Liquid pesticide composition

Abstract

By encapsulating the active ingredients of pesticides in nanoparticles, it becomes possible to improve pesticide efficacy and drug penetration. In particular, there is a need for pesticide formulations that allow for the easy preparation of pesticide nanoparticle dispersions by dilution with water. Therefore, the objective is to provide a pesticide composition in which the particle size of the pesticide component in the aqueous dispersion is 20 nm or less, and which can maintain this particle size for 24 hours or more. [Solution] A liquid pesticide composition comprising (A) an active pesticide component and (B) a surfactant, (A) The pesticide active ingredient is a pesticide active ingredient with a water solubility of 500 ppm or less at 20°C. (B) The surfactant is one or more selected from the group consisting of (b1) styrene-maleic acid-polyoxyalkylene graft copolymer, (b2) polyoxyalkylene-(poly)styrylphenyl ether, and its formaldehyde condensate. A liquid pesticide composition in which the mass content ratio of (A) pesticide active ingredient and (B) surfactant is 1:1 to 100.

Description

Technical Field

[0001] The present invention relates to a liquid agricultural chemical composition containing an agrochemical active ingredient poorly soluble in water and a surfactant, and to a liquid agricultural chemical composition in which a dispersion diluted with water can form a stable nanoparticle dispersion of the agrochemical active ingredient.

Background Art

[0002] Liquid agrochemical formulations are usually used in a state diluted with water. However, many agrochemical active ingredients have poor solubility in water. Therefore, surfactants and the like are blended with the agrochemical active ingredient, and provided as emulsions or emulsion agents that can easily prepare a diluted dispersion with water.

[0003] In a water-diluted dispersion containing an agrochemical active ingredient, as the dispersed particle diameter of the agrochemical component becomes smaller, the surface area of the substance per unit weight becomes larger, so an improvement in the control effect of the agrochemical is expected. Among them, when the particle diameter containing the agrochemical active ingredient is 100 nm or less (hereinafter referred to as nanoparticles), it is generally known that the permeability to plants is improved. In Non-Patent Document 1, it is reported that by reducing gold particles to 50 nm, the gold particles sprayed on the plant surface penetrate to the inside and spread throughout the plant through the vascular bundles. From these findings, a spraying solution containing nanoparticulated agrochemical component particles can be expected to efficiently penetrate into the application plant, so an expansion and labor saving of the agrochemical application method are expected. Conventionally, although a bactericide was only expected to have a preventive effect by controlling pathogenic bacteria attached to the leaf surface, there is also a possibility that the bactericide is made into nanoparticles and penetrates into the plant to show a therapeutic effect against pathogenic bacteria. Furthermore, by improving the permeability to target pests and pathogenic bacteria, an increase in efficacy and an expansion of the spectrum are expected. Non-Patent Document 2 reports that polymer-type nano-agrochemical formulations of β-cyfluthrin, carbofuran, and acephate have improved insecticidal effects compared to existing formulations. It also reports that the residual effect of a liposome-type nano-agrochemical formulation of etofenprox has been extended compared to the existing agent. Non-patent document 3 reports on cases where reducing inorganic particles to the nanoscale improved their effects on plants. For example, using CuO as nanoparticles increased the growth rate of corn by 51%. There is also a report that using TiO2 nanoparticles increased the yield of cowpeas from 26% to 51%. Patent Document 1 discloses a liquid pesticide composition comprising a pesticide compound, a solvent, and a block polymer-type surfactant having an alkylene oxide or styrene oxide moiety (PAO) and a polyethylene oxide moiety (PEO). It describes that diluting this composition with water prepares a nanoparticle dispersion, improving its insecticidal activity. The particle size in the dispersion obtained from this composition is mostly relatively large, ranging from 20 to 100 nm, and its stability was approximately 24 hours. Furthermore, compositions with a particle size of 20 nm or less in the dispersion are limited to pesticide active ingredients with a water solubility of 500 ppm or more. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] ACS Nano 2019, 13, 5, 5291-5305 [Non-Patent Document 2] Environment International 63(2014)224-235 [Non-Patent Document 3] Environ Chem Lett(2017)15:15-22 [Patent Documents]

[0005] [Patent Document 1] Special Publication No. 2008-505150 [Overview of the project] [Problems that the invention aims to solve]

[0006] As described above, by nano-encapsulating the active pesticide component, it is possible to improve pesticide efficacy and drug penetration. Therefore, there is a need for a pesticide formulation that can be easily prepared by diluting with water to create a dispersion of pesticide nanoparticles. The object of the present invention is to provide a pesticide composition that yields stable nanoparticles containing an active pesticide component with a water solubility of 500 ppm or less. Particularly preferred is to provide a pesticide composition in which, when diluted with water, the particle size of the pesticide component in the resulting dispersion is 20 nm or less, and the particle size can be maintained for 24 hours or more. [Means for solving the problem]

[0007] As a result of diligent research to solve the aforementioned problems, the inventors focused on the fact that styrene-maleic acid-polyoxyalkylene graft copolymer, polyoxyalkylene-(poly)styrylphenyl ether, or their formaldehyde condensates have high dispersion performance for various pesticide active ingredients, and by optimizing the content of each component, the present invention was completed.

[0008] In other words, the present invention has the following configurations [1] to [8]. [1] A liquid pesticide composition comprising (A) an active pesticide component and (B) a surfactant, (A) The pesticide active ingredient is a pesticide active ingredient with a water solubility of 500 ppm or less at 20°C. (B) The surfactant is one or more selected from the group consisting of (b1) styrene-maleic acid-polyoxyalkylene graft copolymer, (b2) polyoxyalkylene-(poly)styrylphenyl ether, and its formaldehyde condensate. (A) The mass content ratio of the pesticide active ingredient to (B) the surfactant is 1:1 to 100. Liquid pesticide composition. [2] The liquid pesticide composition described in [1], which is an emulsion or a liquid pesticide. [3] (A) The pesticide active ingredient is a liquid pesticide active ingredient at 20°C and normal pressure, (A) The mass content ratio of the pesticide active ingredient to (B) the surfactant is 1:1 to 10. The liquid pesticide composition described in [1] or [2]. [4] (A) The pesticide active ingredient is a solid pesticide active ingredient at 20°C and normal pressure, (C) Contains solvents, (A) The mass content ratio of the pesticide active ingredient to (B) the surfactant is 1:5 to 100. The liquid pesticide composition described in [1] or [2]. [5] The liquid pesticide composition according to [4], wherein (A) 1 part by mass of the pesticide active ingredient is (C) 2 to 100 parts by mass of the solvent. [6] (D) A liquid pesticide composition according to any one of [1] to [5], comprising a rosin compound. [7] A liquid pesticide composition according to any one of items [1] to [6], wherein the particles containing (A) the pesticide active ingredient in the dispersion diluted 100 times with water are 20 nm or less. [8] An aqueous dispersion containing water of any one of the liquid pesticide compositions described in [1] to [7], wherein (A) the particles containing the pesticide active ingredient are 20 nm or less. [Effects of the Invention]

[0009] This allows for the preparation of aqueous dispersions containing nanoparticles that are stable against a variety of pesticide active ingredients. [Modes for carrying out the invention]

[0010] The liquid pesticide composition of the present invention (hereinafter also referred to as "the present invention composition" in this specification) contains (A) a pesticide active ingredient and (B) a surfactant. A liquid pesticide composition is a pesticide composition that is liquid at 20°C and normal pressure, and is classified, for example, into emulsions, liquid formulations, emulsions, flowable formulations, OD (oil dispersion) formulations, and suspo emulsion (suspo emulsion SE) formulations. The present invention composition is particularly preferably an emulsion or an emulsion formulation, and more preferably an emulsion.

[0011] The (A) pesticide active ingredient applied to this invention is a poorly water-soluble pesticide active ingredient with a water solubility of 500 ppm or less at 20°C. (A) Pesticide active ingredient refers to the active ingredient of agents used to control harmful organisms in the agricultural and horticultural fields, such as insecticides, fungicides, herbicides, rodenticides, and plant growth regulators. A pesticide active ingredient selected from insecticides, fungicides, and herbicides is preferred.

[0012] (A) Examples of active ingredients in insecticides that are used as pesticide active ingredients include the following: Cyanofos, fenthion, fenitrothion, pyrimiphostil, diazinon, isoxathion, chlorpyrifos, malathion, fenthoate, ethylthiometone, fosalon, methidathion, prothiofos, propenofos, EPN, carbaryl, isoprocarb, phenobucarb, carbosulfan, benfuracarb, thiodicarb, alanicarb, pyrethrin, allethrin, permethrin, cyfluthrin, tralomethrin, fenpropato Phosphorus, bifenthrin, fenvalerate, flucitrinate, fluvalinate, acrinatrin, cycloprothrin, tefluthrin, etofenprox, silafluofen, bensultap, imidacloprid, thiacloprid, clothianidin, flubendiamide, chlorantraniliprole, cyantraniliprole, fipronil, ethiprole, emamectin benzoate, milbemectin, lepimectin, abamectin, spino Sado, spinetrum, diflubenzuron, teflubenzuron, lufenuron, flufenoxuron, chlorfluazuron, novaron, tebufenozide, chromafenozide, methoxyfenozide, pyriproxyfen, buprofezin, pymetrozine, pyrifluquinazone, pyridaryl, chlorfenapir, tolfenpyrad, diafenthiuron, metaflumizone, indoxacarb, metaldehyde, propargit (BPPS), amitra Examples include phenothiocarb, hexythiazox, fenbutasin oxide, dienochlor, fenpyroximate, tebufenpyrad, pyridaben, pyrimidifen, clofentin, etoxazole, bifenazate, asequinosyl, cyenopyrafen, piflubmid, fluacrypyrim, spirodiclofen, spirotetramat, spiromesifen, cyflumetofen, kazusafos, nemadectin, cypermethrin, and flomethkin. Preferably, organophosphate insecticides such as cyanophos, fenthion, fenitrothion, pyrimiphostil, diazinon, isoxathion, chlorpyrifos, malathenthate, ethylthiometone, fosalon, methidathion, prothiophos, propenophos, EPN; carbamate insecticides such as carbaryl, isoprocarb, phenobucarb, carbosulfan, benfuracarb, thiodicarb, alanicarb; pyrethrin, allethrin, permethrin, cyfluthrin, tralomethrin, fenpropathrin, bifenthrin, fenvalerate, flucitrinate, fluvalinate, and These include pyrethroid insecticides such as clinathrin, cycloprothrin, tefluthrin, etofenprox, and silafluofen; neonicotinoid insecticides such as imidacloprid, thiacloprid, and clothianidin; phenylpyrazole insecticides such as fipronil and ethiprole; spinosad and spinetoram; hydrazine insecticides such as tebufenozide, chromafenozide, and methoxyfenozide; insect behavior control agents such as pyrifluquinazon; acaricides such as propargit (BPPS); and insecticides such as chlorfenapyr, indoxacarb, cypermethrin, and flomethkin. Preferably, the insecticide has a water solubility of 0.001 ppm to 200 ppm at 20°C, and examples include organophosphate insecticides such as diazinon and prothiophos, carbamate insecticides such as benfuracarb, pyrethroid insecticides such as fluvalinate and cycloprothrin, neonicotinoid insecticides such as thiacloprid and clothianidin, phenylpyrazole insecticides such as fipronil, spinosine insecticides such as spinosad, hydrazine insecticides such as chromafenozide, insect behavior controllers such as pyrifluquinazon, acaricides such as propargit (BPPS), chlorfenapyr, indoxacarb, cypermethrin, and flomethkin. More preferably, diazinon, prothiophos, benfuracarb, fluvalinate, cycloprothrin, thiacloprid, fipronil, spinosad, chromafenozide, pyrifluquinazone, propargit (BPPS), chlorfenapir, indoxacarb, cypermethrin, and flomethquine are mentioned.

[0013] The pesticidal active ingredients selected as fungicides are, for example, as follows. Basic copper chloride, cupric hydroxide, organic copper, dithiram, maneb, mancozeb, thiuram, propineb, iprobenfos, tolclofos-methyl, flusilazole, tricyclazole, carpropamid, diclocymet, phenoxanil, benomyl, thiophanate-methyl, diethofencarb, iprodione, procymidone, mepronil, flutolanil, boscalid, fluopicolide, fluopyram, flutriafol, penflufen, fluxapyroxad, difenoconazole, penconazole, propiconazole, tebuconazole, tetraconazole, triadimefon, azoxystrobin, kresoxim-methyl, trifloxystrobin, metominostrobin, orysastrobin, pyraclostrobin, pyribencarb, famoxadone, fenamidone, mepanipyrim, cyprodinil, flusulfamide, cymoxanil, iminoctadine albesilate, isoprothiolane, fluoroimide, penthiopyrad, fluazinam, diflumetorim, ferimzone, dimethomorph, captan, bentazone isopropyl, probenazole, ametoctradin, tebufloquin, oxolinic acid, quinoxaline-based, dithianon. Preferably, organic sulfur fungicides such as ziram, maneb, mancozeb, thiram, propineb, etc., organophosphorus fungicides such as iprobenfos, tolclofos-methyl, etc., benzimidazole fungicides such as benomyl, thiophanate-methyl, diethofencarb, etc., dicarboximide fungicides such as iprodione, procymidone, etc., amide fungicides such as mepronil, flutolanil, boscalid, fluopicolide, fluopyram, flametopyril, penthiopyrad, ethaboxam, fenhexamid, fenpyrazamine, difenoconazole, mandipropamid, thiazinyl, isothiazinyl, etc., strobilurin fungicides such as azoxystrobin, kresoxim-methyl, trifloxystrobin, metominostrobin, orysastrobin, pyraclostrobin, pyribencarb, famoxadone, fenamidone, etc., anilinopyrimidine fungicides such as mepanipyrim, cyprodinil, etc. are mentioned. Among them, it is more preferable to apply a fungicide having a water solubility of from 0.001 ppm to 200 ppm.

[0014] The pesticidal active ingredient selected as a herbicide is, for example, as follows. MCPA, MCPB ethyl, mecoprop, mecoprop P, triclopyr, clomeprop, cyhalofop butyl, fluadifop, fluadifop P butyl, quizalofop ethyl, metamifop, chlorprofam, fenmedifam, desmedifam, benthiocarb, prosulfocarb, esprocarb, molinate, pyributicarb, alachlor, pretilachlor, metolachlor, S-metholachlor, butachlor, tenylchlor, flufenace Bromobutide, etobenzanide, diflufenican, mefenacet, napropamide, cafenstrol, ibufencarbazone, propizamide, isoxaben, flupoxam, diuron, linuron, dimuron, cumilon, carbchylate, isouron, bensulfuron-methyl, ethoxysulfuron, pyrazosulfuron-ethyl, azimsulfuron, metazosulfuron, halosulfuron-methyl, nicosulfuron, limsulfuron, thifensulfuron-methyl ,propyrisulfuron,cyclosulfamuron, chlorimulon ethyl, flucetosulfuron, pyriftalide, pyriminobacmethyl, florathram, simazine, atrazine, cyanazine, simetryn, dimethametryn, promethrine, indadiflame, triaziflame, terbasil, bromacil, renacil, chloridazone, bentazon, pyrazolate, pyrazoxyfen, trifluralin, veslodin, prodiamine, pendimethalin, oryzalin, imazaquin, dichloro Examples include benyl, chlorthiamide, ioxynil, cethoxydim, chlorphthalim, flumioxazine, mesotrione, benzobicyclon, dithiopyr, quinoclamin, butamiphos, indanophan, benfresate, pyroxasulfone, pentoxazone, phenoxasulfone, pyraclonil, pyraflufen ethyl, carfentrazone ethyl, oxadiazone, oxaziargyl, oxadiclomefone, fluthiaset methyl, phentrazamide, and d-limonene. Preferably, phenoxy acid herbicides such as MCPA, MCPB ethyl, mecoprop, mecoprop P, triclopyr, clomeprop, cyhalofop butyl, fluadifop, fluadifop P butyl, quizalofop ethyl, metamifop; carbamate herbicides such as chlorprofam, fenmedifam, desmedifam, benthiocarb, prosulfocarb, esprocarb, molinate, pyributicarb; alachlor, pretilachlor amide herbicides such as metrachlor, S-metrachlor, butachlor, tenylchlor, flufenacet, bromobutide, etobenzanide, diflufenican, mefenacet, napropamide, cafenstrol, ipfencarbazone, propizamide, isoxaben, flupoxam, etc., urea herbicides such as diuron, linuron, daimuron, cumilon, carbylate, isouron, bensulfuron-methyl, ethoxysulfuron, pyrazolone Sulfonylurea herbicides such as sulfuronethyl, azimsulfuron, metazosulfuron, halosulfuronmethyl, nicosulfuron, limsulfuron, thifensulfuronmethyl, propirisulfuron, cyclosulfamuron, chlorimuronethyl, flucetosulfuron, triazine herbicides such as simazine, atrazine, cyanazine, simetryn, dimethametryn, promethrin, indadiflame, triaziflame, tarbasil, bromacil, lena Examples include diazine herbicides such as sil, chloridazone, and bentazon; pyrazole herbicides such as pyrazolate and pyrazoxyfen; dinitroaniline herbicides such as trifluralin, veslodin, prodiamine, pendimethalin, and oryzarin; nitrile herbicides such as diclobenyl, chlorthiamide, and ioxynil; phenylphthalimide herbicides such as chlorphthalim and flumioxazine; and triketone herbicides such as mesotrione and benzobicyclon. Of the above, it is more preferable to use herbicides with a water solubility of 0.001 ppm to 200 ppm at 20°C.

[0015] In the composition of the present invention, (A) the pesticide active ingredient is preferably contained in an amount of 0.1 to 60% by mass, and more preferably 0.5 to 50% by mass. In the present invention, (A) the pesticide active ingredient can be any active ingredient that is poorly water-soluble and has a water solubility of 500 ppm or less at 20°C, and can be applied without particular limitation whether it is a liquid or a solid at 20°C and normal pressure. When using a liquid pesticide active ingredient at 20°C and normal pressure, it is preferably included in the composition of the present invention at an amount of 0.1 to 60% by mass, and more preferably at an amount of 1 to 50% by mass. On the other hand, when using a solid pesticide active ingredient at 20°C and normal pressure, it is preferably included in the composition of the present invention at an amount of 0.1 to 10% by mass, and more preferably at 0.5 to 5% by mass.

[0016] The (B) surfactant in the composition of the present invention is one or more selected from the group consisting of (b1) styrene-maleic acid-polyoxyalkylene graft copolymer, (b2) polyoxyalkylene-(poly)styrylphenyl ether, and its formaldehyde condensate. (b1) The styrene-maleic acid-polyoxyalkylene graft copolymer is a graft copolymer in which the polyoxyalkylene portion is one of polyoxyethylene polymer, polyoxypropylene polymer, or polyoxyethylene-polyoxypropylene copolymer, and the polyoxyalkylene portion is bonded to one or more carbonyl groups of styrene-maleic acid. (b1) The styrene-maleic acid-polyoxyalkylene graft copolymer can be a commercially available product, for example, TERSPERSE 2612 (trade name, manufactured by INDRAMA). (b1) preferably has an HLB value of 10 to 19, and more preferably 12 to 19. HLB (Hydrophile-Lipophile Balance) is an index that represents the degree of hydrophilicity and lipophilicity of a surfactant, and is expressed as a numerical value from 0 to 20. In this specification, HLB is expressed by the following formula based on the formula weight of the hydrophilic group and the molecular weight. HLB value = 20 × (mass of hydrophilic group %)

[0017] As the surfactant (b2), polyoxyalkylene-(poly)styrylphenyl ether or its formaldehyde condensate can be used. That is, it is a polymeric nonionic surfactant in which a polyoxyalkylene group and a (poly)styrylphenyl group are linked by an ether bond. (b2) also includes the product obtained by formaldehyde condensation of this surfactant. The (poly)styrylphenyl group in surfactant (b2) is styrylphenyl, distyrylphenyl, or tristyrylphenyl. Examples include polyoxyethylene-tristyrylphenyl ether and polyoxyalkylene-tristyrylphenyl ether. Furthermore, a polymerization number of 10 to 20 in the polyoxyalkylene portion is preferred. (b2) preferably has an HLB value of 8 to 18, and more preferably 10 to 16.

[0018] As the surfactant (b2), commercially available polyoxyalkylene-(poly)styrylphenyl ethers can be used, for example, Solpol T-10 (product name Toho Chemical Co., Ltd. HLB 10 (catalog value)), Solpol T-15 (product name Toho Chemical Co., Ltd. HLB 12 (catalog value)), Solpol T-20 (product name Toho Chemical Co., Ltd. HLB 13.3 (catalog value)), Solpol T-26 (product name Toho Chemical Co., Ltd. HLB 14.4 (catalog value)), Solpol T-32 (product name Toho Chemical Co., Ltd. HLB 15.2 (catalog value)), Newcalgen C-120 (product name Takemoto Oil Co., Ltd. HLB 10.9 (catalog value)), Newcalgen C-150 (product name Takemoto Oil Co., Ltd. HLB 12 (catalog value)), Newcalgen C-200 (product name Takemoto Oil Co., Ltd. HLB 13.3 (catalog value)), Newcalgen C-314 (product name Takemoto Oil & Fat Co., Ltd. HLB 15.2 (catalog value), New Calgen CP-50 (Takemoto Oil & Fat Co., Ltd. HLB 11 (catalog value)), New Calgen CP-80 (product name Takemoto Oil & Fat Co., Ltd. HLB 12 (catalog value)), New Calgen CP-120 (product name Takemoto Oil & Fat Co., Ltd. HLB 13.2 (catalog value)), New Calgen CP-150 (product name Takemoto Oil & Fat Co., Ltd. HLB 14 (catalog value)), New Calgen CP-15-150 (product name Takemoto Oil & Fat Co., Ltd. HLB 14.5 (catalog value), New Calgen CP-15-200 (product name, Takemoto Oil Co., Ltd.), New Calgen FS-1 (product name, Takemoto Oil Co., Ltd.), Paionin D-6112 (product name, Takemoto Oil Co., Ltd.), Paionin D-6115 (product name, Takemoto Oil Co., Ltd.), Paionin D-6120 (product name, Takemoto Oil Co., Ltd.), Paionin D-6131 (product name, Takemoto Oil Co., Ltd.), Paionin D-6105-W (product name, Takemoto Oil Co., Ltd.), Paionin 6108-W (product name, Takemoto Oil Co., Ltd.), Paionin 6112-W (product name, Takemoto Oil Co., Ltd.), Paionin 6120-X (product name, Takemoto Oil Co., Ltd.), Paionin 6512 (product name, Takemoto Oil Co., Ltd.), Takesurf D-6413 (product name Takemoto Oil & Fat Co., Ltd., Paionin D-6414 (product name, Takemoto Oil & Fat Co., Ltd.), and DTD-51 (product name, Takemoto Oil & Fat Co., Ltd.) can be used.

[0019] In (b2), the formaldehyde condensate of polyoxyalkylene-(poly)styrylphenyl ether is preferably HLB 9 to 16, and more preferably HLB 10 to 14. A commercially available product may be used, for example, Solpol 3080 (product name Toho Chemical Co., Ltd.).

[0020] The surfactant (B) in the composition of the present invention is characterized by being contained in an amount equal to or greater than the amount of the pesticide active ingredient (A), and the mass content ratio of the pesticide active ingredient (A) to the surfactant (B) is 1:1 to 100. Preferably, (A):(B) is 1:1 to 80. Furthermore, when the pesticide active ingredient (A) is a liquid component at 20°C and normal pressure, it is preferable that (A):(B) be applied in a ratio of 1:1 to 100, and more preferably 1:1 to 50. On the other hand, when the pesticide active ingredient (A) is a solid component at 20°C and normal pressure, it is preferable that (A):(B) be applied in a ratio of 1:1 to 100, and more preferably 1:5 to 100. Furthermore, in the composition of the present invention, (B) surfactant is contained in an amount of 10 to 90% by mass. Preferably, it is 30 to 90% by mass. When (A) the pesticide active ingredient is a liquid component at 20°C and normal pressure, (B) surfactant is preferably contained in an amount of 10 to 90% by mass, and more preferably 30 to 90% by mass. Furthermore, when (A) the pesticide active ingredient is a solid component at 20°C and normal pressure, (B) surfactant is preferably contained in an amount of 10 to 90% by mass, and more preferably 30 to 90% by mass.

[0021] In addition to (b1) and (b2) above, any other surfactant (b3) may be included in combination. Examples include nonionic surfactants, anionic surfactants, nonionic anionic surfactants, cationic surfactants, and amphoteric surfactants. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkylphenol formalin condensates, polyoxyethylene castor oil derivatives, polyoxyethylene fatty acid esters, higher fatty acid glycerol esters, polyoxyethylene fatty acid amides, alkylol amides, polyoxyethylene fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene polyoxypropylene block polymers, sucrose fatty acid esters, and polyglycerin fatty acid esters. Polyoxyethylene sorbitan fatty acid esters are preferred. Examples of anionic compounds include sodium dioctyl sulfosuccinate, sodium alkylnaphthalene sulfonate formaldehyde condensate, sodium lignin sulfonate, sodium alkylbenzene sulfonate, sodium lauryl sulfate, and sodium polycarboxylate. Sodium dioctyl sulfosuccinate is preferably included. Examples of nonionic anionic surfactants include polyoxyalkylene-lauryl ether sulfate ammonium salt, polyoxyalkylene-lauryl sulfate ammonium salt, polyoxyethylene-lauryl ether sulfate sodium salt, polyoxyethylene-alkyl ether sulfate sodium salt, polyoxyalkylene-tristyrylphenyl ether sulfate ammonium salt, polyoxyethylene-allylphenyl ether sulfate amine salt, and polyoxyalkylene-allylphenyl ether sulfate ammonium salt. Examples of cationic surfactants include alkyltrimethylammonium chloride, methylpolyoxyethylenealkylammonium chloride, alkyl N-methylpyridinium bromide, monomethylated ammonium chloride, dialkylmethylated ammonium chloride, alkylpentamethylpropyleneamine dichloride, alkyldimethylbenzalkonium chloride, and benzethonium chloride. Examples of amphoteric surfactants include dialkyldiaminoethylbentaine and alkyldimethylbenzylbentaine.

[0022] In the present invention, (A) the pesticide active ingredient can be any active ingredient that is poorly water-soluble and has a water solubility of 500 ppm or less at 20°C, whether it is a liquid or a solid at 20°C and atmospheric pressure, without any particular limitations. However, when using a pesticide active ingredient that is solid at 20°C and atmospheric pressure, it is contained in the composition of the present invention in a dissolved state. For this reason, when using a solid pesticide active ingredient, it is preferable to use (C) a solvent. This (C) solvent is preferably one that can dissolve the pesticide active ingredient in combination with (B) a surfactant and is miscible with water in any proportion. Examples include solvents of alcohols, ketones, amides, and ethers. Preferably, methanol, ethanol, propanol, acetone, ethyl methyl ketone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, ethylene glycol, propylene glycol, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, etc., and these are used one or a mixture of two or more. More preferred solvents include methanol, acetone, cyclohexanone, N,N-dimethylformamide, diethylene glycol monoethyl ether, and dipropylene glycol monomethyl ether, and more preferably methanol, acetone, cyclohexanone, N,N-dimethylformamide, and diethylene glycol monoethyl ether. The amount of solvent added should be sufficient to dissolve the active pesticide component, preferably at least twice the mass ratio of the active pesticide component. Furthermore, considering ease of use and cost in the context of use of the composition of the present invention, it is even more preferable to be 2 to 100 times, and particularly preferable to be 2 to 50 times. (C) When a solvent is used, it is preferable that it be contained in the composition of the present invention in an amount of 1 to 60% by mass.

[0023] The composition of the present invention preferably contains a rosin compound (D). Rosin is a natural resin mainly composed of abietic acid, palastic acid, etc., obtained by distilling turpentine essential oil from pine resin, which is the sap of pine trees. Rosin compounds, obtained by reacting rosin with other chemicals, have high compatibility and are used as additives in inks, paints, adhesives, etc. Examples of rosin compounds include disproportionated rosin, maleated rosin, gum rosin, and tall rosin. In the composition of the present invention, the rosin compound has the function of enhancing stability in the formulation or in diluted dispersion. In the composition of the present invention, when rosin compound (D) is used, it is preferably contained in an amount of 0.1 to 10% by mass, and more preferably in an amount of 0.5 to 10% by mass.

[0024] The composition of the present invention may optionally contain additives used in agricultural chemical formulations. Examples of additives include stabilizers, thickeners, and defoamers, and one or more of each can be used. Examples of stabilizers include quenchers, radical scavengers, UV absorbers, and antioxidants. Quenchers include epoxidized soybean oil, epoxidized linseed oil, epoxidized octyl fatty acid, epoxidized butyl fatty acid, epoxidized methyl bran fatty acid, and epoxidized rapeseed oil. Radical scavengers include vitamin E, vitamin C, ubiquinol, uric acid, flavonoids, tannins, sesaminol, and curcumin. UV absorbers include benzotriazole-based UV absorbers and benzophenone-based UV absorbers. Antioxidants include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of thickening agents include natural polysaccharides such as xanthan gum, locust bean gum, and xanthan gum; mineral substances such as magnesium aluminum silicate and bentonite; semi-synthetic polysaccharides such as carboxymethylcellulose sodium salt; and synthetic water-soluble polymers such as polyacrylates. Examples of defoaming agents include silicone-based emulsions.

[0025] In this invention, the content of each component is important for dispersing the formulation at the nanoscale when diluted in water. The higher the content of the pesticide active ingredient, the larger the particles become when diluted in water. On the other hand, the higher the content of the surfactant, the smaller the particles become when diluted in water, and the particle size remains stable over a long period of time. The composition of the present invention is preferably a liquid pesticide composition containing (A) 1 to 60% by mass of an active pesticide component, (B) 10 to 90% by mass of a surfactant, and (C) 0 to 60 parts by mass of a solvent. More preferably, (A) 0.5 to 50% by mass of an active pesticide component, (B) 30 to 96% by mass of a surfactant, and (C) 0 to 60 parts by mass of a solvent.

[0026] There are no particular restrictions on the method for preparing the composition of the present invention, but for example, it can be prepared by mixing (A) an active pesticide component, (B) a surfactant, and any (C) solvent to make a homogeneous solution. Alternatively, it can be prepared by mixing (A) an active pesticide component and (C) a homogeneous solution, and then adding (B) a surfactant and mixing.

[0027] It is preferable to dilute the composition of the present invention with water and spray it on the target plant or soil. In this case, the dilution ratio of the composition of the present invention with water is preferably 10 times or more, and more preferably 100 times or more.

[0028] The composition of the present invention, when diluted with water, prepares a dispersion in which (A) the pesticide active ingredient is micronized to the nanoparticle level. Here, "particles" refer to hydrophobic components containing the pesticide active ingredient dispersed in water, and their size is called the particle diameter. Nanoparticles refer to particles with a particle diameter of 100 nm or less. In this specification, particle size refers to the median value when the volume median diameter of all particles contained in an aqueous dispersion obtained by diluting the composition of the present invention 100 times with water is represented as a distribution. The aqueous dispersion of the composition of the present invention is a nanoparticle dispersion with a particle size of 50 nm or less. More preferably, a nanoparticle dispersion with a particle size of 20 nm or less can be prepared. Furthermore, in order for the nanoparticle dispersion to exert its full effect as a pesticide spray solution, it is desirable that the particle size be maintained for a long period of time. The nanoparticle dispersion obtained from the composition of the present invention can maintain its particle size for 24 hours or more. More preferably, it can maintain its particle size for 48 hours or more.

[0029] Dynamic light scattering is used as a method for measuring the particle size of an aqueous dispersion of the composition of the present invention. Here, particle size refers to the diameter of the particle being measured, and represents the median diameter of the volume distribution of the measured particles. Examples of measuring instruments include the Nanotrac Wave2 (manufactured by Microtrac-Bell Corporation, measurable range: 0.8~6500nm). [Examples]

[0030] The following embodiments further illustrate the present invention. (1) Preparation of liquid pesticide composition The pesticide active ingredient (A), surfactants (B - b1 and / or b2, and any b3), and an optional solvent (C - if multiple types are used, denoted as C1, C2, etc.), and a rosin compound (D) were mixed homogeneously to prepare the mixture. (2) Measurement of particle size of aqueous dispersion of liquid pesticide composition (a) Analytical sample A 0.1 mL sample of the prepared liquid pesticide composition was taken and mixed with 10 mL of water to obtain a solution which was used as the particle size measurement sample. (b) Analytical equipment and measurement conditions Equipment: Nanotrac Wave2 (Microtrac Bell Co., Ltd.) Measurement conditions: The median diameter of the diluent was measured by volume distribution. Measurement time: 60 seconds Number of measurements: 3 Particle permeability: transparent

[0031] [Example 1] A: Chromafenozide...1.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 97 parts by mass C1: Methanol...2.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 1. The aqueous dispersion obtained by adding 0.1 mL of the liquid pesticide composition of Example 1 to 10 mL of water and mixing was a particle dispersion with a particle size of 8 nm.

[0032] [Example 2] A: Chromafenozide...1.0 parts by mass b2: Mixture of polyoxyethylene-distyrylphenyl ether formaldehyde condensate and dodecylbenzene sulfonate (Solpol 3080 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 50.0 parts by mass C1: Methanol...2.0 parts by mass C2: Dipropylene glycol monomethyl ether... 47.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 2. The aqueous dispersion obtained by adding 0.1 mL of the liquid pesticide composition of Example 2 to 10 mL of water and mixing it was a particle dispersion with a particle size of 4.8 nm.

[0033] [Example 3] A: Chromafenozide...1.0 parts by mass b2: Polyoxyethylene (19)-tristyrylphenyl ether (Solpol T-20 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 50.0 parts by mass C1: Methanol...2.0 parts by mass C2: Dipropylene glycol monomethyl ether... 47.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 3. 0.1 mL of the liquid pesticide composition from Example 3 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 7.4 nm.

[0034] [Example 4] A: Chromafenozide...1.0 parts by mass b2: Polyoxyethylene-styrylphenyl ether (Newcalgen C-150 (trade name, manufactured by Takemoto Oil Co., Ltd.)) ... 50.0 parts by mass C1: Methanol...2.0 parts by mass C2: Dipropylene glycol monomethyl ether... 47.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 4. 0.1 mL of the liquid pesticide composition of Example 4 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 16 nm.

[0035] [Example 5] A: Chromafenozide...1.0 parts by mass b2: Polyoxyethylene-styrylphenyl ether (Newcalgen CP-120 (trade name, manufactured by Takemoto Oil Co., Ltd.)) ... 50.0 parts by mass C1: Methanol...2.0 parts by mass C2: Dipropylene glycol monomethyl ether... 47.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 5. 0.1 mL of the liquid pesticide composition of Example 5 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 6.7 nm.

[0036] [Example 6] A: Chromafenozide...5.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 80.0 parts by mass C1: Methanol...10.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 5.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 6. 0.1 mL of the liquid pesticide composition of Example 6 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 14 nm.

[0037] [Example 7] A: Chromafenozide...5.0 parts by mass b2: Polyoxyethylene (14)-tristyrylphenyl ether (Solpol T-15 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 70.0 parts by mass b3: Polyoxyethylene-sorbitan laurate ester (Sorbon T-20 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 10.0% C1: Methanol...10.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 5.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 7. When 0.1 mL of the liquid pesticide composition of Example 7 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 11 nm.

[0038] [Example 8] A: Frommetkin...1.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 96.0 parts by mass C1: Cyclohexanone ··· 2.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 1.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 8. 0.1 mL of the liquid pesticide composition of Example 8 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 12 nm.

[0039] [Example 9] A: Frommetkin...1.0 parts by mass b2: Polyoxyethylene (14)-tristyrylphenyl ether (Solpol T-15 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 50.0 parts by mass b3: Polyoxyethylene (20)-sorbitan laurate ester (Sorbon T-20 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 46.0% C1: Cyclohexanone ··· 2.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 1.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 9. 0.1 mL of the liquid pesticide composition of Example 9 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 8.5 nm.

[0040] [Example 10] A: Chlorfenapyr...1.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 98.0 parts by mass C1: Cyclohexanone ··· 1.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 10. 0.1 mL of the liquid pesticide composition of Example 10 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 11 nm.

[0041] [Example 11] A: Thiacloprid...1.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 96.0 parts by mass C1: N,N-dimethylformamide ···3.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 11. When 0.1 mL of the liquid pesticide composition from Example 11 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 8.7 nm.

[0042] [Example 12] A: Thiacloprid...5.0 parts by mass b2: Polyoxyethylene (14)-tristyrylphenyl ether (Solpol T-15 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 40.0 parts by mass b3: Polyoxyethylene (20)-sorbitan laurate ester (Sorbon T-20 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 35.0% C1: N,N-dimethylformamide ··· 15.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 5.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 12. 0.1 mL of the liquid pesticide composition of Example 12 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 10 nm.

[0043] [Example 13] A: Fipronil... 1.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 96.0 parts by mass C1: Acetone...2.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 1.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 13. 0.1 mL of the liquid pesticide composition of Example 13 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 13 nm.

[0044] [Example 14] A: Fipronil...5.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 80.0 parts by mass C1: Acetone ··· 10.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 5.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 14. 0.1 mL of the liquid pesticide composition of Example 14 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 15 nm.

[0045] [Example 15] A: Spinosad...5.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 80.0 parts by mass C1: Cyclohexanone ··· 10.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 5.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 15. 0.1 mL of the liquid pesticide composition of Example 15 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 8 nm.

[0046] [Example 16] A: Spinosad...5.0 parts by mass b2: Polyoxyethylene (15)-tristyrylphenyl ether (Solpol T-15 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 80.0 parts by mass C1: Methanol...10.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 5.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 16. When 0.1 mL of the liquid pesticide composition of Example 16 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 16 nm.

[0047] [Example 17] A: Pyrifluquinazone... 5.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 80.0 parts by mass C1: Cyclohexanone ··· 10.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 5.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 17. 0.1 mL of the liquid pesticide composition of Example 17 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 13 nm.

[0048] [Example 18] A: Indoxacarb...1.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 95.0 parts by mass C1: Cyclohexanone ··· 4.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 18. When 0.1 mL of the liquid pesticide composition of Example 18 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 7.6 nm.

[0049] [Example 19] A: Diazinon...20.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 80.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 19. When 0.1 mL of the liquid pesticide composition of Example 19 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 14 nm.

[0050] [Example 20] A: Diazinon...20.0 parts by mass b2: Mixture of polyoxyethylene-distyrylphenyl ether formaldehyde condensate and dodecylbenzene sulfonate (Solpol 3080 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 80.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 20. 0.1 mL of the liquid pesticide composition of Example 20 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 1.8 nm.

[0051] [Example 21] A: Diazinon... 50.0 parts by mass b2: Polyoxyethylene (20)-tristyrylphenyl ether (Solpol T-20 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 50.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 21. 0.1 mL of the liquid pesticide composition of Example 21 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 18 nm.

[0052] [Example 22] A: Diazinon... 50.0 parts by mass b2: Polyoxyalkylene-styrylphenyl ether (Newcalgen CP-120 (trade name, manufactured by Takemoto Oil Co., Ltd.)) ... 50.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 22. 0.1 mL of the liquid pesticide composition of Example 22 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 20 nm.

[0053] [Example 23] A: Benfuracarb... 10.0 parts by mass b1 and C1: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 90.0 parts by mass The above ingredients were mixed uniformly. The above components were uniformly mixed to prepare the liquid pesticide composition of Example 23. 0.1 mL of the liquid pesticide composition of Example 23 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 13 nm.

[0054] [Example 24] A: Prothiophos...10.0 parts by mass b1 and C1: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 90.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 24. 0.1 mL of the liquid pesticide composition of Example 24 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 12 nm.

[0055] [Example 25] A: Prothiophos...10.0 parts by mass b2: Polyoxyalkylene-styrylphenyl ether (Newcalgen CP-120 (trade name, manufactured by Takemoto Oil Co., Ltd.)) ... 36.0 parts by mass b3: Sodium dialkyl sulfosuccinate (Newcalgen EP-70G (product name, manufactured by Takemoto Oil Co., Ltd.)) ... 24.0 parts by mass C1: Cyclohexanone ···30.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 25. 0.1 mL of the liquid pesticide composition of Example 25 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 4.6 nm.

[0056] [Example 26] A: Cycloprothrin...10.0 parts by mass b1 and C1: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 90.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 26. 0.1 mL of the liquid pesticide composition of Example 26 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 6.1 nm.

[0057] [Example 27] A: Cypermethrin...1.0 parts by mass b1 and C1: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 99.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 27. 0.1 mL of the liquid pesticide composition of Example 27 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 9.4 nm.

[0058] [Example 28] A: Full Valinate... 10.0 parts by mass b1 and C1: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 90.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 28. 0.1 mL of the liquid pesticide composition of Example 28 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 6.3 nm.

[0059] [Example 29] A: Full Valinate... 10.0 parts by mass b2: Polyoxyalkylene-styrylphenyl ether (Newcalgen CP-120 (trade name, manufactured by Takemoto Oil Co., Ltd.)) ... 36.0 parts by mass b2: Sodium dialkyl sulfosuccinate (Newcalgen EP-70G (product name, manufactured by Takemoto Oil Co., Ltd.)) ... 24.0 parts by mass C1: Cyclohexanone ···30.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 29. 0.1 mL of the liquid pesticide composition of Example 29 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 5.1 nm.

[0060] [Example 30] A: Propellgit (BPPS) ... 10.0 parts by mass b1 and C1: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in a dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 90.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Example 30. 0.1 mL of the liquid pesticide composition of Example 30 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle size of 11 nm.

[0061] [Comparative Example 1] A: Chromafenozide...1.0 parts by mass B: Polyoxyethylene alkyl ether (Pegnol ST-12 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 50.0 parts by mass C1: Methanol...2.0 parts by mass C2: Dipropylene glycol monomethyl ether... 47.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Comparative Example 1. When 0.1 mL of the liquid pesticide composition of Comparative Example 1 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 2884 nm.

[0062] [Comparative Example 2] A: Chromafenozide...1.0 parts by mass B: Polyoxyethylene oleate ester (Pegnol 14-0 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 50.0 parts by mass C1: Methanol...2.0 parts by mass C2: Dipropylene glycol monomethyl ether... 47.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Comparative Example 2. When 0.1 mL of the liquid pesticide composition of Comparative Example 2 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 256 nm.

[0063] [Comparative Example 3] A: Chromafenozide...1.0 parts by mass B: Polyoxyethylene sorbitan trioleate (Sorbon T-85 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 50.0 parts by mass C1: Methanol...2.0 parts by mass C2: Dipropylene glycol monomethyl ether... 47.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Comparative Example 3. When 0.1 mL of the liquid pesticide composition of Comparative Example 3 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 472 nm.

[0064] [Comparative Example 4] A: Chromafenozide...1.0 parts by mass B: Dialkyl sulfosuccinate (Newcalgen EP60P (product name, manufactured by Takemoto Oil Co., Ltd.)) ... 50.0 parts by mass C1: Methanol...2.0 parts by mass C2: Dipropylene glycol monomethyl ether... 47.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Comparative Example 4. When 0.1 mL of the liquid pesticide composition of Comparative Example 4 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 3914 nm.

[0065] [Comparative Example 5] A: Chromafenozide...1.0 parts by mass B: Sodium alkylbenzene sulfonate (Newcalgen A-41-B (product name, manufactured by Takemoto Oil Co., Ltd.)) ... 50.0 parts by mass C1: Methanol...2.0 parts by mass C2: Dipropylene glycol monomethyl ether... 47.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Comparative Example 5. When 0.1 mL of the liquid pesticide composition of Comparative Example 5 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 3155 nm.

[0066] [Comparative Example 6] A: Chromafenozide...10.0 parts by mass b1 and C2: 50% styrene-maleate-polyoxyethylene polyoxypropylene graft copolymer in dipropylene glycol monoethyl ether solution (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ... 2.0 parts by mass C1: Methanol...78.0 parts by mass D: Disproportionated rosin (Diplozine A-100 (product name, manufactured by Toho Chemical Co., Ltd.)) ... 10.0 parts by mass The above components were uniformly mixed to prepare the liquid pesticide composition of Comparative Example 6. When 0.1 mL of the liquid pesticide composition of Comparative Example 6 was added to 10 mL of water and mixed, the resulting aqueous dispersion was a particle dispersion with a particle size of 161 nm.

[0067] [Test Example 1] Aqueous dispersion stability test The liquid pesticide compositions of Examples 1-30 and Comparative Examples 1-6 were added to water in a test tube to a 100-fold dilution and mixed. The particle size distribution of the diluted solution was measured immediately after mixing and every day thereafter to confirm the number of days during which the particle size remained unchanged from the time of dilution. Tables 1-1 to 1-4 show the particle size immediately after dilution and the number of days for which the initial particle size was maintained. All of the liquid pesticide compositions of Examples 1 to 30 relating to the composition of the present invention were fine nanoparticle dispersions with a particle size of 20 nm or less immediately after preparation of the aqueous dispersion, and these nanoparticle dispersions exhibited stable physical properties that were maintained for at least one day. On the other hand, the liquid pesticide compositions relating to the comparative examples could not prepare a nanoparticle dispersion of about 20 nm by the water mixing operation, and the stability of the dispersions was poor.

[0068] [Table 1-1] TIFF2026068026000001.tif139170

[0069] [Table 1-2] TIFF2026068026000002.tif140170

[0070] [Table 1-3] TIFF2026068026000003.tif133170

[0071] [Table 1-4] TIFF2026068026000004.tif64170 (*1) TERSPERSE 2612; Dipropylene glycol monoethyl ether (DPGME) solution containing 50% styrene maleate-polyoxyethylene polyoxypropylene copolymer (*2) DPGME; Dipropylene glycol monoethyl ether (*3) DPGMM; Dipropylene glycol monomethyl ether

[0072] [Test Example 2] Permeation and Transfer Test The penetration and translocation properties of the liquid pesticide composition of Example 1 into the plant were tested using an existing formulation containing the same active pesticide ingredient (chromafenozide) (Matric Flowable (product name, sold by Nippon Kayaku Co., Ltd.)) as a control. The test sample was a dispersion prepared by adding 1 mL of the formulation from Example 1 to 99 mL of tap water and mixing. The control agent was a mixture prepared by adding 0.1 mL of Matrix Flowable to 99.9 mL of tap water and mixing. Radish sprouts were grown in plastic pots with soil in between. Holes were made in the bottom of the plastic pots to allow the chemical solution to penetrate from below. Dishes filled with 100 mL of each diluted solution were placed at the bottom of the plastic pots to allow the chemical solution to permeate the soil. After cutting the radish sprouts 1 cm above the soil surface, the active ingredients were extracted with ethyl acetate, and the concentration of the active ingredients was analyzed by LC. The test results are shown in Table 2. In the case of Matrix Flowable, chromafenozide was not detected in radish sprouts. On the other hand, in Example 1, chromafenozide was detected two days after treatment with the chemical solution, confirming the manifestation of systemic properties due to the nanoparticle form of the active ingredient. Due to systemic properties, the active ingredient can be absorbed by the roots along with moisture in the soil and move to the stems and leaves of the upper layers of the crop, spreading throughout the entire plant. Therefore, even if there are inconsistencies in the application of the pesticide, the active ingredient of the pesticide can be distributed evenly throughout the plant. Furthermore, systemic properties make it easier to control pests that hide on the underside of leaves such as aphids and spider mites, pests that hide deep inside petals, and diseases that hide inside the plant body, resulting in stable effectiveness.

[0073] [Table 2] Permeability test results TIFF2026068026000005.tif57170

[0074] [Test Example 3] Confirmation of soil adsorption properties The soil adsorption properties of the dispersion of the liquid pesticide composition of Example 1 were tested using an existing formulation containing the same pesticide active ingredient (chromafenozide) (Matric Flowable (product name, sold by Nippon Kayaku Co., Ltd.)) as a control. One sample was prepared by adding 1 mL of the formulation from Example 1 to 99 mL of tap water and mixing it. The other sample was prepared by adding 0.1 mL of Matrix Flowable to 99.9 mL of tap water and mixing it. This was used as the control agent. A simple column was created by packing a 5 mL plastic tube with a paper rag and adding 5 g of soil sifted through a 2 mL sieve. 10 mL of each chemical solution was passed through the simple column. The chemical solutions after soil filtration were analyzed by high-performance liquid chromatography, and the concentration of the active ingredient was calculated. The soil adsorption rate was calculated using the following formula. Soil adsorption rate (%) = 100 × (1 - concentration of active ingredient after soil filtration / concentration of active ingredient in the treatment solution) The test results are shown in Table 3. The average soil adsorption rate of the control agent, a diluted matrix flowable solution, was 73%. On the other hand, the average soil adsorption rate of the diluted solution from Example 1 was 35%, confirming that the reduction in soil adsorption rate was due to the nanoparticle formation of the active ingredient. Reducing soil adsorption is expected to allow pesticides to be absorbed more efficiently into the plant, leading to benefits such as reduced pesticide use and labor savings.

[0075] [Table 3] Soil adsorption test results TIFF2026068026000006.tif83170

Claims

1. (A) A liquid pesticide composition comprising a pesticide active ingredient and (B) a surfactant. (A) The pesticide active ingredient is a pesticide active ingredient with a water solubility of 500 ppm or less at 20°C. (B) The surfactant is one or more selected from the group consisting of (b1) styrene maleic acid-polyoxyalkylene graft copolymer, (b2) polyoxyalkylene-(poly)styrylphenyl ether, and its formaldehyde condensate. (A) The mass content ratio of the pesticide active ingredient to (B) the surfactant is 1:1 to 100. Liquid pesticide composition.

2. The liquid pesticide composition according to claim 1, which is an emulsion and an emulsion agent.

3. (A) The pesticide active ingredient is a liquid pesticide active ingredient at 20°C and normal pressure. (A) The mass content ratio of the pesticide active ingredient to (B) the surfactant is 1:1 to 10. The liquid pesticide composition according to claim 1 or 2.

4. (A) The pesticide active ingredient is a solid pesticide active ingredient at 20°C under normal pressure. (C) Contains solvent, (A) The mass content ratio of the pesticide active ingredient to (B) the surfactant is 1:5 to 100. The liquid pesticide composition according to claim 1 or 2.

5. The liquid pesticide composition according to claim 4, wherein (A) the amount of the pesticide active ingredient is 1 part by mass, and (C) the amount of the solvent is 2 to 100 parts by mass.

6. (D) A liquid pesticide composition according to any one of claims 1 to 5, comprising a rosin compound.

7. A liquid pesticide composition according to any one of claims 1 to 6, wherein the particles containing (A) the pesticide active ingredient in a dispersion diluted 100 times with water are 20 nm or less.

8. An aqueous dispersion comprising the liquid pesticide composition according to any one of claims 1 to 7, (A) The particles containing the active ingredient of the pesticide are 20 nm or smaller. Aqueous dispersion.