b: Number of parasitic larvae in treated area
  • the untreated area means an area in which the same operation as the treated area is performed except that the suspoemulsion of Example 8 is not used.
  • Control value was 99.

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Abstract

This liquid agrochemical composition contains pyriproxyfen, clothianidin, a hydrophobic organic solvent, an ethylene-oxide-propylene-oxide block copolymer, and water, a liquid in which the pyriproxyfen is dissolved in the hydrophobic organic solvent being dispersed in the water and the clothianidin being suspended in the water. The ethylene-oxide-propylene-oxide block copolymer has an HLB value of 5.0-20.0 inclusive, the ratio of the mass W2 of the hydrophobic organic solvent relative to the mass W1 of the pyriproxyfen is 1.0-6.0 inclusive, and the ratio of the total mass W4 of the pyriproxyfen, the clothianidin, and the hydrophilic organic solvent relative to the mass W3 of the ethylene-oxide-propylene-oxide block copolymer is 2.0-80.0 inclusive.

Description

液体農薬組成物liquid pesticide composition
　本発明は、液体農薬組成物に関する。 The present invention relates to a liquid pesticide composition.
　農薬活性化合物としてピリプロキシフェンが知られている（例えば、特開２００６－１９３５１３号公報（特許文献１）を参照）。また、別の農薬活性化合物としてクロチアニジンが知られている（例えば、特開２００３－３２１３０３号公報（特許文献２）を参照）。 Pyriproxyfen is known as an agrochemically active compound (see, for example, Japanese Patent Application Laid-Open No. 2006-193513 (Patent Document 1)). Clothianidin is also known as another pesticide active compound (see, for example, JP-A-2003-321303 (Patent Document 2)).
特開２００６－１９３５１３号公報Japanese Patent Application Laid-Open No. 2006-193513 特開２００３－３２１３０３号公報Japanese Patent Application Laid-Open No. 2003-321303
　本発明は、農薬活性化合物としてピリプロキシフェン及びクロチアニジンを含む液体農薬組成物であって、優れた保存安定性を有する液体農薬組成物の提供を目的とする。 An object of the present invention is to provide a liquid agricultural chemical composition containing pyriproxyfen and clothianidin as agricultural chemical active compounds and having excellent storage stability.
　本発明は、以下の液体農薬組成物を提供する。
　［１］　ピリプロキシフェン、クロチアニジン、疎水性有機溶媒、エチレンオキサイドプロピレンオキサイドブロックコポリマー、及び水を含み、
　水中に、前記疎水性有機溶媒に前記ピリプロキシフェンが溶解した液体が分散し、かつ、前記クロチアニジンが懸濁している液体農薬組成物であって、
　前記エチレンオキサイドプロピレンオキサイドブロックコポリマーは、ＨＬＢ値が５．０以上２０．０以下であり、
　前記ピリプロキシフェンの質量Ｗ１に対する、前記疎水性有機溶媒の質量Ｗ２の比（Ｗ２／Ｗ１）が、１．０以上６．０以下であり、
　前記エチレンオキサイドプロピレンオキサイドブロックコポリマーの質量Ｗ３に対する、前記ピリプロキシフェン、前記クロチアニジン、及び前記疎水性有機溶媒の合計質量Ｗ４の比（Ｗ４／Ｗ３）が、２．０以上８０．０以下である、液体農薬組成物。
　［２］　ピリプロキシフェン、クロチアニジン、疎水性有機溶媒、エチレンオキサイドプロピレンオキサイドブロックコポリマー、リグニンスルホン酸塩、増粘剤、消泡剤、凍結防止剤、防腐剤及び水から実質的になり、
　水中に、前記疎水性有機溶媒に前記ピリプロキシフェンが溶解した液体が分散し、かつ、前記クロチアニジンが懸濁している液体農薬組成物であって、
　前記エチレンオキサイドプロピレンオキサイドブロックコポリマーは、ＨＬＢ値が５．０以上２０．０以下であり、
　前記ピリプロキシフェンの質量Ｗ１に対する、前記疎水性有機溶媒の質量Ｗ２の比（Ｗ２／Ｗ１）が、１．０以上６．０以下であり、
　前記エチレンオキサイドプロピレンオキサイドブロックコポリマーの質量Ｗ３に対する、前記ピリプロキシフェン、前記クロチアニジン、及び前記疎水性有機溶媒の合計質量Ｗ４の比（Ｗ４／Ｗ３）が、２．０以上８０．０以下である、液体農薬組成物。
　［３］　前記疎水性有機溶媒は、密度が０．８５ｇ／ｃｍ３以上１．２０ｇ／ｃｍ３以下の溶媒を含む、［１］または［２］に記載の液体農薬組成物。
　［４］　第２界面活性剤をさらに含む、［１］に記載の液体農薬組成物。
　［５］　前記第２界面活性剤は、リグニンスルホン酸塩を含む、［４］に記載の液体農薬組成物。
　［６］　前記ピリプロキシフェンの質量Ｗ１に対する、前記クロチアニジンの質量Ｗ５の比（Ｗ５／Ｗ１）が、０．０３以上３０以下である、［１］～［５］のいずれか１項に記載の液体農薬組成物。
　［７］　前記液体農薬組成物の全質量を１００質量％としたときに、前記ピリプロキシフェン及び前記クロチアニジンの合計質量Ｗ６が、０．１質量％以上５０質量％以下である、［１］～［６］のいずれか１項に記載の液体農薬組成物。 The present invention provides the following liquid agricultural chemical composition.
[1] comprising pyriproxyfen, clothianidin, a hydrophobic organic solvent, an ethylene oxide propylene oxide block copolymer, and water;
A liquid pesticide composition in which a liquid in which the pyriproxyfen is dissolved in the hydrophobic organic solvent is dispersed in water and the clothianidin is suspended,
The ethylene oxide propylene oxide block copolymer has an HLB value of 5.0 or more and 20.0 or less,
a ratio (W 2 /W 1 ) of the weight W 2 of the hydrophobic organic solvent to the weight W 1 of the pyriproxyfen is 1.0 or more and 6.0 or less;
The ratio of the total weight W4 of the pyriproxyfen, the clothianidin, and the hydrophobic organic solvent to the weight W3 of the ethylene oxide propylene oxide block copolymer ( W4 / W3 ) is 2.0 or more and 80.0. A liquid pesticide composition, which is:
[2] consisting essentially of pyriproxyfen, clothianidin, a hydrophobic organic solvent, an ethylene oxide propylene oxide block copolymer, a lignin sulfonate, a thickener, an antifoaming agent, an antifreeze agent, a preservative and water;
A liquid pesticide composition in which a liquid in which the pyriproxyfen is dissolved in the hydrophobic organic solvent is dispersed in water and the clothianidin is suspended,
The ethylene oxide propylene oxide block copolymer has an HLB value of 5.0 or more and 20.0 or less,
a ratio (W 2 /W 1 ) of the weight W 2 of the hydrophobic organic solvent to the weight W 1 of the pyriproxyfen is 1.0 or more and 6.0 or less;
A ratio (W 4 /W 3 ) of the total weight W 4 of the pyriproxyfen, the clothianidin , and the hydrophobic organic solvent to the weight W 3 of the ethylene oxide propylene oxide block copolymer is 2.0 or more and 80.0. A liquid pesticide composition, which is:
[3] The liquid agricultural chemical composition according to [1] or [2], wherein the hydrophobic organic solvent contains a solvent having a density of 0.85 g/cm 3 or more and 1.20 g/cm 3 or less.
[4] The liquid agricultural chemical composition according to [1], further comprising a second surfactant.
[5] The liquid agricultural chemical composition according to [4], wherein the second surfactant comprises a ligninsulfonate.
[6] Any one of [1] to [ 5] , wherein the ratio of the mass W5 of the clothianidin to the mass W1 of the pyriproxyfen ( W5 / W1 ) is 0.03 or more and 30 or less. 10. Liquid pesticide composition according to paragraph.
[7] When the total mass of the liquid agricultural chemical composition is 100% by mass, the total mass W6 of the pyriproxyfen and the clothianidin is 0.1% by mass or more and 50% by mass or less [1] The liquid agricultural chemical composition according to any one of [6].
　本発明によれば、農薬活性化合物としてピリプロキシフェン及びクロチアニジンを含む液体農薬組成物であって、優れた保存安定性を有する液体農薬組成物を提供することができる。 According to the present invention, it is possible to provide a liquid agricultural chemical composition containing pyriproxyfen and clothianidin as agricultural chemical active compounds and having excellent storage stability.
　本発明に係る液体農薬組成物（以下、「本発明組成物」ということがある。）は、ピリプロキシフェン、クロチアニジン、疎水性有機溶媒、第１界面活性剤、及び水を含む。 The liquid agricultural chemical composition according to the present invention (hereinafter sometimes referred to as "the composition of the present invention") contains pyriproxyfen, clothianidin, a hydrophobic organic solvent, a first surfactant, and water.
　本発明組成物は、農薬活性化合物として、少なくともピリプロキシフェンとクロチアニジンとを含む。ピリプロキシフェンは、４－フェノキシフェニル－２（２－ピリジルオキシ）プロピルエーテルの一般名であり、例えば特開昭６０－２１５６７１号公報に記載の方法により製造することができ、市販品を使用することもできる。クロチアニジンは、１－（２－クロロ－５－チアゾリルメチル）－３－メチル－２－ニトログアニジンの一般名であり、例えば特開平３－１５７３０８号公報に記載の方法により製造することができ、市販品を使用することもできる。 The composition of the present invention contains at least pyriproxyfen and clothianidin as pesticide active compounds. Pyriproxyfen is a generic name for 4-phenoxyphenyl-2(2-pyridyloxy)propyl ether, and can be produced, for example, by the method described in JP-A-60-215671, and a commercially available product is used. can also Clothianidin is a general name for 1-(2-chloro-5-thiazolylmethyl)-3-methyl-2-nitroguanidine, and can be produced, for example, by the method described in JP-A-3-157308. can also be used.
　本発明組成物は、水中に、前記疎水性有機溶媒にピリプロキシフェンが溶解した液体が分散し、かつ、クロチアニジンが懸濁している。本発明組成物は、連続相が水相であり、連続相に、ピリプロキシフェンは前記疎水性有機溶媒に溶解して液体状態で、クロチアニジンは固体状態で、それぞれ分散しているサスポエマルジョン（suspoemulsion）である。 In the composition of the present invention, a liquid in which pyriproxyfen is dissolved in the hydrophobic organic solvent is dispersed in water, and clothianidin is suspended. In the composition of the present invention, the continuous phase is an aqueous phase, pyriproxyfen is dissolved in the hydrophobic organic solvent in a liquid state, and clothianidin is in a solid state, respectively dispersed in the continuous phase Suspoemulsion ( suspoemulsion).
　本発明組成物中のピリプロキシフェンの含有量は、通常０．１質量％以上であり、好ましくは０．５質量％以上であり、より好ましくは１質量％以上である。本発明組成物中のピリプロキシフェンの含有量は、通常５０質量％以下であり、好ましくは３０質量％以下であり、より好ましくは２５質量％以下である。 The content of pyriproxyfen in the composition of the present invention is usually 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The content of pyriproxyfen in the composition of the present invention is generally 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.
　本発明組成物中のクロチアニジンの含有量は、通常０．１質量％以上であり、好ましくは０．５質量％以上であり、より好ましくは２質量％以上である。本発明組成物中のクロチアニジンの含有量は、通常５０質量％以下であり、好ましくは３０質量％以下であり、より好ましくは２５質量％以下である。 The content of clothianidin in the composition of the present invention is usually 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 2% by mass or more. The content of clothianidin in the composition of the present invention is generally 50% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.
　本発明組成物中のピリプロキシフェンの質量Ｗ１とクロチアニジンの質量Ｗ５の比（Ｗ５／Ｗ１）は、通常０．０３以上３０以下であり、好ましくは０．０５以上２０以下であり、より好ましくは０．１以上１０以下である。 The ratio of the weight W1 of pyriproxyfen to the weight W5 of clothianidin in the composition of the present invention ( W5 / W1 ) is usually 0.03 or more and 30 or less, preferably 0.05 or more and 20 or less. , more preferably 0.1 or more and 10 or less.
　本発明組成物中のピリプロキシフェン及びクロチアニジンの合計質量Ｗ６は、本発明組成物の全質量を１００質量％としたときに、通常５０質量％以下であり、好ましくは３０質量％以下であり、より好ましくは、２５質量％以下である。本発明組成物中のピリプロキシフェン及びクロチアニジンの合計質量Ｗ６は、本発明組成物の全質量を１００質量％としたときに、通常０．１質量％以上であり、好ましくは０．５質量％以上であり、より好ましくは２質量％以上である。 The total mass W6 of pyriproxyfen and clothianidin in the composition of the present invention is usually 50% by mass or less, preferably 30% by mass or less, when the total mass of the composition of the present invention is 100% by mass. , more preferably 25% by mass or less. The total mass W6 of pyriproxyfen and clothianidin in the composition of the present invention is usually at least 0.1% by mass, preferably 0.5% by mass, when the total mass of the composition of the present invention is 100% by mass. % or more, more preferably 2 mass % or more.
　本発明組成物において、水相には、疎水性有機溶媒にピリプロキシフェンが溶解した液体が分散しており、当該液体にはピリプロキシフェン以外の農薬活性化合物が溶解又は懸濁していてもよい。かかる農薬活性化合物としては、例えば、殺虫活性化合物、殺菌活性化合物、除草活性化合物、昆虫成長制御活性化合物、植物成長調整活性化合物が挙げられる。 In the composition of the present invention, a liquid in which pyriproxyfen is dissolved in a hydrophobic organic solvent is dispersed in the aqueous phase, and an agriculturally active compound other than pyriproxyfen may be dissolved or suspended in the liquid. . Such agrochemical active compounds include, for example, insecticidal active compounds, fungicidal active compounds, herbicidal active compounds, insect growth-regulating active compounds, and plant growth-regulating active compounds.
　本発明組成物は、疎水性有機溶媒を含む。本明細書において、疎水性有機溶媒とは、温度２５℃における水溶解度が１０質量％以下である有機溶媒をいう。疎水性有機溶媒は、ピリプロキシフェンを溶解させることができる有機溶媒であれば特に限定されない。また、２種以上の疎水性有機溶媒を混合して用いてもよい。 The composition of the present invention contains a hydrophobic organic solvent. As used herein, the term “hydrophobic organic solvent” refers to an organic solvent having a water solubility of 10% by mass or less at a temperature of 25°C. The hydrophobic organic solvent is not particularly limited as long as it can dissolve pyriproxyfen. Also, two or more hydrophobic organic solvents may be mixed and used.
　疎水性有機溶媒としては、例えば、
　ベンジルアルコール等のアルコール；
　酢酸エチル、酢酸ベンジル、安息香酸ベンジル等のエステル；
　アセトフェノン、シクロヘキサノン等のケトン；
　Ｎ，Ｎ－ジメチルオクタンアミド、Ｎ，Ｎ－ジメチルデカンアミド等のアミド；
　トルエン、キシレン等のアルキルベンゼン、メチルナフタレン、ジメチルナフタレン等のアルキルナフタレン、並びにフェニルキシリルエタン及び１－フェニル－１－エチルフェニルエタン、並びにこれらの混合物等の芳香族炭化水素；
が挙げられる。 Hydrophobic organic solvents include, for example,
alcohols such as benzyl alcohol;
Esters such as ethyl acetate, benzyl acetate, benzyl benzoate;
Ketones such as acetophenone and cyclohexanone;
Amides such as N,N-dimethyloctanamide and N,N-dimethyldecanamide;
alkylbenzenes such as toluene and xylene; alkylnaphthalenes such as methylnaphthalene and dimethylnaphthalene; and aromatic hydrocarbons such as phenylxylylethane and 1-phenyl-1-ethylphenylethane, and mixtures thereof;
is mentioned.
　好ましい疎水性有機溶媒としては、アセトフェノン、酢酸ベンジル、安息香酸ベンジル及び芳香族炭化水素等の芳香族化合物が挙げられるが、より好ましくは、芳香族炭化水素が挙げられる。 Preferred hydrophobic organic solvents include aromatic compounds such as acetophenone, benzyl acetate, benzyl benzoate and aromatic hydrocarbons, more preferably aromatic hydrocarbons.
　疎水性有機溶媒は、好ましくは密度が０．８５ｇ／ｃｍ３以上１．２０ｇ／ｃｍ３以下の溶媒であり、より好ましくは密度が０．８９ｇ／ｃｍ３以上１．１２ｇ／ｃｍ３以下の溶媒である。本明細書において密度はＪＩＳ　Ｋ２２４９－３（制定年月日２０１１年１１月２１日）で測定される密度を意味する。 The hydrophobic organic solvent is preferably a solvent having a density of 0.85 g/cm 3 or more and 1.20 g/cm 3 or less, more preferably a solvent having a density of 0.89 g/cm 3 or more and 1.12 g/cm 3 or less. is. Density as used herein means density measured according to JIS K2249-3 (enacted on November 21, 2011).
　本発明組成物中の疎水性有機溶媒の含有量は、通常は０．１質量％以上であり、好ましくは０．５質量％以上であり、より好ましくは１質量％以上であり、また、通常は５０質量％以下であり、好ましくは３０質量％以下であり、より好ましくは２０質量％以下である。疎水性有機溶媒の含有量は、２種以上の疎水性有機溶媒を含む場合は、その合計質量をいう。 The content of the hydrophobic organic solvent in the composition of the present invention is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more. is 50% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less. The content of the hydrophobic organic solvent refers to the total mass when two or more hydrophobic organic solvents are included.
　本発明組成物中の疎水性有機溶媒の含有量のうち、芳香族炭化水素の含有量は、疎水性有機溶媒全量を１００質量％としたときに、好ましくは３０質量％以上であり、より好ましくは５０質量％以上であり、７０質量％以上であってもよく、９０質量％以上であってもよく、１００質量％であってもよい。 Of the content of the hydrophobic organic solvent in the composition of the present invention, the content of the aromatic hydrocarbon is preferably 30% by mass or more, more preferably 100% by mass of the total amount of the hydrophobic organic solvent. is 50% by mass or more, may be 70% by mass or more, may be 90% by mass or more, or may be 100% by mass.
　本発明組成物中の、ピリプロキシフェンの質量Ｗ１と疎水性有機溶媒Ｗ２の質量比（Ｗ２／Ｗ１）は、通常は１．０以上６．０以下、好ましくは１．０以上５．０以下、より好ましくは１．０以上３．０以下である。 The mass ratio (W 2 /W 1 ) of pyriproxyfen mass W 1 and hydrophobic organic solvent W 2 in the composition of the present invention is usually 1.0 or more and 6.0 or less, preferably 1.0 or more. 5.0 or less, more preferably 1.0 or more and 3.0 or less.
　本発明組成物は、疎水性有機溶媒以外の有機溶媒を含有していてもよい。 The composition of the present invention may contain an organic solvent other than the hydrophobic organic solvent.
　本発明組成物において、水相には、クロチアニジンが懸濁しており、クロチアニジン以外の農薬活性化合物が懸濁していてもよい。かかる農薬活性化合物としては、例えば、殺虫活性化合物、殺菌活性化合物、除草活性化合物、昆虫成長制御活性化合物、植物成長調整活性化合物が挙げられる。 In the composition of the present invention, clothianidin is suspended in the aqueous phase, and an agriculturally active compound other than clothianidin may also be suspended. Such agrochemical active compounds include, for example, insecticidal active compounds, fungicidal active compounds, herbicidal active compounds, insect growth-regulating active compounds, and plant growth-regulating active compounds.
　本発明組成物は、第１界面活性剤を含む。本発明組成物において、第１界面活性剤は、脂肪酸エチレンオキサイド付加物、多価アルコール脂肪酸エステルエチレンオキサイド付加物、及びエチレンオキサイドプロピレンオキサイドブロックコポリマーからなる群から選ばれる１種または２種以上の成分からなる。本発明組成物に含まれる第１界面活性剤は、ＨＬＢ値が５．０以上２０．０以下であり、好ましくは１０．０以上１９．０以下である。本発明組成物は第１界面活性剤を含むことにより、液体農薬組成物の保存安定性を向上させることができる。本明細書において保存安定性を向上させるとは、高温及び／または低温での保存において農薬活性化合物の凝集や粒子成長を抑制することを含む。 The composition of the present invention contains a first surfactant. In the composition of the present invention, the first surfactant is one or more components selected from the group consisting of fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, and ethylene oxide propylene oxide block copolymers. consists of The first surfactant contained in the composition of the present invention has an HLB value of 5.0 or more and 20.0 or less, preferably 10.0 or more and 19.0 or less. By including the first surfactant in the composition of the present invention, the storage stability of the liquid agricultural chemical composition can be improved. As used herein, improving the storage stability includes suppressing aggregation and particle growth of the agricultural chemical active compound during storage at high and/or low temperatures.
　本明細書において、ＨＬＢ値はグリフィン法によるＨＬＢ値を意味し、第１界面活性剤のＨＬＢ値は、第１界面活性剤が１種の界面活性剤からなる場合にはその界面活性剤のＨＬＢ値を意味し、２種以上の界面活性剤からなる場合には個々の界面活性剤のＨＬＢ値に配合比を掛け合わせた値の合計値を意味する。例えば、第１界面活性剤が、ＨＬＢ値が１２の界面活性剤を配合比５０質量％で含み、ＨＬＢ値が６の界面活性剤を配合比５０質量％で含む場合、第１界面活性剤のＨＬＢ値は９（＝１２×０．５＋６×０．５）となる。 As used herein, the HLB value means the HLB value according to the Griffin method, and the HLB value of the first surfactant is the HLB value of the surfactant when the first surfactant consists of one surfactant. When two or more surfactants are used, it means the total value obtained by multiplying the HLB value of each surfactant by the compounding ratio. For example, when the first surfactant contains a surfactant with an HLB value of 12 at a blending ratio of 50% by mass and a surfactant with an HLB value of 6 at a blending ratio of 50% by mass, the first surfactant The HLB value is 9 (=12×0.5+6×0.5).
　本明細書において、脂肪酸エチレンオキサイド付加物（以下、「エチレンオキサイド付加物」を「ＥＯ付加物」とも称する）は、脂肪酸にエチレンオキサイドが付加している化合物を意味し、ポリエチレングリコール脂肪酸エステルとも呼ばれる。脂肪酸ＥＯ付加物は、モノエステルであってもよく、ジエステルであってもよい。脂肪酸ＥＯ付加物における脂肪酸は、通常、炭素数１０～２０の脂肪酸であり、好ましくは、炭素数１２～１８の脂肪酸である。脂肪酸ＥＯ付加物としては、例えば、モノラウリン酸ＥＯ付加物、モノステアリン酸ＥＯ付加物、ジオレイン酸ＥＯ付加物が挙げられる。脂肪酸ＥＯ付加物におけるＥＯ付加モル数は、通常、２～１００であり、好ましくは、１０～１００である。脂肪酸ＥＯ付加物のＨＬＢ値は、好ましくは５以上であり、より好ましくは７以上であり、１０以上であってもよい。また、好ましくは２０以下であり、より好ましくは１９以下である。 As used herein, fatty acid ethylene oxide adduct (hereinafter, "ethylene oxide adduct" is also referred to as "EO adduct") means a compound in which ethylene oxide is added to a fatty acid, and is also called polyethylene glycol fatty acid ester. . Fatty acid EO adducts may be monoesters or diesters. The fatty acid in the fatty acid EO adduct is usually a C10-20 fatty acid, preferably a C12-18 fatty acid. Fatty acid EO adducts include, for example, monolauric acid EO adducts, monostearic acid EO adducts, and dioleic acid EO adducts. The number of EO addition moles in the fatty acid EO adduct is usually 2-100, preferably 10-100. The HLB value of the fatty acid EO adduct is preferably 5 or more, more preferably 7 or more, and may be 10 or more. Also, it is preferably 20 or less, more preferably 19 or less.
　本明細書において、多価アルコール脂肪酸エステルＥＯ付加物は、多価アルコールと脂肪酸とのエステルにエチレンオキサイドが付加している化合物を意味する。多価アルコールは、水酸基を３～６個有するアルコールである。多価アルコールと脂肪酸とのエステルは、好ましくはグリセリン脂肪酸エステル（例えば、ひまし油等のトリグリセリド）、ソルビタン脂肪酸エステルまたはソルビトール（ソルビット）脂肪酸エステルである。多価アルコールと脂肪酸とのエステルにおける脂肪酸は、通常、炭素数１０～２０の脂肪酸であり、好ましくは、炭素数１２～１８の脂肪酸である。多価アルコール脂肪酸エステルＥＯ付加物としては、例えば、ソルビタンモノステアリン酸エステルＥＯ付加物、ソルビタントリオレイン酸エステルＥＯ付加物、ひまし油ＥＯ付加物が挙げられる。多価アルコール脂肪酸エステルＥＯ付加物におけるＥＯ付加モル数は、通常、２～１００であり、好ましくは、１０～５５である。多価アルコール脂肪酸エステルＥＯ付加物のＨＬＢ値は、好ましくは５以上であり、より好ましくは７以上であり、１０以上であってもよい。また、好ましくは２０以下であり、より好ましくは１９以下である。 As used herein, a polyhydric alcohol fatty acid ester EO adduct means a compound in which ethylene oxide is added to an ester of polyhydric alcohol and fatty acid. Polyhydric alcohols are alcohols having 3 to 6 hydroxyl groups. Esters of polyhydric alcohols and fatty acids are preferably glycerine fatty acid esters (eg, triglycerides such as castor oil), sorbitan fatty acid esters or sorbitol (sorbit) fatty acid esters. Fatty acids in esters of polyhydric alcohols and fatty acids are usually fatty acids with 10 to 20 carbon atoms, preferably fatty acids with 12 to 18 carbon atoms. Polyhydric alcohol fatty acid ester EO adducts include, for example, sorbitan monostearate EO adducts, sorbitan trioleate EO adducts, and castor oil EO adducts. The number of EO addition moles in the polyhydric alcohol fatty acid ester EO adduct is usually 2-100, preferably 10-55. The HLB value of the polyhydric alcohol fatty acid ester EO adduct is preferably 5 or more, more preferably 7 or more, and may be 10 or more. Also, it is preferably 20 or less, more preferably 19 or less.
　エチレンオキサイドプロピレンオキサイドブロックコポリマーのＨＬＢ値は、好ましくは５以上であり、より好ましくは７以上であり、１０以上であってもよい。また、好ましくは２０以下であり、より好ましくは１９以下である。エチレンオキサイドプロピレンオキサイドブロックコポリマーの平均分子量は、好ましくは１５００以上であり、より好ましくは２０００以上であり、２５００以上であってもよい。また、好ましくは８０００以下であり、より好ましくは７５００以下であり、７０００以下であってもよい。 The HLB value of the ethylene oxide propylene oxide block copolymer is preferably 5 or more, more preferably 7 or more, and may be 10 or more. Also, it is preferably 20 or less, more preferably 19 or less. The average molecular weight of the ethylene oxide propylene oxide block copolymer is preferably 1500 or more, more preferably 2000 or more, and may be 2500 or more. Also, it is preferably 8,000 or less, more preferably 7,500 or less, and may be 7,000 or less.
　本発明組成物中の第１界面活性剤の含有量は、好ましくは０．１質量％以上であり、より好ましくは０．５質量％以上であり、さらに好ましくは０．７質量％以上であり、また、好ましくは２０．０質量％以下であり、より好ましくは１０．０質量％以下であり、さらに好ましくは８．５質量％以下である。 The content of the first surfactant in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.7% by mass or more. Also, it is preferably 20.0% by mass or less, more preferably 10.0% by mass or less, and still more preferably 8.5% by mass or less.
　本発明組成物において、前記第１界面活性剤の質量Ｗ３に対する、前記ピリプロキシフェン、前記クロチアニジン、及び前記疎水性有機溶媒の合計質量Ｗ４の比（Ｗ４／Ｗ３）が、２．０以上８０．０以下であり、好ましくは２．０以上７０．０以下であり、より好ましくは２．０以上６０．０以下である。本発明組成物において、比（Ｗ４／Ｗ３）が上記範囲であることにより、液体農薬組成物の保存安定性を向上させることができる。 In the composition of the present invention, the ratio (W 4 /W 3 ) of the total weight W 4 of the pyriproxyfen, the clothianidin and the hydrophobic organic solvent to the weight W 3 of the first surfactant is 2. It is 0 or more and 80.0 or less, preferably 2.0 or more and 70.0 or less, more preferably 2.0 or more and 60.0 or less. In the composition of the present invention, when the ratio (W 4 /W 3 ) is within the above range, the storage stability of the liquid agricultural chemical composition can be improved.
　本発明組成物において、前記第１界面活性剤の質量Ｗ３に対する、前記ピリプロキシフェンの質量Ｗ１の比（Ｗ１／Ｗ３）は、好ましくは０．１以上３５．０以下であり、より好ましくは０．１５以上３０．０以下である。 In the composition of the present invention, the ratio (W 1 /W 3 ) of the mass W 1 of the pyriproxyfen to the mass W 3 of the first surfactant is preferably 0.1 or more and 35.0 or less, It is more preferably 0.15 or more and 30.0 or less.
　本発明組成物において、前記第１界面活性剤の質量Ｗ３に対する、前記ピリプロキシフェンの質量Ｗ１と前記疎水性有機溶媒の質量Ｗ２の合計質量の比（（Ｗ１＋Ｗ２）／Ｗ３）は、好ましくは０．２５以上７０．０以下であり、より好ましくは０．３０以上６０．０以下である。 In the composition of the present invention, the ratio of the total mass of the mass W1 of the pyriproxyfen and the mass W2 of the hydrophobic organic solvent to the mass W3 of the first surfactant (( W1 + W2 )/W 3 ) is preferably from 0.25 to 70.0, more preferably from 0.30 to 60.0.
　本発明組成物において、前記第１界面活性剤の質量Ｗ３に対する、前記クロチアニジンの質量Ｗ５の比（Ｗ５／Ｗ３）は、好ましくは０．４以上２０以下である。 In the composition of the present invention, the ratio of the mass W5 of the clothianidin to the mass W3 of the first surfactant ( W5 / W3 ) is preferably 0.4 or more and 20 or less.
　本発明組成物は、さらに、第１界面活性剤とは異なる他の界面活性剤（以下、「第２界面活性剤」とも称する）を含んでいてもよい。第２界面活性剤は、脂肪酸ＥＯ付加物、多価アルコール脂肪酸エステルＥＯ付加物、エチレンオキサイドプロピレンオキサイドブロックコポリマー以外の界面活性剤であれば限定されず、ノニオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤及びこれらの混合物が挙げられる。 The composition of the present invention may further contain another surfactant (hereinafter also referred to as "second surfactant") different from the first surfactant. The second surfactant is not limited as long as it is a surfactant other than fatty acid EO adduct, polyhydric alcohol fatty acid ester EO adduct, ethylene oxide propylene oxide block copolymer, nonionic surfactant, anionic surfactant. , cationic surfactants, amphoteric surfactants and mixtures thereof.
　ノニオン性界面活性剤としては、例えば、ポリオキシエチレンジスチリルフェニルエーテル、ポリオキシエチレントリスチリルフェニルエーテル、ショ糖脂肪酸エステル、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレンアルキルアミン、アルキルアルカノールアミド、アルキルポリグコシドが挙げられる。 Examples of nonionic surfactants include polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, sucrose fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide, alkyl polyglycosides.
　アニオン性界面活性剤としては、例えば、スルホン酸塩、硫酸エステル塩、リン酸エステル塩、カルボン酸塩及びこれらの混合物である。スルホン酸塩としては、例えば、ナフタレンスルホン酸又はアルキルナフタレンスルホン酸の塩、ナフタレンスルホン酸又はアルキルナフタレンスルホン酸のホルマリン縮合物の塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、α－オレフィンスルホン酸塩、リグニンスルホン酸塩、ポリオキシエチレンアルキルフェニルエーテルスルホン酸塩並びにジアルキルスルホこはく酸塩が挙げられる。硫酸エステル塩としては、例えば、アルキル硫酸エステル塩、ポリオキシエチレンアルキルエーテル硫酸エステル塩及びポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩が挙げられる。リン酸エステル塩としては、例えば、ポリオキシエチレンアルキルアリールエーテルリン酸エステル塩及びポリオキシエチレントリスチリルフェニルエーテルリン酸エステル塩が挙げられる。カルボン酸塩としては、例えば、脂肪酸塩やポリアクリル酸塩等のポリカルボン酸塩が挙げられる。アニオン性界面活性剤を構成する塩としては、ナトリウム、カリウム等のアルカリ金属；カルシウム、マグネシウム等のアルカリ土類金属；アンモニウム；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等に由来する有機アンモニウム等が挙げられる。 Examples of anionic surfactants include sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates include salts of naphthalenesulfonic acid or alkylnaphthalenesulfonic acid, salts of formalin condensates of naphthalenesulfonic acid or alkylnaphthalenesulfonic acid, alkylbenzenesulfonates, alkyldiphenylether disulfonates, and α-olefinsulfonic acids. salts, lignin sulfonates, polyoxyethylene alkylphenyl ether sulfonates and dialkyl sulfosuccinates. Sulfate ester salts include, for example, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts and polyoxyethylene alkylphenyl ether sulfate ester salts. Phosphate salts include, for example, polyoxyethylene alkylaryl ether phosphate salts and polyoxyethylene tristyrylphenyl ether phosphate salts. Examples of carboxylates include polycarboxylates such as fatty acid salts and polyacrylates. Salts constituting anionic surfactants include alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; ammonium; organic ammonium derived from monoethanolamine, diethanolamine, triethanolamine, and the like. be done.
　カチオン性界面活性剤としては、アルキルアミン塩及び第四級アンモニウム塩が挙げられる。 Cationic surfactants include alkylamine salts and quaternary ammonium salts.
　好ましい第２界面活性剤としては、第１界面活性剤以外のノニオン性界面活性剤、及び／又は、アニオン性界面活性剤である。さらに好ましい第２界面活性剤としては、アニオン性界面活性剤が挙げられる。特に第２界面活性剤として、リグニンスルホン酸塩を用いることにより、本発明組成物は農薬活性化合物の凝集を効果的に抑制することができる。 Preferred second surfactants are nonionic surfactants other than the first surfactant and/or anionic surfactants. More preferred second surfactants include anionic surfactants. In particular, by using ligninsulfonate as the second surfactant, the composition of the present invention can effectively suppress aggregation of the agricultural chemical active compound.
　本発明組成物中の第２界面活性剤の含有量は、好ましくは０．１質量％以上であり、より好ましくは０．５質量％以上であり、１質量％以上であってもよく、また、好ましくは１０質量％以下であり、より好ましくは７質量％以下であり、５質量％以下であってもよい。第２界面活性剤の含有量は、第２界面活性剤が２種以上の界面活性剤を含む場合は、その合計含有量をいう。 The content of the second surfactant in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and may be 1% by mass or more. , preferably 10% by mass or less, more preferably 7% by mass or less, and may be 5% by mass or less. The content of the second surfactant refers to the total content when the second surfactant contains two or more surfactants.
　本発明組成物中の第２界面活性剤の含有量のうち、リグニンスルホン酸塩の含有量は、第２界面活性剤全量を１００質量％としたときに、好ましくは３０質量％以上であり、より好ましくは５０質量％以上である。 Of the content of the second surfactant in the composition of the present invention, the content of lignin sulfonate is preferably 30% by mass or more when the total amount of the second surfactant is 100% by mass, More preferably, it is 50% by mass or more.
　本発明組成物が第１界面活性剤及び第２界面活性剤を含む場合、その含有量の質量比は、第１界面活性剤／第２界面活性剤が、好ましくは０．１以上であり、０．２以上であってもよく、０．２５以上であってもよく、また、好ましくは１０以下であり、８以下であってもよく、６以下であってもよい。 When the composition of the present invention contains a first surfactant and a second surfactant, the mass ratio of the content of the first surfactant/second surfactant is preferably 0.1 or more, It may be 0.2 or more, or 0.25 or more, preferably 10 or less, 8 or less, or 6 or less.
　本発明組成物は、水を含む。水としては、例えばイオン交換水、蒸留水、濾過水、水道水及び地下水が挙げられる。本発明組成物中の水の含有量は、通常２０質量％以上であり、３０質量％以上であってもよく、４０質量％以上であってもよく、また、通常９０質量％以下であり、８５質量％以下であってもよく、８０質量％以下であってもよい。 The composition of the present invention contains water. Examples of water include ion-exchanged water, distilled water, filtered water, tap water and groundwater. The content of water in the composition of the present invention is usually 20% by mass or more, may be 30% by mass or more, may be 40% by mass or more, and is usually 90% by mass or less, It may be 85% by mass or less, or may be 80% by mass or less.
　本発明組成物は必要に応じその他製剤用補助剤を含有していてもよい。その他の製剤用補助剤としては、例えば、増粘剤、消泡剤、凍結防止剤、防腐剤等が挙げられる。 The composition of the present invention may contain other formulation adjuvants as necessary. Other formulation adjuvants include, for example, thickeners, antifoaming agents, antifreezing agents, preservatives and the like.
　増粘剤としては、例えばキサンタンガム等の多糖類、粘土、ケイ酸塩等が挙げられる。本発明組成物中の増粘剤の含有量は、通常０．０５質量％以上であり、０．１質量％以上であってもよく、また、通常５質量％以下であり、３質量％以下であってもよい。 Examples of thickeners include polysaccharides such as xanthan gum, clays, and silicates. The content of the thickening agent in the composition of the present invention is usually 0.05% by mass or more, and may be 0.1% by mass or more, and is usually 5% by mass or less and 3% by mass or less. may be
　消泡剤としては、例えばシリコーン系消泡剤が挙げられる。本発明組成物中の消泡剤の含有量は、通常０．０１質量％以上であり、０．０５質量％以上であってもよく、また、通常１質量％以下であり、０．５質量％以下であってもよい。 Examples of antifoaming agents include silicone antifoaming agents. The content of the antifoaming agent in the composition of the present invention is usually 0.01% by mass or more, may be 0.05% by mass or more, and is usually 1% by mass or less, and 0.5% by mass. % or less.
　凍結防止剤としては、例えばエチレングリコール、プロピレングリコール、尿素、グリセリン等が挙げられる。本発明組成物中の凍結防止剤の含有量は、通常１質量％以上であり、２質量％以上であってもよく、また、通常１０質量％以下であり、８質量％以下であってもよい。 Antifreeze agents include, for example, ethylene glycol, propylene glycol, urea, and glycerin. The content of the antifreeze agent in the composition of the present invention is usually 1% by mass or more, may be 2% by mass or more, and is usually 10% by mass or less, and may be 8% by mass or less. good.
　防腐剤としては、例えばイソチアゾリノン系防腐剤が挙げられる。本発明組成物中の防腐剤の含有量は、通常０．０５質量％以上であり、０．１質量％以上であってもよく、また、通常０．５質量％以下であり、０．３質量％以下であってもよい。 Examples of preservatives include isothiazolinone-based preservatives. The content of the antiseptic in the composition of the present invention is usually 0.05% by mass or more, may be 0.1% by mass or more, and is usually 0.5% by mass or less, and 0.3% by mass. % by mass or less.
　本発明組成物は、水希釈時の良好な安定性（希釈から散布までを想定した期間、散布ムラの原因となり得る沈殿や相分離が起こらない、ノズル閉塞を起こし得る析出物の発生がない）、容器からの良好な排出性、低温、及び／または高温環境下における保管時の良好な物理的安定性（経時的な沈殿・ケーキングの発生、固体粒子の結晶成長・凝集、油滴の合一、相分離、及び色目の変化がない、または少ない）、化学的安定性（クロチアニジン及び／またはピリプロキシフェンの経時的な分解がない、または少ない）、及び良好な殺虫活性を示す。 The composition of the present invention has good stability when diluted with water (there is no precipitation or phase separation that can cause uneven spraying, and no precipitate that can cause nozzle clogging during the period assumed from dilution to spraying). , good dischargeability from containers, good physical stability during storage in low and/or high temperature environments (precipitation/caking over time, crystal growth/aggregation of solid particles, coalescence of oil droplets , phase separation, and color change), chemical stability (no or little degradation of clothianidin and/or pyriproxyfen over time), and good insecticidal activity.
　本発明組成物は、例えば、農薬活性化合物であるピリプロキシフェン及びクロチアニジン、疎水性有機溶媒、第１界面活性剤、水並びに必要に応じて、第２界面活性剤及び製剤用補助剤を用いて製造することができる。本発明組成物は、例えば次の方法で製造することができる。 The composition of the present invention is prepared by using, for example, the agricultural chemical active compounds pyriproxyfen and clothianidin, a hydrophobic organic solvent, a first surfactant, water, and, if necessary, a second surfactant and formulation aids. can be manufactured. The composition of the present invention can be produced, for example, by the following method.
　（方法１）
　ピリプロキシフェン、第１界面活性剤、疎水性有機溶媒、及び必要に応じて製剤用補助剤を水に添加し、ホモジナイザー等の撹拌機で撹拌・分散することにより、エマルジョンを調製する。このとき、第１界面活性剤は疎水性有機溶媒に添加してもよく、水に添加してもよく、また両者に添加してもよい。一方で、クロチアニジン、第１界面活性剤及び／又は第２界面活性剤、必要に応じて製剤用補助剤を水に添加し、ガラスビーズ、ジルコニアビーズ等のメディアを用いた湿式粉砕により粉砕・懸濁させることにより、サスペンジョンを調製する。次に、エマルジョン、サスペンジョン、及び、必要に応じて増粘剤、防腐剤、消泡剤等の製剤用補助剤を混合して、本発明組成物を得る。 (Method 1)
An emulsion is prepared by adding pyriproxyfen, a first surfactant, a hydrophobic organic solvent, and optionally formulation aids to water and stirring and dispersing with a stirrer such as a homogenizer. At this time, the first surfactant may be added to the hydrophobic organic solvent, water, or both. On the other hand, clothianidin, a first surfactant and/or a second surfactant, and optionally a formulation adjuvant are added to water, and pulverized and suspended by wet pulverization using media such as glass beads and zirconia beads. Suspensions are prepared by turbidity. Next, the emulsion, suspension, and, if necessary, formulation aids such as thickeners, preservatives and antifoaming agents are mixed to obtain the composition of the present invention.
　（方法２）
　クロチアニジン、第１界面活性剤及び／又は第２界面活性剤、及び必要に応じて製剤用補助剤を水に添加し、ガラスビーズ、ジルコニアビーズ等のメディアを用いた湿式粉砕により粉砕・懸濁させることにより、サスペンジョンを調製する。次に、ピリプロキシフェン、疎水性有機溶媒、並びに必要に応じて第１界面活性剤及び必要に応じて第２界面活性剤、製剤用補助剤をサスペンジョンに添加し、ホモジナイザー等の撹拌機で撹拌・分散することにより、乳化を行う。次に、必要に応じて増粘剤、防腐剤、消泡剤等の製剤用補助剤を混合して、本発明組成物を得る。 (Method 2)
Clothianidin, a first surfactant and/or a second surfactant, and, if necessary, formulation aids are added to water, and pulverized and suspended by wet pulverization using media such as glass beads and zirconia beads. to prepare the suspension. Next, pyriproxyfen, a hydrophobic organic solvent, and optionally a first surfactant and optionally a second surfactant and formulation aids are added to the suspension and stirred with a stirrer such as a homogenizer.・Emulsify by dispersing. Next, formulation aids such as thickeners, preservatives and antifoaming agents are mixed as necessary to obtain the composition of the present invention.
　（方法３）
　ピリプロキシフェン、疎水性有機溶媒、並びに、必要に応じて第１界面活性剤及び必要に応じて第２界面活性剤、製剤用補助剤を混合し油相を調製する。一方で、クロチアニジン、第１界面活性剤及び／又は第２界面活性剤、必要に応じて製剤用補助剤を水に添加し、水相を調製する。油相と水相を混合し、ガラスビーズ、ジルコニアビーズ等のメディアを用いた湿式粉砕により乳化および粉砕・懸濁を同時に行い、必要に応じて増粘剤、防腐剤、消泡剤等の製剤用補助剤と混合して、本発明組成物を得る。 (Method 3)
An oil phase is prepared by mixing pyriproxyfen, a hydrophobic organic solvent, and optionally a first surfactant, optionally a second surfactant, and formulation aids. On the other hand, clothianidin, a first surfactant and/or a second surfactant, and optionally formulation aids are added to water to prepare an aqueous phase. The oil phase and water phase are mixed, emulsified, pulverized, and suspended simultaneously by wet pulverization using media such as glass beads and zirconia beads. to obtain the composition of the present invention.
　本発明組成物を、植物またはその生育環境に施用することにより害虫を防除することができる。本発明組成物により防除し得る害虫としては、例えば、コナジラミ、アブラムシ、ヨコバイ、ワタゾウムシが挙げられる。 Pests can be controlled by applying the composition of the present invention to plants or their growing environment. Pests that can be controlled by the composition of the present invention include, for example, whiteflies, aphids, leafhoppers, and cotton weevils.
　使用者は、本発明組成物を、通常、背負式散布機（knapsack　sprayer）、スプレータンク（spray　tank）、散布航空機（spray　plane）、または灌漑システム（irrigation　system）から施用する。通常、本発明組成物は所望の施用濃度になるように水で希釈され、散布液が得られる。通常、１ヘクタールあたり、１００～１０００Ｌ、好ましくは３００～８００Ｌの散布液が施用される。 The user typically applies the composition of the present invention from a knapsack sprayer, spray tank, spray plane, or irrigation system. The compositions according to the invention are usually diluted with water to the desired application concentration to give a spray liquor. Generally, 100 to 1000 L, preferably 300 to 800 L of spray solution are applied per hectare.
　本発明組成物の施用量は、植物の種類、防除対象である害虫の種類や発生頻度、施用時期、施用方法、施用場所、気象条件等によっても異なるが、ピリプロキシフェンの施用量として、１ヘクタールあたり、通常５５～２５０ｇであり、クロチアニジンの施用量として、１ヘクタールあたり、通常２５～１００ｇである。 The application amount of the composition of the present invention varies depending on the type of plant, the type and frequency of occurrence of pests to be controlled, the timing of application, the application method, the place of application, weather conditions, etc., but the application amount of pyriproxyfen is 1. It is usually 55 to 250 g per hectare, and the application amount of clothianidin is usually 25 to 100 g per hectare.
　以下、本発明を実施例及び比較例等によりさらに詳しく説明するが、本発明はこれらの例に限定されるものではない。 The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.
　液体農薬組成物の調製に用いた製品を以下に示す。以下においてｄは密度（ｇ／ｃｍ３）、Ｍｗは平均分子量を表す。 The products used to prepare the liquid pesticide compositions are shown below. In the following, d represents density (g/cm 3 ) and Mw represents average molecular weight.
　［疎水性有機溶媒］
・ＧａｒｏＳＯＬ　２００ＮＤ：芳香族炭化水素（Ｇａｎｇａ　Ｒａｓａｙｎｉｅ社製）（ｄ＝０．９９）
・アセトフェノン：アセトフェノン（関東化学株式会社製）（ｄ＝１．０３）
・酢酸ベンジル：酢酸ベンジル（東京化成工業株式会社製）（ｄ＝１．０６）
・ＧａｒｏＳＯＬ　１５０ＮＤ：芳香族炭化水素（Ｇａｎｇａ　Ｒａｓａｙｎｉｅ社製）（ｄ＝０．８９）
・安息香酸ベンジル：安息香酸ベンジル（富士フィルム和光純薬株式会社製）（ｄ＝１．１２）
・Ｓｏｌｖｅｓｓｏ　１５０ＮＤ：芳香族炭化水素（Ｅｘｘｏｎ　Ｍｏｂｉｌ　Ｃｈｅｍｉｃａｌ　Ｃｏｍｐａｎｙ製）（ｄ＝０．８９）
・Ｓｏｌｖｅｓｓｏ　２００ＮＤ：芳香族炭化水素（Ｅｘｘｏｎ　Ｍｏｂｉｌ　Ｃｈｅｍｉｃａｌ　Ｃｏｍｐａｎｙ製）（ｄ＝０．９９） [Hydrophobic organic solvent]
・ GaroSOL 200ND: aromatic hydrocarbon (manufactured by Ganga Rasaynie) (d = 0.99)
· Acetophenone: Acetophenone (manufactured by Kanto Chemical Co., Ltd.) (d = 1.03)
・ Benzyl acetate: benzyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) (d = 1.06)
・ GaroSOL 150ND: aromatic hydrocarbon (manufactured by Ganga Rasaynie) (d = 0.89)
・ Benzyl benzoate: benzyl benzoate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (d = 1.12)
Solvesso 150ND: aromatic hydrocarbon (manufactured by Exxon Mobil Chemical Company) (d = 0.89)
Solvesso 200ND: aromatic hydrocarbon (manufactured by Exxon Mobil Chemical Company) (d = 0.99)
　［第１界面活性剤］
　＜エチレンオキサイドプロピレンオキサイドブロックコポリマー＞
・Ｓｔｅｐｆｌｏｗ２６Ｆ：エチレンオキサイドプロピレンオキサイドブロックコポリマー（Ｓｔｅｐａｎ社製）（ＨＬＢ１３，Ｍｗ５９００）（表１～６で「Ｓ１１」と表記）・Ｔｏｘｉｍｕｌ　８３２０：エチレンオキサイドプロピレンオキサイドブロックコポリマー（Ｓｔｅｐａｎ社製）（ＨＬＢ１２，Ｍｗ５５００）（表１～６で「Ｓ１２」と表記）
・Ｇｅｎａｐｏｌ　ＰＦ４０：エチレンオキサイドプロピレンオキサイドブロックコポリマー（Ｃｌａｒｉａｎｔ社製）（ＨＬＢ１６，Ｍｗ２８００）（表１～６で「Ｓ１３」と表記）
・Ｐｅｐｏｌ　Ｂ－１８４：エチレンオキサイドプロピレンオキサイドブロックコポリマー（東邦化学工業株式会社製）（ＨＬＢ１０，ポリオキシエチレン（２５）ポリオキシプロピレングリコール（３０））（表１～６で「Ｓ１４」と表記） [First surfactant]
<Ethylene oxide propylene oxide block copolymer>
・Stepflow26F: ethylene oxide propylene oxide block copolymer (manufactured by Stepan) (HLB13, Mw5900) (denoted as “S11” in Tables 1 to 6) ・Toximul 8320: ethylene oxide propylene oxide block copolymer (manufactured by Stepan) (HLB12, Mw5500) ) (denoted as “S12” in Tables 1 to 6)
- Genapol PF40: Ethylene oxide propylene oxide block copolymer (manufactured by Clariant) (HLB16, Mw2800) (denoted as "S13" in Tables 1 to 6)
・ Pepol B-184: Ethylene oxide propylene oxide block copolymer (manufactured by Toho Chemical Industry Co., Ltd.) (HLB10, polyoxyethylene (25) polyoxypropylene glycol (30)) (denoted as “S14” in Tables 1 to 6)
　＜脂肪酸ＥＯ付加物＞
・Ｍｙｒｊ　Ｓ１００：ステアリン酸ＥＯ付加物（Ｃｒｏｄａ社製）（ＥＯ付加モル数１００、ＨＬＢ１９）（表１～６で「Ｓ２１」と表記）
・Ｍｙｒｊ　Ｓ５０：ステアリン酸ＥＯ付加物（Ｃｒｏｄａ社製）（ＥＯ付加モル数５０、ＨＬＢ１８）（表１～６で「Ｓ２２」と表記） <Fatty acid EO adduct>
・Myrj S100: Stearic acid EO adduct (manufactured by Croda) (EO addition mole number 100, HLB 19) (denoted as “S21” in Tables 1 to 6)
・Myrj S50: stearic acid EO adduct (manufactured by Croda) (EO addition mole number 50, HLB 18) (denoted as “S22” in Tables 1 to 6)
　＜多価アルコール脂肪酸エステルＥＯ付加物＞
・Ｅｍｕｌｓｏｇｅｎ　ＥＬ５４０：ひまし油ＥＯ付加物（Ｃｌａｒｉａｎｔ社製）（ＥＯ付加モル数５４，ＨＬＢ１５）（表１～６で「Ｓ３１」と表記）
・Ｔｗｅｅｎ８５：ソルビタントリオレイン酸ＥＯ付加物（Ｃｒｏｄａ社製）（ＥＯ付加モル数２０，ＨＬＢ１１）（表１～６で「Ｓ３２」と表記）
・Ａｔｌａｓ　Ｇ－１０９６：ソルビトールヘキサオレイン酸ＥＯ付加物（Ｃｒｏｄａ社製）（ＥＯ付加モル数５０、ＨＬＢ１１）（表１～６で「Ｓ３３」と表記） <Polyhydric alcohol fatty acid ester EO adduct>
- Emulsogen EL540: castor oil EO adduct (manufactured by Clariant) (EO addition mole number 54, HLB 15) (denoted as "S31" in Tables 1 to 6)
・Tween 85: Sorbitan trioleic acid EO adduct (manufactured by Croda) (EO addition mole number 20, HLB 11) (denoted as “S32” in Tables 1 to 6)
・Atlas G-1096: Sorbitol hexaoleic acid EO adduct (manufactured by Croda) (EO addition mole number 50, HLB 11) (denoted as “S33” in Tables 1 to 6)
　［第２界面活性剤］
ＲＥＡＸ９１０：リグニンスルホン酸ナトリウム（Ｉｎｇｅｖｉｔｙ社製）
（アニオン性界面活性剤）
ＳｏｐｒｏｐｈｏｒＦＬＫ：ポリオキシエチレントリスチリルフェニルエーテルリン酸エステルカリウム塩（Ｓｏｌｖａｙ社製）（アニオン性界面活性剤） [Second surfactant]
REAX910: sodium ligninsulfonate (manufactured by Ingevity)
(Anionic surfactant)
SoprophorFLK: polyoxyethylene tristyrylphenyl ether phosphate potassium salt (manufactured by Solvay) (anionic surfactant)
　［増粘剤］
Ｋｅｌｚａｎ：キサンタンガム（ＣＰ　Ｋｅｌｃｏ社製）
Ｖｅｅｇｕｍ　Ｒ：ケイ酸マグネシウムアルミニウム（Ｖａｎｄｅｒｂｉｌｔ　Ｍｉｎｅｒａｌｓ社製）
　[消泡剤］
ＸＩＡＭＥＴＥＲ　ＡＣＰ－１５００　Ａｎｔｉｆｏａｍ　Ｃｏｍｐｏｕｎｄ：シリコーン系混合物（東レ・ダウコーニング社製）
　[凍結防止剤］
プロピレングリコール：プロピレングリコール（Ａｄｅｋａ社製）
　[防腐剤］
Ｐｒｏｘｅｌ　ＧＸＬ：１，２－ベンゾイソチアゾリン－３－オン（Ｌｏｎｚａ社製） [Thickener]
Kelzan: xanthan gum (manufactured by CP Kelco)
Veegum R: magnesium aluminum silicate (manufactured by Vanderbilt Minerals)
[Antifoaming agent]
XIAMETER ACP-1500 Antifoam Compound: silicone-based mixture (manufactured by Dow Corning Toray)
[Antifreezing agent]
Propylene glycol: propylene glycol (manufactured by Adeka)
[Preservative]
Proxel GXL: 1,2-benzisothiazolin-3-one (manufactured by Lonza)
　＜実施例１～６：疎水性有機溶媒の種類等を検討＞
　（実施例１）
　イオン交換水　３１．３７ｇにＸＩＡＭＥＴＥＲ　ＡＣＰ－１５００　Ａｎｔｉｆｏａｍ　Ｃｏｍｐｏｕｎｄ　０．２０ｇ、ＲＥＡＸ９１０　２．６０ｇ、Ｖｅｅｇｕｍ　Ｒ　０．４４ｇを添加し、攪拌・混合して水相を調製した。これにクロチアニジン（純度９９．８％）　３．５１ｇを加え攪拌・混合した。得られた混合物をダイノミル（１．０ｍｍガラスビーズ、充填率８０％、周速１０ｍ／ｓ）を用いて湿式粉砕し、クロチアニジン懸濁液を得た。
　一方、ピリプロキシフェン（純度９９．３％）　８．０６ｇ、ＧａｒｏＳＯＬ　２００ＮＤ　８．００ｇ、ＧａｒｏＳＯＬ　１５０ＮＤ　８．００ｇ、Ｓｔｅｐｆｌｏｗ２６Ｆ　３．００ｇを混合し均一な溶液とし油相を調製した。上記のクロチアニジン懸濁液、油相を混合した。得られた混合物をポリトロンを用いて撹拌し、サスポエマルジジョンを得た。
　Ｋｅｌｚａｎ　０．２２ｇ、Ｐｒｏｘｅｌ　ＧＸＬ　０．２０ｇ、プロピレングリコール　４．５０ｇ、イオン交換水　２４．４０ｇを混合して増粘剤溶液を調製した。該増粘剤溶液と上記サスポエマルジョンとを混合し、合計１００.００ｇとなるようイオン交換水を追加・混合して３．５ｗ／ｗ％のクロチアニジン及び８．０ｗ／ｗ％のピリプロキシフェンを含有する実施例１のサスポエマルジョンを得た。 <Examples 1 to 6: Examination of the type of hydrophobic organic solvent>
(Example 1)
0.20 g of XIAMETER ACP-1500 Antifoam Compound, 2.60 g of REAX910, and 0.44 g of Veegum R were added to 31.37 g of ion-exchanged water and stirred and mixed to prepare an aqueous phase. To this, 3.51 g of clothianidin (99.8% purity) was added and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a clothianidin suspension.
On the other hand, 8.06 g of pyriproxyfen (purity 99.3%), 8.00 g of GaroSOL 200ND, 8.00 g of GaroSOL 150ND, and 3.00 g of Stepflow26F were mixed to form a uniform solution and an oil phase was prepared. The above clothianidin suspension and oil phase were mixed. The resulting mixture was stirred using a polytron to obtain a suspoemulsion.
A thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water. The thickener solution and the Suspo emulsion were mixed, and ion-exchanged water was added and mixed to make a total of 100.00 g. A suspoemulsion of Example 1 containing was obtained.
　（実施例２～６）
　実施例２～５は疎水性有機溶媒の種類を変えた以外は実施例１と同じ方法で製造した。実施例６は疎水性有機溶媒の種類、第１界面活性剤の添加量と種類を変えた以外は実施例１と同じ方法で製造した。 (Examples 2-6)
Examples 2 to 5 were produced in the same manner as in Example 1 except that the type of hydrophobic organic solvent was changed. Example 6 was prepared in the same manner as in Example 1, except that the type of hydrophobic organic solvent and the amount and type of first surfactant added were changed.
　＜実施例７～１１：第１界面活性剤の種類および量等を検討＞
　（実施例７）
　ピリプロキシフェン（純度９９．３％）　８．０６ｇ、ＧａｒｏＳＯＬ　２００ＮＤ　１６．００ｇ、Ｓｔｅｐｆｌｏｗ２６Ｆ　１．００ｇを混合し均一な溶液とし油相を調製した。イオン交換水　３８．８７ｇにＸＩＡＭＥＴＥＲ　ＡＣＰ－１５００　Ａｎｔｉｆｏａｍ　Ｃｏｍｐｏｕｎｄ　０．２０ｇ、ＲＥＡＸ９１０　２．６０ｇ、Ｖｅｅｇｕｍ　Ｒ　０．４４ｇを添加し、攪拌・混合して水相を調製した。これにクロチアニジン（純度９９．８％）　３．５１ｇを加え攪拌・混合し、更に調製した油相２５．０６ｇを加えて撹拌・混合した。得られた混合物をダイノミル（１．０ｍｍガラスビーズ、充填率８０％、周速１０ｍ／ｓ）を用いて湿式粉砕し、サスポエマルジョンを得た。
　Ｋｅｌｚａｎ　０．２２ｇ、Ｐｒｏｘｅｌ　ＧＸＬ　０．２０ｇ、プロピレングリコール　４．５０ｇ、イオン交換水　２４．４０ｇを混合して増粘剤溶液を調製した。該増粘剤溶液と上記サスポエマルジョンとを混合し、合計１００.００ｇとなるようイオン交換水を追加・混合して３．５ｗ／ｗ％のクロチアニジン及び８．０ｗ／ｗ％のピリプロキシフェンを含有する実施例７のサスポエマルジョンを得た。 <Examples 7 to 11: Examination of the type and amount of the first surfactant>
(Example 7)
8.06 g of pyriproxyfen (purity 99.3%), 16.00 g of GaroSOL 200ND and 1.00 g of Stepflow26F were mixed to form a uniform solution to prepare an oil phase. 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 2.60 g of REAX910, and 0.44 g of Veegum R were added to 38.87 g of ion-exchanged water, and the mixture was stirred and mixed to prepare an aqueous phase. To this, 3.51 g of clothianidin (purity 99.8%) was added and stirred and mixed, and 25.06 g of the prepared oil phase was further added and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a suspo emulsion.
A thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water. The thickener solution and the Suspo emulsion were mixed, and ion-exchanged water was added and mixed to make a total of 100.00 g. A suspoemulsion of Example 7 containing was obtained.
　（実施例８）
　実施例８は疎水性有機溶媒の種類を変えた以外は実施例７と同じ方法で製造した。 (Example 8)
Example 8 was produced in the same manner as in Example 7, except that the type of hydrophobic organic solvent was changed.
　（実施例９～１１）
　実施例９～１１は疎水性有機溶媒の種類、第１界面活性剤の添加量と種類を変えた以外は実施例１と同じ方法で製造した。 (Examples 9-11)
Examples 9 to 11 were produced in the same manner as in Example 1 except that the type of hydrophobic organic solvent and the amount and type of first surfactant added were changed.
　＜実施例１２～１８：比（Ｗ４／Ｗ３）等を検討＞
　（実施例１２）
　イオン交換水　２０．２９ｇにＸＩＡＭＥＴＥＲ　ＡＣＰ－１５００　Ａｎｔｉｆｏａｍ　Ｃｏｍｐｏｕｎｄ　０．２０ｇ、ＲＥＡＸ９１０　２．６０ｇ、Ｖｅｅｇｕｍ　Ｒ　０．４４ｇを添加し、攪拌・混合して水相を調製した。これにクロチアニジン（純度９９．８％）　２．０１ｇを加え攪拌・混合した。得られた混合物をダイノミル（１．０ｍｍガラスビーズ、充填率８０％、周速１０ｍ／ｓ）を用いて湿式粉砕し、クロチアニジン懸濁液を得た。
　一方、ピリプロキシフェン（純度９９．３％）　２０．１４ｇ、ＧａｒｏＳＯＬ　２００ＮＤ　２０．００ｇ、Ｓｔｅｐｆｌｏｗ２６Ｆ　５．００ｇを混合し均一な溶液とし油相を調製した。上記のクロチアニジン懸濁液、油相を混合した。得られた混合物をポリトロンを用いて撹拌し、サスポエマルジジョンを得た。
　Ｋｅｌｚａｎ　０．２２ｇ、Ｐｒｏｘｅｌ　ＧＸＬ　０．２０ｇ、プロピレングリコール　４．５０ｇ、イオン交換水　２４．４０ｇを混合して増粘剤溶液を調製した。該増粘剤溶液と上記サスポエマルジョンとを混合し、合計１００.００ｇとなるようイオン交換水を追加・混合して２．０ｗ／ｗ％のクロチアニジン及び２０．０ｗ／ｗ％のピリプロキシフェンを含有する実施例１２のサスポエマルジョンを得た。 <Examples 12 to 18: Examination of the ratio (W 4 /W 3 ) etc.>
(Example 12)
0.20 g of XIAMETER ACP-1500 Antifoam Compound, 2.60 g of REAX910, and 0.44 g of Veegum R were added to 20.29 g of ion-exchanged water and stirred and mixed to prepare an aqueous phase. 2.01 g of clothianidin (purity 99.8%) was added thereto and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a clothianidin suspension.
On the other hand, 20.14 g of pyriproxyfen (purity 99.3%), 20.00 g of GaroSOL 200ND, and 5.00 g of Stepflow26F were mixed to form a uniform solution and an oil phase was prepared. The above clothianidin suspension and oil phase were mixed. The resulting mixture was stirred using a polytron to obtain a suspoemulsion.
A thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water. The thickener solution and the Suspoemulsion were mixed, and deionized water was added and mixed to make a total of 100.00 g, and 2.0 w/w% clothianidin and 20.0 w/w% pyriproxyfen A suspoemulsion of Example 12 containing was obtained.
　（実施例１３）
　イオン交換水　２０．００ｇにＸＩＡＭＥＴＥＲ　ＡＣＰ－１５００　Ａｎｔｉｆｏａｍ　Ｃｏｍｐｏｕｎｄ　０．２０ｇ、ＲＥＡＸ９１０　２．６０ｇ、Ｖｅｅｇｕｍ　Ｒ　０．４４ｇを添加し、攪拌・混合して水相を調製した。これにクロチアニジン（純度９９．８％）　２０．０５ｇを加え攪拌・混合した。得られた混合物をダイノミル（１．０ｍｍガラスビーズ、充填率８０％、周速１０ｍ／ｓ）を用いて湿式粉砕し、クロチアニジン懸濁液を得た。
　一方、ピリプロキシフェン（純度９９．３％）　２．０１ｇ、ＧａｒｏＳＯＬ　２００ＮＤ　２．００ｇ、Ｓｔｅｐｆｌｏｗ２６Ｆ　１．００ｇを混合し均一な溶液とし油相を調製した。上記のクロチアニジン懸濁液、油相を混合した。得られた混合物をポリトロンを用いて撹拌し、サスポエマルジジョンを得た。
　Ｋｅｌｚａｎ　０．２２ｇ、Ｐｒｏｘｅｌ　ＧＸＬ　０．２０ｇ、プロピレングリコール　４．５０ｇ、イオン交換水　２４．４０ｇを混合して増粘剤溶液を調製した。該増粘剤溶液と上記サスポエマルジョンとを混合し、合計１００.００ｇとなるようイオン交換水を追加・混合して２０．０ｗ／ｗ％のクロチアニジン及び２．０ｗ／ｗ％のピリプロキシフェンを含有する実施例１３のサスポエマルジョンを得た。 (Example 13)
0.20 g of XIAMETER ACP-1500 Antifoam Compound, 2.60 g of REAX910, and 0.44 g of Veegum R were added to 20.00 g of ion-exchanged water, and the mixture was stirred and mixed to prepare an aqueous phase. 20.05 g of clothianidin (purity 99.8%) was added thereto and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a clothianidin suspension.
On the other hand, 2.01 g of pyriproxyfen (purity 99.3%), 2.00 g of GaroSOL 200ND and 1.00 g of Stepflow26F were mixed to form a uniform solution and an oil phase was prepared. The above clothianidin suspension and oil phase were mixed. The resulting mixture was stirred using a polytron to obtain a suspoemulsion.
A thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water. The thickener solution and the above suspoemulsion are mixed, ion-exchanged water is added and mixed to make a total of 100.00 g, and 20.0 w/w% clothianidin and 2.0 w/w% pyriproxyfen are mixed. A suspoemulsion of Example 13 containing was obtained.
　（実施例１４～１７）
　実施例１４、１６，１７は疎水性有機溶媒の種類、第１界面活性剤の添加量と種類を変えた以外は実施例１２と同じ方法で製造した。実施例１５は疎水性有機溶媒の種類、第１界面活性剤の添加量と種類を変えた以外は実施例１３と同じ方法で製造した。 (Examples 14-17)
Examples 14, 16 and 17 were produced in the same manner as in Example 12 except that the type of hydrophobic organic solvent and the amount and type of first surfactant added were changed. Example 15 was prepared in the same manner as in Example 13 except that the type of hydrophobic organic solvent and the amount and type of first surfactant added were changed.
　（実施例１８）
　イオン交換水　２０．００ｇにＸＩＡＭＥＴＥＲ　ＡＣＰ－１５００　Ａｎｔｉｆｏａｍ　Ｃｏｍｐｏｕｎｄ　０．２０ｇ、ＲＥＡＸ９１０　１．００ｇ、Ｖｅｅｇｕｍ　Ｒ　０．４４ｇを添加し、攪拌・混合して水相を調製した。これにクロチアニジン（純度９９．８％）　１０．０３ｇを加え攪拌・混合した。得られた混合物をダイノミル（１．０ｍｍガラスビーズ、充填率８０％、周速１０ｍ／ｓ）を用いて湿式粉砕し、クロチアニジン懸濁液を得た。
　一方、ピリプロキシフェン（純度９９．３％）　１．０１ｇ、Ｓｏｌｖｅｓｓｏ　１５０ＮＤ　１．００ｇを混合し均一な溶液とし油相を調製した。上記のクロチアニジン懸濁液、油相、Ｇｅｎａｐｏｌ　ＰＦ４０　１．００ｇ、Ｍｙｒｊ　Ｓ１００　５．００ｇを混合した。得られた混合物をポリトロンを用いて撹拌し、サスポエマルジジョンを得た。
　Ｋｅｌｚａｎ　０．２２ｇ、Ｐｒｏｘｅｌ　ＧＸＬ　０．２０ｇ、プロピレングリコール　４．５０ｇ、イオン交換水　２４．４０ｇを混合して増粘剤溶液を調製した。該増粘剤溶液と上記サスポエマルジョンとを混合して、合計１００.００ｇとなるようイオン交換水を追加・混合して１０．０ｗ／ｗ％のクロチアニジン及び１．０ｗ／ｗ％のピリプロキシフェンを含有する実施例１８のサスポエマルジョンを得た。 (Example 18)
0.20 g of XIAMETER ACP-1500 Antifoam Compound, 1.00 g of REAX910, and 0.44 g of Veegum R were added to 20.00 g of ion-exchanged water, and the mixture was stirred and mixed to prepare an aqueous phase. To this, 10.03 g of clothianidin (99.8% purity) was added and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a clothianidin suspension.
On the other hand, 1.01 g of pyriproxyfen (purity 99.3%) and 1.00 g of Solvesso 150ND were mixed to form a uniform solution to prepare an oil phase. The above clothianidin suspension, oil phase, Genapol PF40 1.00 g, Myrj S100 5.00 g were mixed. The resulting mixture was stirred using a polytron to obtain a suspoemulsion.
A thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water. The thickener solution and the above suspoemulsion are mixed, and ion-exchanged water is added and mixed to make a total of 100.00 g to obtain 10.0 w/w% clothianidin and 1.0 w/w% pyriproxy. A suspoemulsion of Example 18 containing fen was obtained.
　＜実施例１９～２４：第１界面活性剤の種類等を検討＞
　（実施例１９～２３）
　実施例１９～２３は疎水性有機溶媒の種類、第１界面活性剤の種類を変えた以外は実施例１と同じ方法で製造した。 <Examples 19 to 24: Examination of the type of the first surfactant>
(Examples 19-23)
Examples 19 to 23 were produced in the same manner as in Example 1 except that the type of hydrophobic organic solvent and the type of first surfactant were changed.
　（実施例２４）
　イオン交換水　３１．３７ｇにＸＩＡＭＥＴＥＲ　ＡＣＰ－１５００　Ａｎｔｉｆｏａｍ　Ｃｏｍｐｏｕｎｄ　０．２０ｇ、ＲＥＡＸ９１０　２．６０ｇ、Ｖｅｅｇｕｍ　Ｒ　０．４４ｇを添加し、攪拌・混合して水相を調製した。これにクロチアニジン（純度９９．８％）　３．５１ｇを加え攪拌・混合した。得られた混合物をダイノミル（１．０ｍｍガラスビーズ、充填率８０％、周速１０ｍ／ｓ）を用いて湿式粉砕し、クロチアニジン懸濁液を得た。
　一方、ピリプロキシフェン（純度９９．３％）　８．０６ｇ、ＧａｒｏＳＯＬ　２００ＮＤ　１６．００ｇを混合し均一な溶液とし油相を調製した。上記のクロチアニジン懸濁液、油相、Ｍｙｒｊ　Ｓ５０　３．００ｇを混合した。得られた混合物をポリトロンを用いて撹拌し、サスポエマルジジョンを得た。
　Ｋｅｌｚａｎ　０．２２ｇ、Ｐｒｏｘｅｌ　ＧＸＬ　０．２０ｇ、プロピレングリコール　４．５０ｇ、イオン交換水　２４．４０ｇを混合して増粘剤溶液を調製した。該増粘剤溶液と上記サスポエマルジョンとを混合して、合計１００.００ｇとなるようイオン交換水を追加・混合して３．５ｗ／ｗ％のクロチアニジン及び８．０ｗ／ｗ％のピリプロキシフェンを含有する実施例２４のサスポエマルジョンを得た。 (Example 24)
0.20 g of XIAMETER ACP-1500 Antifoam Compound, 2.60 g of REAX910, and 0.44 g of Veegum R were added to 31.37 g of ion-exchanged water and stirred and mixed to prepare an aqueous phase. To this, 3.51 g of clothianidin (99.8% purity) was added and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a clothianidin suspension.
On the other hand, 8.06 g of pyriproxyfen (purity 99.3%) and 16.00 g of GaroSOL 200ND were mixed to form a homogeneous solution and an oil phase was prepared. The above clothianidin suspension, the oil phase and 3.00 g of Myrj S50 were mixed. The resulting mixture was stirred using a polytron to obtain a suspoemulsion.
A thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water. The thickener solution and the above suspoemulsion were mixed, and ion-exchanged water was added and mixed to make a total of 100.00 g, and 3.5 w/w% clothianidin and 8.0 w/w% pyriproxy. A suspoemulsion of Example 24 containing fen was obtained.
　＜実施例２５～２９：界面活性剤の種類等を検討＞
　（実施例２５～２７）
　実施例２５～２７は疎水性有機溶媒の種類、第１界面活性剤の添加量と種類を変えた以外は実施例１と同じ方法で製造した。 <Examples 25 to 29: Examination of types of surfactants>
(Examples 25-27)
Examples 25 to 27 were prepared in the same manner as in Example 1 except that the type of hydrophobic organic solvent and the amount and type of first surfactant added were changed.
　（実施例２８）
　ピリプロキシフェン（純度９９．３％）　８．０６ｇ、Ｓｏｌｖｅｓｓｏ　１５０ＮＤ　１６．００ｇを混合し均一な溶液とし油相を調製した。イオン交換水　３１．３７ｇにＸＩＡＭＥＴＥＲ　ＡＣＰ－１５００　Ａｎｔｉｆｏａｍ　Ｃｏｍｐｏｕｎｄ　０．２０ｇ、Ｖｅｅｇｕｍ　Ｒ　０．４４ｇ、Ｇｅｎａｐｏｌ　ＰＦ４０　２．５０ｇ、ＥｍｕｌｓｏｇｅｎＥＬ５４０　２．５０ｇを添加し、攪拌・混合して水相を調製した。これにクロチアニジン（純度９９．８％）　３．５１ｇを加え攪拌・混合し、更に調製した油相２４．０６ｇを加えて撹拌・混合した。得られた混合物をダイノミル（１．０ｍｍガラスビーズ、充填率８０％、周速１０ｍ／ｓ）を用いて湿式粉砕し、サスポエマルジョンを得た。
　Ｋｅｌｚａｎ　０．２２ｇ、Ｐｒｏｘｅｌ　ＧＸＬ　０．２０ｇ、プロプレングリコール　４．５０ｇ、イオン交換水　２４．４０ｇを混合して増粘剤溶液を調製した。該増粘剤溶液と上記サスポエマルジョンとを混合し、合計１００.００ｇとなるようイオン交換水を追加・混合して３．５ｗ／ｗ％のクロチアニジン及び８．０ｗ／ｗ％のピリプロキシフェンを含有する実施例２８のサスポエマルジョンを得た。 (Example 28)
8.06 g of pyriproxyfen (purity 99.3%) and 16.00 g of Solvesso 150ND were mixed to form a uniform solution to prepare an oil phase. 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 0.44 g of Veegum R, 2.50 g of Genapol PF40, and 2.50 g of Emulsogen EL540 were added to 31.37 g of ion-exchanged water, and stirred and mixed to prepare an aqueous phase. To this, 3.51 g of clothianidin (99.8% purity) was added and stirred and mixed, and 24.06 g of the prepared oil phase was further added and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a suspo emulsion.
A thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water. The thickener solution and the Suspo emulsion were mixed, and ion-exchanged water was added and mixed to make a total of 100.00 g. A suspoemulsion of Example 28 containing was obtained.
　（実施例２９）
　ピリプロキシフェン（純度９９．３％）　８．０６ｇ、ＧａｒｏＳＯＬ　２００ＮＤ　１６．００ｇを混合し均一な溶液とし油相を調製した。イオン交換水　３１．３７ｇにＸＩＡＭＥＴＥＲ　ＡＣＰ－１５００　Ａｎｔｉｆｏａｍ　Ｃｏｍｐｏｕｎｄ　０．２０ｇ、Ｖｅｅｇｕｍ　Ｒ　０．４４ｇ、Ｓｔｅｐｆｌｏｗ２６Ｆ　３.００ｇ、ＳｏｐｒｏｐｈｏｒＦＬＫ　１．００ｇを添加し、攪拌・混合して水相を調製した。これにクロチアニジン（純度９９．８％）　３．５１ｇを加え攪拌・混合し、更に調製した油相２４．０６ｇを加えて撹拌・混合した。得られた混合物をダイノミル（１．０ｍｍガラスビーズ、充填率８０％、周速１０ｍ／ｓ）を用いて湿式粉砕し、サスポエマルジョンを得た。
　Ｋｅｌｚａｎ　０．２２ｇ、Ｐｒｏｘｅｌ　ＧＸＬ　０．２０ｇ、プロピレングリコール　４．５０ｇ、イオン交換水　２４．４０ｇを混合して増粘剤溶液を調製した。該増粘剤溶液と上記サスポエマルジョンとを混合し、合計１００.００ｇとなるようイオン交換水を追加・混合して３．５ｗ／ｗ％のクロチアニジン及び８．０ｗ／ｗ％のピリプロキシフェンを含有する実施例２９のサスポエマルジョンを得た。 (Example 29)
8.06 g of pyriproxyfen (purity 99.3%) and 16.00 g of GaroSOL 200ND were mixed to form a uniform solution to prepare an oil phase. 0.20 g of XIAMETER ACP-1500 Antifoam Compound, 0.44 g of Veegum R, 3.00 g of Stepflow26F, and 1.00 g of SoprophorFLK were added to 31.37 g of ion-exchanged water, and stirred and mixed to prepare an aqueous phase. To this, 3.51 g of clothianidin (99.8% purity) was added and stirred and mixed, and 24.06 g of the prepared oil phase was further added and stirred and mixed. The resulting mixture was wet pulverized using a dyno mill (1.0 mm glass beads, filling rate 80%, peripheral speed 10 m/s) to obtain a suspo emulsion.
A thickener solution was prepared by mixing 0.22 g of Kelzan, 0.20 g of Proxel GXL, 4.50 g of propylene glycol and 24.40 g of deionized water. The thickener solution and the Suspo emulsion were mixed, and ion-exchanged water was added and mixed to make a total of 100.00 g. A suspoemulsion of Example 29 containing was obtained.
　＜比較例１、２：比（Ｗ４／Ｗ３）等を検討＞
　（比較例１）
　比較例１は疎水性有機溶媒の種類、第１界面活性剤の種類と添加量を変えた以外は実施例１２と同じ方法で製造した。 <Comparative Examples 1 and 2: Examining the ratio (W 4 /W 3 ) etc.>
(Comparative example 1)
Comparative Example 1 was prepared in the same manner as in Example 12 except that the type of hydrophobic organic solvent and the type and amount of the first surfactant were changed.
　（比較例２）
　比較例２は第１界面活性剤の添加量を変えた以外は実施例１８と同じ方法で製造した。 (Comparative example 2)
Comparative Example 2 was produced in the same manner as in Example 18, except that the amount of the first surfactant added was changed.
　［試験例１］
　実施例１～２９および比較例１、２で得られたサスポエマルジョンの体積中位径を測定した。製造直後の粒子径Ｄ１（表１～６において、「初期粒子径」と表記する）、および５４℃で２週間保存した後の粒子径Ｄ２（表１～６において、「保存後粒子径」と表記する）をマスターサイザー２０００（レーザー回折式粒度分布測定装置、マルバーン・パナリティカル製）にて測定した。表１～６に、実施例１～２９および比較例１、２のサスポエマルジョンの組成（各成分の質量（ｇ））とともにＤ１およびＤ２の測定結果を示し、さらに保存による粒径の増加比（＝（Ｄ２－Ｄ１）／Ｄ１）を示す。増加比は、粒径が増加していない場合（同じ場合または減少している場合）は０（ゼロ）とする。 [Test Example 1]
The volume median diameters of the suspoemulsions obtained in Examples 1 to 29 and Comparative Examples 1 and 2 were measured. Particle diameter D1 immediately after production (referred to as "initial particle diameter" in Tables 1 to 6), and particle diameter D2 after storage at 54 ° C. for 2 weeks (referred to as "particle diameter after storage" in Tables 1 to 6) ) was measured with a Mastersizer 2000 (laser diffraction particle size distribution analyzer, manufactured by Malvern Panalytical). Tables 1 to 6 show the composition (mass (g) of each component) of the suspoemulsions of Examples 1 to 29 and Comparative Examples 1 and 2, together with the measurement results of D1 and D2. (=(D2-D1)/D1) is shown. The increase ratio is 0 (zero) if the particle size is not increasing (same or decreasing).
　[試験例２]
　実施例８のサスポエマルジョンを、クロチアニジン及びピリプロキシフェンの濃度がそれぞれ１．１ｐｐｍ及び２．５ｐｐｍとなるようにイオン交換水で希釈し、クロチアニジン及びピリプロキシフェン含有する散布液を調製した。培土を充填した９０ｍｌ容プラスチック容器に植えた３－４葉期キャベツ（Ｂｒａｓｓｉｃａ　ｏｌｅｒａｃｅａ）苗に、タバココナジラミ成虫を放して約２４時間産卵させた。この苗に、該散布液を３苗あたりの散布液量が２０ｍＬとなるようにスプレーガンを用いて散布した。１３日後、キャベツ葉に寄生しているタバココナジラミ幼虫数を調査し、次の式により防除価を求めた。
防除価＝（ａ－ｂ）／ａ×１００
ａ：無処理区の寄生幼虫数、ｂ：処理区の寄生幼虫数
　ここで無処理区とは、実施例８のサスポエマルジョンを使用しないこと以外は処理区と同じ操作をする区を意味する。
　防除価は９９であった。 [Test Example 2]
The suspoemulsion of Example 8 was diluted with ion-exchanged water so that the concentrations of clothianidin and pyriproxyfen were 1.1 ppm and 2.5 ppm, respectively, to prepare a spray liquid containing clothianidin and pyriproxyfen. Adults of Bemisia tabaci were released to 3-4 leaf stage cabbage (Brassica oleracea) seedlings planted in 90 ml plastic containers filled with potting soil and allowed to lay eggs for about 24 hours. The spray solution was sprayed on the seedlings using a spray gun so that the amount of the spray solution per 3 seedlings was 20 mL. After 13 days, the number of Bemisia tabaci larvae parasitic on the cabbage leaves was investigated, and the control value was determined by the following formula.
Prevention value = (ab) / a × 100
a: Number of parasitic larvae in untreated area, b: Number of parasitic larvae in treated area Here, the untreated area means an area in which the same operation as the treated area is performed except that the suspoemulsion of Example 8 is not used. .
Control value was 99.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

Claims (7)

  1. 　ピリプロキシフェン、クロチアニジン、疎水性有機溶媒、エチレンオキサイドプロピレンオキサイドブロックコポリマー、及び水を含み、
    　水中に、前記疎水性有機溶媒に前記ピリプロキシフェンが溶解した液体が分散し、かつ、前記クロチアニジンが懸濁している液体農薬組成物であって、
    　前記エチレンオキサイドプロピレンオキサイドブロックコポリマーは、ＨＬＢ値が５．０以上２０．０以下であり、
    　前記ピリプロキシフェンの質量Ｗ１に対する、前記疎水性有機溶媒の質量Ｗ２の比（Ｗ２／Ｗ１）が、１．０以上６．０以下であり、
    　前記エチレンオキサイドプロピレンオキサイドブロックコポリマーの質量Ｗ３に対する、前記ピリプロキシフェン、前記クロチアニジン、及び前記疎水性有機溶媒の合計質量Ｗ４の比（Ｗ４／Ｗ３）が、２．０以上８０．０以下である、液体農薬組成物。     comprising pyriproxyfen, clothianidin, a hydrophobic organic solvent, an ethylene oxide propylene oxide block copolymer, and water;
    A liquid pesticide composition in which a liquid in which the pyriproxyfen is dissolved in the hydrophobic organic solvent is dispersed in water and the clothianidin is suspended,
    The ethylene oxide propylene oxide block copolymer has an HLB value of 5.0 or more and 20.0 or less,
    a ratio (W 2 /W 1 ) of the weight W 2 of the hydrophobic organic solvent to the weight W 1 of the pyriproxyfen is 1.0 or more and 6.0 or less;
    The ratio of the total weight W4 of the pyriproxyfen, the clothianidin, and the hydrophobic organic solvent to the weight W3 of the ethylene oxide propylene oxide block copolymer ( W4 / W3 ) is 2.0 or more and 80.0. A liquid pesticide composition, which is:
  2. 　ピリプロキシフェン、クロチアニジン、疎水性有機溶媒、エチレンオキサイドプロピレンオキサイドブロックコポリマー、リグニンスルホン酸塩、増粘剤、消泡剤、凍結防止剤、防腐剤及び水から実質的になり、
    　水中に、前記疎水性有機溶媒に前記ピリプロキシフェンが溶解した液体が分散し、かつ、前記クロチアニジンが懸濁している液体農薬組成物であって、
    　前記エチレンオキサイドプロピレンオキサイドブロックコポリマーは、ＨＬＢ値が５．０以上２０．０以下であり、
    　前記ピリプロキシフェンの質量Ｗ１に対する、前記疎水性有機溶媒の質量Ｗ２の比（Ｗ２／Ｗ１）が、１．０以上６．０以下であり、
    　前記エチレンオキサイドプロピレンオキサイドブロックコポリマーの質量Ｗ３に対する、前記ピリプロキシフェン、前記クロチアニジン、及び前記疎水性有機溶媒の合計質量Ｗ４の比（Ｗ４／Ｗ３）が、２．０以上８０．０以下である、液体農薬組成物。     consisting essentially of pyriproxyfen, clothianidin, a hydrophobic organic solvent, an ethylene oxide propylene oxide block copolymer, a lignin sulfonate, a thickening agent, an antifoaming agent, an antifreeze agent, a preservative and water;
    A liquid pesticide composition in which a liquid in which the pyriproxyfen is dissolved in the hydrophobic organic solvent is dispersed in water and the clothianidin is suspended,
    The ethylene oxide propylene oxide block copolymer has an HLB value of 5.0 or more and 20.0 or less,
    a ratio (W 2 /W 1 ) of the weight W 2 of the hydrophobic organic solvent to the weight W 1 of the pyriproxyfen is 1.0 or more and 6.0 or less;
    The ratio of the total weight W4 of the pyriproxyfen, the clothianidin, and the hydrophobic organic solvent to the weight W3 of the ethylene oxide propylene oxide block copolymer ( W4 / W3 ) is 2.0 or more and 80.0. A liquid pesticide composition, which is:
  3. 　前記疎水性有機溶媒は、密度が０．８５ｇ／ｃｍ３以上１．２０ｇ／ｃｍ３以下の溶媒を含む、請求項１または２に記載の液体農薬組成物。 3. The liquid agricultural chemical composition according to claim 1 or 2, wherein the hydrophobic organic solvent contains a solvent having a density of 0.85 g/ cm3 or more and 1.20 g/ cm3 or less.
  4. 　第２界面活性剤をさらに含む、請求項１に記載の液体農薬組成物。 The liquid pesticide composition according to claim 1, further comprising a second surfactant.
  5. 　前記第２界面活性剤は、リグニンスルホン酸塩を含む、請求項４に記載の液体農薬組成物。 The liquid agricultural chemical composition according to claim 4, wherein the second surfactant comprises lignin sulfonate.
  6. 　前記ピリプロキシフェンの質量Ｗ１に対する、前記クロチアニジンの質量Ｗ５の比（Ｗ５／Ｗ１）が、０．０３以上３０以下である、請求項１～５のいずれか１項に記載の液体農薬組成物。 The liquid according to any one of claims 1 to 5 , wherein the ratio (W 5 /W 1 ) of the mass W 5 of the clothianidin to the mass W 1 of the pyriproxyfen is 0.03 or more and 30 or less. pesticide composition.
  7. 　前記液体農薬組成物の全質量を１００質量％としたときに、前記ピリプロキシフェン及び前記クロチアニジンの合計質量Ｗ６が、０．１質量％以上５０質量％以下である、請求項１～６のいずれか１項に記載の液体農薬組成物。 The total mass W6 of the pyriproxyfen and the clothianidin is 0.1% by mass or more and 50% by mass or less when the total mass of the liquid agricultural chemical composition is 100% by mass. A liquid pesticide composition according to any one of the preceding claims.
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JP5125126B2 (en) * 2007-01-31 2013-01-23 住友化学株式会社 Pesticide solution containing hydrophobic agrochemical active compound
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JPH10130103A (en) * 1996-11-01 1998-05-19 Sumitomo Chem Co Ltd Agrochemical composition
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