JP2023113291A - Liquid agrochemical composition - Google Patents

Abstract

To make it possible to improve the drug efficacy and the drug permeability by forming the agrochemical active ingredient into nanoparticles, in particular, an agrochemical formulation capable of easily preparing an agrochemical nanoparticle dispersion by dilution with water is required, therefore, an object of the present invention is to provide an agrochemical composition having an agrochemical ingredient particle size of 20nm or less in an aqueous dispersion and capable of maintaining the particle size for 24 hours or more.SOLUTION: A liquid agrochemical composition according to the present invention includes (A) an agrochemical active ingredient and (B) a surfactant. (A) is an agrochemical active ingredient having a water-solubility of 500 ppm or less at 20°C; (B) is one or more selected from the group consisting of (b1) styrene maleic acid-polyoxyalkylene graft copolymers, (b2) polyoxyalkylene-(poly) styryl phenyl ethers, and formaldehyde condensates thereof; wherein the liquid agrochemical composition has a mass content ratio of (A) the agrochemical active ingredient to (B) the surfactant of 1:1-100.SELECTED DRAWING: None

Description

The present invention relates to a liquid agricultural chemical composition containing a poorly water-soluble agricultural chemical active ingredient 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 agricultural chemical active ingredient. .

Liquid pesticide formulations are usually used after being diluted with water. However, many of the pesticidal active ingredients have poor solubility in water. For this reason, surfactants and the like are added to agricultural chemical active ingredients to provide emulsions and emulsions that can be easily diluted and dispersed with water.

In water-diluted dispersions containing pesticidal active ingredients, the smaller the dispersed particle size of the pesticidal component, the larger the surface area of the substance per unit weight, and thus the pesticidal effect of the pesticide is expected to improve. In particular, it is generally known that when the particle size containing the pesticidal active ingredient is 100 nm or less (hereinafter referred to as nanoparticles), the permeability to plants is improved. Non-Patent Document 1 reports that by making the gold particles as small as 50 nm, the gold particles sprayed on the surface of the plant penetrate into the interior and spread throughout the plant through vascular bundles. Based on these findings, it is expected that a spray solution containing nanoparticles of pesticide component particles will efficiently permeate the plants to which it is applied. In the past, fungicides were only expected to have a preventive effect by exterminating pathogens adhering to the leaves. There is also sex. Furthermore, by improving the permeability to target pests and pathogens, it is expected to increase efficacy and expand the spectrum.
Non-Patent Document 2 reports that polymer-type nano pesticide formulations of β-cyfluthrin, carbofuran, and acephate have improved insecticidal effects compared to existing formulations. They also reported that the residual effect of the liposomal nanopesticide formulation of etofenprox was longer than that of existing agents.
Non-Patent Literature 3 reports a case where the effect on plants was improved by reducing the size of inorganic particles to the nano level. For example, the use of CuO nanoparticles increased the growth rate of corn by 51%. It is also reported that the use of TiO ₂ nanoparticles improved cowpea yield by 26% to 51%.
US Pat. No. 5,300,001 discloses a liquid pesticide composition comprising a pesticide compound, a solvent, and a block polymer-type surfactant having alkylene oxide or styrene oxide moieties (PAO) and polyethylene oxide moieties (PEO). It describes that a nanoparticle dispersion can be prepared by dilution in water to improve insecticidal activity. Most of the particles in the dispersion liquid obtained from this composition had a rather large particle size of 20 to 100 nm, and the stability was about 24 hours. Moreover, the composition in which the particle size in the dispersion is 20 nm or less is limited to an agriculturally active ingredient with a water solubility of 500 ppm or more.

ACS Nano 2019, 13, 5, 5291-5305 Environment International 63 (2014) 224-235 Environ Chem Lett (2017) 15:15-22

Japanese translation of PCT publication No. 2008-505150

As described above, nanoparticulation of an agrochemical active ingredient can improve drug efficacy and drug permeability. Therefore, there is a demand for an agricultural chemical formulation that can be easily prepared into an agricultural chemical nanoparticle dispersion liquid by diluting it with water. An object of the present invention is to provide an agrochemical composition that provides stable nanoparticles containing an agrochemical active ingredient with a water solubility of 500 ppm or less. Particularly preferably, the objective is to provide an agricultural chemical composition in which the particle size of the agricultural chemical component in the resulting dispersion is 20 nm or less when diluted with water, and the particle size can be maintained for 24 hours or more.

As a result of intensive research to solve the above problems, the present inventors have found that styrene maleic acid-polyoxyalkylene graft copolymers, polyoxyalkylene-(poly)styrylphenyl ethers or their formaldehyde condensates are highly effective against various agrochemical active ingredients. Focusing attention on having dispersibility, the present invention was completed by optimizing the content of each component.

That is, the present invention has the following configurations [1] to [8].
[1] A liquid agricultural chemical composition containing (A) an agricultural chemical active ingredient and (B) a surfactant,
(A) the agricultural chemical active ingredient is an agricultural chemical active ingredient having 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 formaldehyde condensates thereof and
(A) the pesticidal active ingredient and (B) the surfactant have a mass content ratio of 1:1 to 100;
A liquid pesticide composition.
[2] The liquid agricultural chemical composition according to [1], which is an emulsion or emulsion.
[3] (A) the agricultural chemical active ingredient is a liquid agricultural chemical active ingredient at 20° C. under normal pressure;
(A) the pesticidal active ingredient and (B) the surfactant have a mass content ratio of 1:1 to 10;
The liquid agricultural chemical composition according to [1] or [2].
[4] (A) the agricultural chemical active ingredient is a solid agricultural chemical active ingredient at 20° C. under normal pressure;
(C) contains a solvent;
(A) the pesticidal active ingredient and (B) the surfactant have a mass content ratio of 1:5 to 100;
The liquid agricultural chemical composition according to [1] or [2].
[5] The liquid agricultural chemical composition according to [4], wherein (C) the solvent is 2 to 100 parts by mass per 1 part by mass of (A) the active ingredient of the agricultural chemical.
[6] The liquid agricultural chemical composition according to any one of [1] to [5], containing (D) a rosin compound.
[7] The liquid pesticide composition according to any one of [1] to [6], wherein (A) particles containing the pesticidal active ingredient in the dispersion diluted 100 times with water are 20 nm or less.
[8] An aqueous dispersion containing the water of the liquid agricultural chemical composition according to any one of [1] to [7], wherein (A) the particles containing the agricultural chemical active ingredient are 20 nm or less. .

Aqueous dispersions containing nanoparticles that are stable to a wide variety of pesticidal active ingredients can be prepared.

The liquid agricultural chemical composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains (A) an agricultural chemical active ingredient and (B) a surfactant. A liquid agricultural chemical composition is an agricultural chemical composition that is liquid at 20° C. under normal pressure, and is classified into, for example, an emulsion, a liquid, an emulsion, a flowable agent, an OD (oil dispersion) agent, and a suspo emulsion SE. be. The composition of the present invention is particularly preferably an emulsion or an emulsion, more preferably an emulsion.

The (A) agricultural chemical active ingredient applied to the present invention is a sparingly water-soluble agricultural chemical active ingredient having a water solubility of 500 ppm or less at 20°C. (A) Agrochemical active ingredients are active ingredients of agents, such as insecticides, fungicides, herbicides, rodenticides, and plant growth regulators, which are applied to control pests in the agricultural and horticultural fields. Agrochemical active ingredients selected from insecticides, fungicides and herbicides are preferred.

(A) Active ingredients of insecticides applied as agricultural chemical active ingredients include, for example, the following.
cyanophos, fenthion, fenitrothion, pyrimifostil, diazinon, isoxathion, chlorpyrifos, marathon, phenthate, ethylthiomethone, fosarone, methidathion, prothiophos, propenophos, EPN, carbaryl, isoprocarb, fenocarb, carbosulfan, benfuracarb, thiodicarb, alanicarb, pyrethrin, allethrin, permethrin, cyfluthrin, tralomethrin, fenpropathrin, bifenthrin, fenvalerate, flucythrinate, fluvalinate, acrinathrin, cycloprothrin, tefluthrin, etofenprox, silafluofen, bensultap, imidacloprid, thiacloprid, clothianidin, flubendiamide, chlorantrani Riprole, cyantraniliprole, fipronil, ethiprole, emamectin benzoate, milbemectin, lepimectin, abamectin, spinosad, spinetoram, diflubenzuron, teflubenzuron, lufenuron, flufenoxuron, chlorfluazuron, novaluron, tebufenozide, chromafenozide, methoxyfenozide, pyriproxyfen, buprofezin, pymetrozine, pyrifluquinazone, pyridalyl, chlorfenapyr, tolfenpyrad, diafenthiuron, metaflumizone, indoxacarb, metaldehyde, propargite (BPPS), amitraz, phenothiocarb, hexythiazox, fenbutatin oxide, dienochlor, fenpyroximate, tebufenpyrad, pyridaben, pyrimidifen, clofentezine, ethoxazole, bifenazate, acequinosyl, cyenopyrafen, piflubumide, fluacrypyrim, spirodiclofen, spirotetramat, spiromesifen, cyflumetofen, cassafos, nemadectin, cypermethrin, flometkin.
Preferably, cyanophos, fenthion, fenitrothion, pyrimifostil, diazinon, isoxathion, chlorpyrifos, marathonfenthate, ethylthiomethone, fosarone, methidathion, prothiophos, propenophos, EPN organophosphorus insecticides, carbaryl, isoprocarb, fenocarb, carbosulfan, benfuracarb, Thiodicarb, alanicarb carbamate insecticides, pyrethrins, allethrin, permethrin, cyfluthrin, tralomethrin, fenpropathrin, bifenthrin, fenvalerate, flucythrinate, fluvalinate, acrinathrin, cycloprothrin, tefluthrin, etofenprox, silafluofen pyrethroids neonicotinoid insecticides such as imidacloprid, thiacloprid and clothianidin; phenylpyrazole insecticides such as fipronil and ethiprole; spinosad and spinosyn insecticides such as spinetoram; Insect behavior control agents, acaricides such as propargite (BPPS), and insecticides such as chlorfenapyr, indoxacarb, cypermethrin, flometkin.
Preferably, among the above insecticides, the water solubility at 20° C. is from 0.001 ppm to 200 ppm. Pyrethroid insecticides such as thrin; neonicotinoid insecticides such as thiacloprid and clothianidin; phenylpyrazole insecticides such as fipronil; spinosyn insecticides such as spinosad; Control agents, acaricides such as propargite (BPPS), chlorfenapyr, indoxacarb, cypermethrin, flometoquine.
More preferred are diazinon, prothiophos, benfuracarb, fluvalinate, cycloprothrin, thiacloprid, fipronil, spinosad, chromafenozide, pyrifluquinazone, propargite (BPPS), chlorfenapyr, indoxacarb, cypermethrin, and flometkin.

Examples of agrochemical active ingredients selected as fungicides are as follows.
Basic copper chloride, cupric hydroxide, organic copper, ziram, maneb, mancozeb, thiuram, propineb, iprobenfos, tolclofos-methyl, furaside, tricyclazole, carpropamide, diclocimet, phenoxanyl, benomyl, thiophanate-methyl, diethofencarb, iprodione, procymidone, mepronil , flutolanil, boscalid, fluopicolide, fluopyram, furametpyr, penflufen, fluxapyroxad, thifluzamide, penthiopyrad, ethaboxam, fenhexamide, fenpyrazamine, cyflufenamide, mandipropamide, thiazinyl, isotianil, trifoline, fenarimol, oxpoconazole fumarate, pefurazoate, prochloraz, triflumizole, bitertanol, cyproconazole, difenoconazole, fenbuconazole, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanil, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, azoxy strobin, cresoxime methyl, trifloxystrobin, metominostrobin, orysastrobin, pyraclostrobin, pyribencarb, famoxadone, fenamidone, mepanipyrim, cyprodinil, fursulfamide, cymoxanil, iminoctadine albesilate, isoplatiolane, fluorimide, penciclon, fludioxonil, cyazofamide , flutianil, amisulbrom, chlorothalonil, pyriophenone, fluazinam, diflumetrim, ferimzone, dimethomorph, captan, benthiavalicarbisopropyl, probenazole, amethoctrazine, tebufloquine, oxolinic acid, quinoxaline series, dithianone.
Preferably, organic sulfur fungicides such as ziram, maneb, manzeb, thiuram and propineb; organic phosphorus fungicides such as iprobenfos and tolclofos-methyl; benomyl, thiophanate-methyl, benzimidazole fungicides such as diethofencarb; Amide fungicides such as carboximide fungicides, mepronil, flutolanil, boscalid, fluopicolide, fluopyram, furametpyr, penflufen, fluxapyroxad, thifluzamide, penthiopyrad, ethaboxam, fenhexamide, fenpyrazamine, cyflufenamide, mandipropamide, thiazinyl, isotianil , azoxystrobin, cresoxime methyl, trifloxystrobin, metminostrobin, orysastrobin, pyraclostrobin, pyribencarb, famoxadone, strobilurin fungicides such as fenamidone, mepanipyrim, anilinopyrimidine fungicides such as cyprodinil. .
Among the above, it is more preferable to apply a fungicide with a water solubility of 0.001 ppm to 200 ppm

Agrochemical active ingredients selected as herbicides are, for example, as follows.
MCPA, MCPB ethyl, mecoprop, mecoprop P, triclopyr, clomeprop, cyhalofop-butyl, fluazifop, fluazifop-P-butyl, quizalofop-ethyl, metamifop, chlorpropham, fenmedifam, desmedifam, benchocarb, prosulfocarb, esprocarb, molinate, piributicarb, alachlor, pretilachlor, metolachlor, S-metolachlor, butachlor, thenylchlor, flufenacet, bromobutide, etobenzanide, diflufenican, mefenacet, napropamide, caffenstrol, ipfencarbazone, propyzamide, isoxaben, flupoxam, diuron, linuron, daimuron, cumyluron, carbyrate, isouron, bensulfuron-methyl, ethoxysulfuron-ethyl, pyrazosulfuron-ethyl, azimsulfuron, metazosulfuron, halosulfuron-methyl, nicosulfuron, rimsulfuron, thifensulfuron-methyl, propyrisulfuron, Cyclosulfamuron, chlorimuron ethyl, flucetosulfuron, pyriftalide, pyriminobacmethyl, florasulam, simazine, atrazine, cyanazine, simetryne, dimethamethrin, prometryn, indaziflam, triaziflam, terbacil, bromacil, renacil, chloridazone, bentazone, pyrazolate , pyrazoxifene, trifluralin, bethlodin, prodiamine, pendimethalin, oryzaline, imazaquin, dichlobenil, chlorthiamid, ioxynil, sethoxydim, chlorphthalim, flumioxazin, mesotrione, benzobicyclone, dithiopyr, quinocramine, butamiphos, indanophan, benfuresate, pyroxasulfone , pentoxazone, phenoxasulfone, pyraclonil, pyraflufen-ethyl, carfentrazone-ethyl, oxadiazone, oxadiargyl, oxadichromefone, fluthiacet-methyl, fentrazamide, d-limonene.
Preferably, MCPA, MCPB ethyl, mecoprop, mecoprop P, triclopyr, clomeprop, cyhalofop-butyl, fluazifop, fluazifop-P-butyl, quizalofop-ethyl, metamifop, and other phenoxy acid herbicides, chlorpropham, fenmedifam, Carbamate herbicides such as desmedifam, bentiocarb, prosulfocarb, esprocarb, molinate, and piributicarb, alachlor, pretilachlor, metolachlor, S-metolachlor, butachlor, thenylchlor, flufenacet, bromobutide, etobenzanide, diflufenican, mefenacet , napropamide, caffenstrol, ipfencarbazone, propyzamide, isoxaben, flupoxam and other amide herbicides, diuron, linuron, daimuron, cumyluron, carbyrate, isouron and other urea herbicides, bensulfuron-methyl, ethoxysulfuron, pyrazos sulfonylurea herbicides such as rufuron-ethyl, azimsulfuron, metazosulfuron, halosulfuron-methyl, nicosulfuron, rimsulfuron, thifensulfuron-methyl, propyrisulfuron, cyclosulfamuron, chlorimuron-ethyl, flucetosulfuron, simazine, triazine herbicides such as atrazine, cyanazine, simetryn, dimethamethrin, prometryn, indaziflam, and triazifuram; diazine herbicides such as terbasil, bromacil, renacil, chloridazone, and bentazone; Dinitroaniline herbicides such as prodiamine, pendimethalin and oryzaline; nitrile herbicides such as dichlobenil, chlorthiamid and ioxynil; phenylphthalimide herbicides such as chlorphthalim and flumioxazine; triketone herbicides such as mesotrione and benzobicyclone. agents.
Among the above, it is more preferable to apply a herbicide having a water solubility of 0.001 ppm to 200 ppm at 20°C.

In the composition of the present invention, (A) the agricultural chemical active ingredient is preferably contained in an amount of 0.1 to 60% by mass, more preferably 0.5 to 50% by mass.
In the present invention, (A) the pesticidal active ingredient is not particularly limited as long as it is a slightly water-soluble active ingredient with a water solubility of 500 ppm or less at 20°C, whether it is liquid or solid at 20°C under normal pressure. can be applied. When an agriculturally active ingredient that is liquid at 20° C. under normal pressure is used, it is preferably contained in an amount of 0.1 to 60% by mass, more preferably 1 to 50% by mass, in the composition of the present invention. On the other hand, when an agriculturally active ingredient that is solid at 20° C. under normal pressure is used, it is preferably contained in the composition of the present invention in an amount of 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

The (B) surfactant of the composition of the present invention is selected from the group consisting of (b1) styrene maleic acid-polyoxyalkylene graft copolymer, (b2) polyoxyalkylene-(poly)styrylphenyl ether, and formaldehyde condensates thereof. one or more of the following apply.
(b1) In the styrene maleic acid-polyoxyalkylene graft copolymer, the polyoxyalkylene portion is any one of a polyoxyethylene polymer, a polyoxypropylene polymer, and a polyoxyethylene-polyoxypropylene copolymer, and the polyoxyalkylene portion is It is a graft copolymer in which one or more are bonded to the carbonyl group of styrene maleic acid. As the (b1) styrene-maleic acid-polyoxyalkylene graft copolymer, a commercially available one can be applied, for example, TERSPERSE 2612 (trade name, manufactured by INDRAMA).
(b1) preferably has an HLB value of 10-19, more preferably 12-19.
Note that HLB (Hydrophile-Lipophile Balance) is an index representing the degree of hydrophilicity and lipophilicity of a surfactant and is represented by a numerical value from 0 to 20. HLB in the present specification is represented by the following formula based on the formula weight and molecular weight of the hydrophilic group.
HLB value = 20 x (mass% of hydrophilic group)

As surfactant (b2), polyoxyalkylene-(poly)styrylphenyl ether or its formaldehyde condensate can be applied. That is, it is a polymerized nonionic surfactant in which a polyoxyalkylene group and a (poly)styrylphenyl group are ether-bonded. (b2) also includes a formaldehyde-condensed product. The (poly)styrylphenyl group in the surfactant (b2) is styrylphenyl, distyrylphenyl or tristyrylphenyl. Examples include polyoxyethylene-tristyrylphenyl ether, polyoxyalkylene-tristyrylphenyl ether and the like. Further, the polyoxyalkylene portion preferably has a polymerization number of 10 to 20.
(b2) preferably has an HLB value of 8-18, more preferably 10-16.

As the surfactant (b2), a commercially available polyoxyalkylene-(poly)styrylphenyl ether can be applied. ), Solpol T-15 (trade name Toho Chemical Co., Ltd. HLB12 (catalog value)), Solpol T-20 (trade name Toho Chemical Co., Ltd. HLB13.3 (catalog value)), Solpol T-26 (trade name Toho Chemical Co., Ltd.) Company HLB 14.4 (catalog value)), Solpol T-32 (trade name Toho Chemical Co., Ltd. HLB 15.2 (catalog value)), Nucalgen C-120 (trade name Takemoto Oil Co., Ltd. HLB 10.9 (catalog value)) , Nucalgen C-150 (trade name: Takemoto Oil Co., Ltd. HLB12 (catalog value)), Nucalgen C-200 (trade name: Takemoto Oil Co., Ltd. HLB13.3 (catalog value)), Nucalgen C-314 (trade name: Takemoto Oils and Fats Co., Ltd. HLB15.2 (catalog value)), Nucalgen CP-50 (Takemoto Oil & Fat Co., Ltd. HLB11 (catalog value)), Nucalgen CP-80 (trade name Takemoto Oil & Fat Co., Ltd. HLB12 (catalog value)), Nucalgen CP-120 (trade name: Takemoto Oil Co., Ltd. HLB13.2 (catalog value)), Nucalgen CP-150 (trade name: Takemoto Oil Co., Ltd. HLB14 (catalog value)), Nucalgen CP-15-150 (trade name: Takemoto Oil) Co., Ltd. HLB14.5 (catalog value)), Nucalgen CP-15-200 (trade name Takemoto Oil Co., Ltd.), Nucalgen FS-1 (trade name Takemoto Oil Co., Ltd.), Pionin D-6112 (trade name Takemoto Oil) Co., Ltd.), Pionin D-6115 (trade name: Takemoto Oil Co., Ltd.), Pionin D-6120 (trade name: Takemoto Oil Co., Ltd.), Pionin D-6131 (trade name: Takemoto Oil Co., Ltd.), Pionin D-6105-W (trade name: Takemoto Oil Co., Ltd.) Trade name: Takemoto Oil Co., Ltd.), Pionin 6108-W (trade name: Takemoto Oil Co., Ltd.), Pionin 6112-W (trade name: Takemoto Oil Co., Ltd.), Pionin 6120-X (trade name: Takemoto Oil Co., Ltd.), Pionin 6512 (trade name: Takemoto Oil & Fat Co., Ltd.) (trade name: Takemoto Oil Co., Ltd.), Takesurf D-6413 (trade name: Takemoto Oil & Fat Co., Ltd.), Pionin D-6414 (trade name: Takemoto Oil & Fat Co., Ltd.), and DTD-51 (trade name: Takemoto Oil & Fat Co., Ltd.) can be used. .

The formaldehyde condensate of polyoxyalkylene-(poly)styrylphenyl ether in (b2) preferably has an HLB of 9-16, more preferably 10-14. A commercially available product may be used, for example, Solpol 3080 (trade name, Toho Chemical Co., Ltd.).

The (B) surfactant in the composition of the present invention is characterized by containing at least the same mass as the (A) agricultural chemical active ingredient, and the mass content ratio of (A) the agricultural chemical active ingredient and (B) the surfactant is 1:1 to 100. Preferably, (A):(B) is 1:1-80. When (A) the pesticidal active ingredient is liquid at 20° C. under normal pressure, the ratio of (A):(B) is preferably 1:1 to 100, more preferably 1:1 to 50. . On the other hand, when (A) the pesticide active ingredient is a solid component at 20° C. under normal pressure, (A):(B) is preferably applied at a ratio of 1:1 to 100, more preferably 1:5 to 100. .
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. (A) When a pesticidal active ingredient is liquid at 20° C. under normal pressure, (B) a surfactant is preferably contained in an amount of 10 to 90% by mass, more preferably 30 to 90% by mass. Further, when (A) the pesticidal active ingredient is a solid component at 20° C. under normal pressure, (B) the surfactant is preferably contained in an amount of 10 to 90% by mass, more preferably 30 to 90% by mass. .

In addition to the above (b1) and (b2), any other surfactant (b3) can be included in combination. Examples thereof include nonionic surfactants, anionic surfactants, nonionic anionic surfactants, cationic surfactants and amphoteric surfactants.
Nonionic surfactants include polyoxyethylene-alkyl ethers, polyoxyethylene-alkylaryl ethers, polyoxyethylene-alkylphenol formalin condensates, polyoxyethylene-castor oil derivatives, polyoxyethylene-fatty acid esters, higher fatty acid glycerin esters. , polyoxyethylene-fatty acid amides, alkylolamides, polyoxyethylene-fatty acid esters, polyoxyethylene-sorbitol fatty acid esters, polyoxyethylene-sorbitan fatty acid esters, polyoxyethylene-polyoxypropylene block polymers, sucrose fatty acid esters, poly Glycerin fatty acid ester and the like are included. Polyoxyethylene-sorbitan fatty acid esters are preferred.
Examples of anionic include dioctylsulfosuccinate sodium salt, alkylnaphthalenesulfonate formaldehyde condensate sodium salt, ligninsulfonate sodium salt, alkylbenzenesulfonate sodium salt, laurylsulfate sodium salt, polycarboxylic acid sodium salt, and the like. Dioctyl sulfosuccinate sodium salt is preferably included.
Nonionic anionic surfactants include polyoxyalkylene-lauryl ether sulfate ammonium salt, polyoxyalkylene-lauryl sulfate ammonium salt, polyoxyethylene-lauryl ether sulfate sodium salt, polyoxyethylene-alkyl ether sodium sulfate, poly oxyalkylene-tristyrylphenyl ether sulfate ammonium salt, polyoxyethylene-allylphenyl ether sulfate ester amine salt, polyoxyalkylene-allylphenyl ether sulfate ammonium salt and the like.
Cationic surfactants include alkyltrimethylammonium chloride, methylpolyoxyethylene alkylammonium chloride, alkyl N-methylpyridinium bromide, monomethylated ammonium chloride, dialkylmethylated ammonium chloride, alkylpentamethylpropyleneamine dichloride, alkyldimethylbenzalco. nium chloride, benzethonium chloride and the like.
Examples of amphoteric surfactants include dialkyldiaminoethylpentine, alkyldimethylbenzylpentine and the like.

In the present invention, (A) the pesticidal active ingredient is not particularly limited as long as it is a slightly water-soluble active ingredient with a water solubility of 500 ppm or less at 20°C, whether it is liquid or solid at 20°C under normal pressure. However, when using an agrochemically active ingredient that is solid at 20° C. under normal pressure, it is contained in a dissolved state in the composition of the present invention. Therefore, when using a solid agricultural chemical active ingredient, it is preferable to use (C) a solvent. The solvent (C) is preferably a solvent that can dissolve the pesticidal active ingredient in combination with the surfactant (B) and is miscible with water at any ratio. For example, solvents for 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 and the like can be mentioned, and these can be used singly or in combination of two or more. More preferred solvents include methanol, acetone, cyclohexanone, N,N-dimethylformamide, diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether, more preferably methanol, acetone, cyclohexanone, N,N-dimethylformamide and diethylene glycol. and monoethyl ether.
The amount of the solvent to be added may be sufficient to dissolve the active ingredient of the agricultural chemical, and it is preferably twice or more by mass the active ingredient of the agricultural chemical. Further, when the composition of the present invention is used, it is more preferably 2 to 100 times, particularly preferably 2 to 50 times, in consideration of ease of use and cost.
(C) When a solvent is used, it is preferably contained in an amount of 1 to 60% by mass in the composition of the present invention.

The composition of the present invention preferably contains a rosin compound (D). Rosin is obtained by collecting pine resin, which is the sap of plants of the pine family, and distilling turpentine essential oil, and is a natural resin mainly composed of abietic acid, parastric acid, and the like. Rosin compounds obtained by reacting rosin with other chemicals have high compatibility properties, and are used as additives for inks, paints, adhesives, and the like. Types of rosin compounds include disproportionated rosin, maleated rosin, gum rosin, tall rosin and the like. The rosin compound in the composition of the present invention has a function of enhancing stability during formulation or dilution and dispersion.
When the rosin compound (D) is used in the composition of the present invention, it is preferably contained in an amount of 0.1 to 10% by mass, more preferably 0.5 to 10% by mass.

Additives used in agricultural chemical formulations can optionally be added to the composition of the present invention. Additives include, for example, stabilizers, thickeners, antifoaming agents and the like, and one or more of each can be used.
Examples of stabilizers include quenchers, radical scavengers, ultraviolet absorbers, antioxidants, and the like. Examples of quenchers include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl, epoxidized fatty acid butyl, epoxidized fatty acid methyl, and epoxidized rapeseed oil. Radical scavengers include vitamin E, vitamin C, ubiquinol, uric acid, flavonoids, tannins, sesaminol, curcumin and the like. Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers. Examples of antioxidants include phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
Examples of thickeners 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 a flexible polymer.
Antifoaming agents include silicone-based emulsions and the like.

In the present invention, the content of each component is important in order to disperse the formulation at the nano level when diluted with water. The higher the content of the agricultural chemical active ingredient, the larger the particles when diluted with water. On the other hand, the higher the surfactant content, the smaller the particles when diluted with water, and the particle size is stable for a long period of time.
The composition of the present invention is preferably a liquid agricultural chemical composition containing (A) 1 to 60% by mass of an agricultural chemical active ingredient, (B) 10 to 90% by mass of a surfactant, and (C) 0 to 60% by mass of a solvent. . More preferably, (A) 0.5 to 50% by mass of an agrochemical active ingredient, (B) 30 to 96% by mass of a surfactant, and (C) 0 to 60% by mass of a solvent.

The method for producing the composition of the present invention is not particularly limited, but for example, it can be prepared by mixing (A) an agriculturally active ingredient, (B) a surfactant, and an arbitrary (C) solvent to form a uniform solution. . Alternatively, it can be prepared by a method of adding (B) a surfactant to a homogenized solution obtained by mixing (A) an agricultural chemical active ingredient and (C) a solvent and mixing them.

It is preferable to dilute the composition of the present invention with water and apply it to target plants or soil. In this case, the dilution ratio of the composition of the present invention with respect to water is preferably 10 times or more, more preferably 100 times or more.

By diluting the composition of the present invention with water, (A) a dispersion liquid in which the pesticidal active ingredient is micronized to a nanoparticle level is prepared. The particles here are particles of a hydrophobic component containing an agriculturally active ingredient dispersed in water, and the size thereof is referred to as the particle size. In addition, nanoparticles refer to particles having a particle diameter of 100 nm or less.
As used herein, the term "particle size" refers to the median value of the distribution of 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.
The aqueous dispersion of the composition of the present invention is a nanoparticle dispersion having a particle size of 50 nm or less. More preferably, a nanoparticle dispersion of 20 nm or less can be prepared. In order to fully exhibit the effect of the nanoparticulate dispersion liquid as an agricultural chemical spray liquid, it is desirable that the particle size is maintained for a long time. The nanoparticle dispersion obtained from the composition of the present invention can maintain its particle size for 24 hours or more. More preferably, the particle size can be maintained for 48 hours or longer.

A dynamic light scattering method is used as a method for measuring the particle size of the aqueous dispersion of the composition of the present invention. The particle diameter referred to here is the diameter of the particles to be measured, and means the median diameter of the volume distribution of the measured particles. Examples of measuring instruments include Nanotrac Wave2 (manufactured by Microtrack Bell Co., Ltd., measurable range: 0.8 to 6500 nm).

The following examples further illustrate the invention.
(1) Preparation of liquid agricultural chemical composition Agricultural active ingredient (A), surfactant (B... b1 and / or b2, and optional b3), and optional component solvent (C... when multiple types are used are represented as C1, C2, etc.) and the rosin compound (D) were uniformly mixed and prepared.
(2) Measurement of particle size of aqueous dispersion of liquid pesticide composition (a) Analysis sample 0.1 mL of the prepared liquid pesticide composition was sampled and mixed with 10 mL of water to obtain a solution, which was used as a particle size measurement sample. did.
(b) Analysis equipment/measurement conditions Equipment: Nanotrac Wave2 (Microtrac Bell Co., Ltd.)
Measurement conditions: The median diameter of the diluted solution was measured by volume distribution.
Measurement time: 60 seconds Number of measurements: 3 Particle permeability: Permeation

[Example 1]
A: Chromafenozide ... 1.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (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 a liquid agricultural chemical composition of Example 1.
An aqueous dispersion obtained by adding and mixing 0.1 mL of the liquid agricultural chemical composition of Example 1 to 10 mL of water was a particle dispersion having a particle diameter of 8 nm.

[Example 2]
A: Chromafenozide...1.0 parts by mass b2: A mixture of polyoxyethylene-distyrylphenyl ether formaldehyde condensate and dodecylbenzenesulfonate (Solpol 3080 (trade name, manufactured by Toho Chemical Co., Ltd.))...50.0 parts by mass Part 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 a liquid agricultural chemical composition of Example 2.
An aqueous dispersion obtained by adding and mixing 0.1 mL of the liquid agricultural chemical composition of Example 2 to 10 mL of water was a particle dispersion having a particle diameter of 4.8 nm.

[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 a liquid agricultural chemical composition of Example 3.
0.1 mL of the liquid pesticidal composition of Example 3 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 7.4 nm.

[Example 4]
A: Chromafenozide...1.0 parts by mass b2: Polyoxyethylene-styrylphenyl ether (Nucalgen C-150 (trade name, manufactured by Takemoto Yushi 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 a liquid agricultural chemical composition of Example 4.
0.1 mL of the liquid pesticidal composition of Example 4 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 16 nm.

[Example 5]
A: Chromafenozide...1.0 parts by mass b2: Polyoxyethylene-styrylphenyl ether (Nucalgen CP-120 (trade name, manufactured by Takemoto Yushi 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 a liquid agricultural chemical 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 having a particle diameter of 6.7 nm.

[Example 6]
A: Chromafenozide...5.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) 80.0 parts by mass C1: methanol 10.0 parts by mass D: disproportionated rosin (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.)) 5.0 parts by mass The liquid pesticide composition of Example 6 was prepared by mixing uniformly.
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 having a particle diameter of 14 nm.

[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: Poly Oxyethylene-sorbitan laurate (Sorbon T-20 (trade name, manufactured by Toho Chemical Co., Ltd.)): 10.0%
C1: Methanol...10.0 parts by mass D: Disproportionated rosin (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.))...5.0 parts by mass 7 liquid pesticide compositions were prepared.
0.1 mL of the liquid pesticidal composition of Example 7 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 11 nm.

[Example 8]
A: Flometkin ... 1.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) 96.0 parts by mass C1: Cyclohexanone 2.0 parts by mass D: Disproportionated rosin (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.)) 1.0 parts by mass They were uniformly mixed to prepare a liquid agricultural chemical composition of Example 8.
0.1 mL of the liquid pesticidal composition of Example 8 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 12 nm.

[Example 9]
A: Flometkin...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: Poly Oxyethylene (20)-sorbitan laurate (Sorbon T-20 (trade name, manufactured by Toho Chemical Co., Ltd.)): 46.0%
C1: Cyclohexanone...2.0 parts by mass D: Disproportionated rosin (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.))...1.0 parts by mass Nine liquid pesticide compositions were prepared.
0.1 mL of the liquid pesticidal composition of Example 9 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 8.5 nm.

[Example 10]
A: Chlorfenapyr ... 1.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (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 a liquid agricultural chemical composition of Example 10.
0.1 mL of the liquid pesticidal composition of Example 10 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion with a particle diameter of 11 nm.

[Example 11]
A: Thiacloprid...1.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA))) 96.0 parts by mass C1: N,N-dimethylformamide 3.0 parts by mass The above ingredients were uniformly mixed to prepare a liquid agricultural chemical composition of Example 11.
0.1 mL of the liquid pesticidal composition of Example 11 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 8.7 nm.

[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: Poly Oxyethylene (20)-sorbitan laurate (Sorbon T-20 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 35.0%
C1: N,N-dimethylformamide...15.0 parts by mass D: Disproportionated rosin (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.))...5.0 parts by mass Uniformly By mixing, the liquid pesticide composition of Example 12 was prepared.
0.1 mL of the liquid pesticide composition of Example 12 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 10 nm.

[Example 13]
A: fipronil 1.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) 96.0 parts by mass C1: Acetone 2.0 parts by mass D: Disproportionated rosin (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.)) 1.0 parts by mass They were uniformly mixed to prepare a liquid agricultural chemical composition of Example 13.
0.1 mL of the liquid pesticidal composition of Example 13 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 13 nm.

[Example 14]
A: Fipronil...5.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)...・ 80.0 parts by mass C1: acetone 10.0 parts by mass D: disproportionated rosin (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.)) 5.0 parts by mass Uniformly to prepare a liquid agricultural chemical composition of Example 14.
0.1 mL of the liquid pesticidal composition of Example 14 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 15 nm.

[Example 15]
A: Spinosad...5.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) 80.0 parts by mass C1: Cyclohexanone 10.0 parts by mass D: Disproportionated rosin (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.)) 5.0 parts by mass They were uniformly mixed to prepare a liquid agricultural chemical composition of Example 15.
0.1 mL of the liquid pesticidal composition of Example 15 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 8 nm.

[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 (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.)) ... 5.0 parts by mass The above components were uniformly mixed, and the liquid of Example 16 A pesticide composition was prepared.
0.1 mL of the liquid pesticidal composition of Example 16 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 16 nm.

[Example 17]
A: Pyrifluquinazone 5.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) 80.0 parts by mass C1: Cyclohexanone 10.0 parts by mass D: Disproportionated rosin (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.)) 5.0 parts by mass They were uniformly mixed to prepare a liquid agricultural chemical composition of Example 17.
0.1 mL of the liquid pesticidal composition of Example 17 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 13 nm.

[Example 18]
A: Indoxacarb 1.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) )...95.0 parts by mass C1: Cyclohexanone...4.0 parts by mass The above ingredients were uniformly mixed to prepare a liquid agricultural chemical composition of Example 18.
0.1 mL of the liquid pesticidal composition of Example 18 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 7.6 nm.

[Example 19]
A: Diazinon...20.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)... · 80.0 parts by mass The above components were uniformly mixed to prepare a liquid agricultural chemical composition of Example 19.
0.1 mL of the liquid pesticidal composition of Example 19 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 14 nm.

[Example 20]
A: Diazinon...20.0 parts by mass b2: A mixture of polyoxyethylene-distyrylphenyl ether formaldehyde condensate and dodecylbenzenesulfonate (Solpol 3080 (trade name, manufactured by Toho Chemical Co., Ltd.))...80.0 parts by mass Part The above components were uniformly mixed to prepare a liquid agricultural chemical composition of Example 20.
0.1 mL of the liquid pesticidal composition of Example 20 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 1.8 nm.

[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 They were uniformly mixed to prepare a liquid agricultural chemical composition of Example 21.
0.1 mL of the liquid pesticide composition of Example 21 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 18 nm.

[Example 22]
A: Diazinon...50.0 parts by mass b2: Polyoxyalkylene-styrylphenyl ether (Nucalgen CP-120 (trade name, manufactured by Takemoto Yushi Co., Ltd.))...50.0 parts by mass Uniformly mixing the above components Then, the liquid agricultural chemical composition of Example 22 was prepared.
0.1 mL of the liquid pesticidal composition of Example 22 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 20 nm.

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

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

[Example 25]
A: Prothiophos...10.0 parts by mass b2: Polyoxyalkylene-styrylphenyl ether (Nucalgen CP-120 (trade name, manufactured by Takemoto Yushi Co., Ltd.))...36.0 parts by mass b3: Sodium dialkyl sulfosuccinate (Nucalgen EP-70G (trade 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, and the liquid pesticide composition of Example 25 was prepared. prepared the product.
0.1 mL of the liquid pesticidal composition of Example 25 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 4.6 nm.

[Example 26]
A: Cycloprothrin...10.0 parts by mass b1 and C1: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) )...90.0 parts by mass The above ingredients were uniformly mixed to prepare a liquid agricultural chemical composition of Example 26.
0.1 mL of the liquid pesticidal composition of Example 26 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 6.1 nm.

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

[Example 28]
A: Fluvalinate...10.0 parts by mass b1 and C1: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) ...90.0 parts by mass The above ingredients were uniformly mixed to prepare a liquid agricultural chemical composition of Example 28.
0.1 mL of the liquid pesticidal composition of Example 28 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 6.3 nm.

[Example 29]
A: Fluvalinate...10.0 parts by mass b2: Polyoxyalkylene-styrylphenyl ether (Nucalgen CP-120 (trade name, manufactured by Takemoto Yushi Co., Ltd.))...36.0 parts by mass b2: Dialkyl sulfosuccinic acid Sodium (Nucalgen EP-70G (trade name, manufactured by Takemoto Oil Co., Ltd.)) ... 24.0 parts by mass C1: Cyclohexanone ... 30.0 parts by mass The above ingredients are uniformly mixed, and the liquid pesticide of Example 29 A composition was prepared.
0.1 mL of the liquid pesticidal composition of Example 29 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle diameter of 5.1 nm.

[Example 30]
A: Propargite (BPPS) ... 10.0 parts by mass b1 and C1: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA) ))...90.0 parts by mass The above components were uniformly mixed to prepare a liquid agricultural chemical composition of Example 30.
0.1 mL of the liquid pesticidal composition of Example 30 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 11 nm.

[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 part by mass C2: Dipropylene glycol monomethyl ether...47.0 parts by mass The above components were uniformly mixed to prepare a liquid agricultural chemical composition of Comparative Example 1.
0.1 mL of the liquid pesticide composition of Comparative Example 1 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle diameter of 2884 nm.

[Comparative Example 2]
A: Chromafenozide ... 1.0 parts by mass B: Polyoxyethylene-oleic acid 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 ingredients were uniformly mixed to prepare a liquid agricultural chemical composition of Comparative Example 2.
0.1 mL of the liquid pesticide composition of Comparative Example 2 was added to 10 mL of water, and the mixed aqueous dispersion was a particle dispersion having a particle diameter of 256 nm.

[Comparative Example 3]
A: Chromafenozide...1.0 parts by mass B: Polyoxyethylene-sorbitan trioleate (Sorbon T-85 (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 a liquid pesticide composition of Comparative Example 3.
0.1 mL of the liquid pesticide composition of Comparative Example 3 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion having a particle diameter of 472 nm.

[Comparative Example 4]
A: Chromafenozide...1.0 parts by mass B: Dialkyl sulfosuccinate (Nucalgen EP60P (trade name, manufactured by Takemoto Yushi 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 a liquid agricultural chemical composition of Comparative Example 4.
0.1 mL of the liquid pesticide composition of Comparative Example 4 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle diameter of 3914 nm.

[Comparative Example 5]
A: Chromafenozide...1.0 parts by mass B: Sodium alkylbenzenesulfonate (Nucalgen A-41-B (trade name, manufactured by Takemoto Oil & Fat 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 a liquid agricultural chemical composition of Comparative Example 5.
0.1 mL of the liquid pesticide composition of Comparative Example 5 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle diameter of 3155 nm.

[Comparative Example 6]
A: Chromafenozide...10.0 parts by mass b1 and C2: 50% dipropylene glycol monoethyl ether solution of styrene maleic acid-polyoxyethylene polyoxypropylene graft copolymer (TERSPERSE 2612 (trade name, manufactured by INDORAMA)) 2.0 parts by mass C1: methanol 78.0 parts by mass D: disproportionated rosin (Diplosin A-100 (trade name, manufactured by Toho Chemical Co., Ltd.)) 10.0 parts by mass They were uniformly mixed to prepare a liquid agricultural chemical composition of Comparative Example 6.
0.1 mL of the liquid pesticide composition of Comparative Example 6 was added to 10 mL of water, and the resulting aqueous dispersion was a particle dispersion with a particle diameter of 161 nm.

[Test Example 1] Aqueous dispersion stability test The liquid agricultural chemical compositions of Examples 1 to 30 and Comparative Examples 1 to 6 were added to water in a test tube so as to be 100-fold diluted and mixed. The particle size distribution of the diluted solution was measured immediately after mixing and every day after standing, and the number of days for which the particle size remained unchanged from immediately after dilution was confirmed.
Tables 1-1 to 1-4 show the particle size immediately after dilution and the number of days the initial particle size was maintained. Each of the liquid pesticide compositions of Examples 1 to 30 according to the composition of the present invention is a fine nanoparticle dispersion having a particle size of 20 nm or less immediately after preparation of the aqueous dispersion, and the nanoparticle dispersion is maintained for at least one day. It was a stable physical property maintained above. On the other hand, the liquid agricultural chemical composition according to the comparative example could not be prepared into a nanoparticle dispersion of about 20 nm by the water mixing operation, and the stability of the dispersion was poor.

[Table 1-1]

[Table 1-2]

[Table 1-3]

（＊１）ＴＥＲＳＰＥＲＳＥ ２６１２；スチレンマレイン酸‐ポリオキシエチレンポリオキシプロピレンコポリマー５０％を含むジプロピレングリコールモノエチルエーテル（ＤＰＧＭＥ）溶液
（＊２）ＤＰＧＭＥ；ジプロピレングリコールモノエチルエーテル
（＊３）ＤＰＧＭＭ；ジプロピレングリコールモノメチルエーテル [Table 1-4]

(*1) TERSPERSE 2612; dipropylene glycol monoethyl ether (DPGME) solution containing 50% styrene maleic acid-polyoxyethylene polyoxypropylene copolymer (*2) DPGME; dipropylene glycol monoethyl ether (*3) DPGMM; Dipropylene glycol monomethyl ether

[Test Example 2] Systemic migration test The systemic migration of the liquid pesticide composition of Example 1 into the plant body was evaluated using an existing formulation (matrix flowable (trade name: Nippon Kayaku Co., Ltd.) containing the same pesticide active ingredient (chromafenozide). marketed)) was tested as a control agent.
As a test sample, a dispersion obtained by adding 1 mL of the preparation of Example 1 to 99 mL of tap water and mixing was used. As a control agent, a mixture of 0.1 mL of matrix flowable and 99.9 mL of tap water was used.
Radish sprouts were grown in plastic pots through soil. A hole was made in the bottom of the plastic pot so that the chemical solution could permeate from the bottom. A dish filled with 100 mL of each diluted solution was placed under the plastic pot to permeate the chemical solution into the soil.
After cutting the radish sprouts 1 cm above the surface of the soil, 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.
Chromafenozide was not detected in radish sprouts with matric flowable. On the other hand, in Example 1, Chromafenozide was detected 2 days after treatment with the chemical solution, confirming the expression of permeation and transfer properties due to nanoparticulation of the active ingredient. Due to the expression of systemic transfer, the active ingredient can be absorbed from the roots together with moisture in the soil, move to the stems and leaves of the upper layer of the crop, and spread throughout the crop. Therefore, even if the chemical agent is applied unevenly, the active ingredient of the agricultural chemical can be evenly spread over the crop body. In addition, if it has systemic migration properties, it is easy to control pests hiding under the leaves such as aphids and spider mites, pests hidden in the depths of petals, and diseases hidden in the body of crops. .

[Table 2] Penetration test results

[Test Example 3] Confirmation of Soil Adsorption The soil adsorption of the dispersion of the liquid pesticide composition of Example 1 was evaluated using an existing formulation (matrix flowable (trade name: Nippon Kayaku Co., Ltd.) containing the same pesticide active ingredient (chromafenozide). marketed)) was tested as a control agent.
1 mL of the preparation of Example 1 was added to 99 mL of tap water and mixed to prepare a drug solution, which was used as a test sample. On the other hand, 0.1 mL of matrix flowable was added to 99.9 mL of tap water and mixed to prepare a drug solution, which was used as a control agent.
A 5-mL plastic tube was filled with a paper waste cloth, and 5 g of soil sieved through a 2-mL sieve was added to form a simple column. 10 mL of each drug solution was passed through a simple column. The chemical solution after soil filtration was analyzed by high performance liquid chromatography to calculate the active ingredient concentration. The soil adsorption rate was calculated by the following formula.
Soil adsorption rate (%) = 100 × (1-active ingredient concentration after soil filtration/treatment chemical active ingredient concentration)
Test results are presented in Table 3.
The average value of the soil adsorption rate of the matrix flowable diluted solution, which is the control agent, was 73%. On the other hand, the average value of the soil adsorption rate of the diluted solution of Example 1 was 35%, and it was confirmed that the soil adsorption rate was reduced by making the active ingredient into nanoparticles.
If soil adsorption is reduced, it is expected that the chemical agent will be taken up into the plant body more efficiently, which has the advantage of reducing the amount of chemical agent to be used and saving labor.

[Table 3] Soil adsorption test results

Claims (8)

(A) a pesticide active ingredient, and (B) a liquid pesticide composition containing a surfactant,
(A) the agricultural chemical active ingredient is an agricultural chemical active ingredient having 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 formaldehyde condensates thereof and
(A) the pesticidal active ingredient and (B) the surfactant have a mass content ratio of 1:1 to 100;
A liquid pesticide composition. The liquid pesticide composition according to claim 1, which is an emulsion or emulsion. (A) the pesticidal active ingredient is a liquid pesticidal active ingredient at 20° C. under normal pressure;
(A) the pesticidal active ingredient and (B) the surfactant have a mass content ratio of 1:1 to 10;
The liquid agricultural chemical composition according to claim 1 or 2. (A) the agricultural chemical active ingredient is a solid agricultural chemical active ingredient at 20° C. under normal pressure;
(C) contains a solvent;
(A) the pesticidal active ingredient and (B) the surfactant have a mass content ratio of 1:5 to 100;
The liquid agricultural chemical composition according to claim 1 or 2. 5. The liquid agricultural chemical composition according to claim 4, wherein (C) the solvent is 2 to 100 parts by mass per 1 part by mass of the agricultural chemical active ingredient (A). (D) The liquid agricultural chemical composition according to any one of claims 1 to 5, which contains a rosin compound. 7. The liquid pesticide composition according to any one of claims 1 to 6, wherein (A) the particles containing the pesticidal active ingredient in the dispersion diluted 100 times with water have a size of 20 nm or less. An aqueous dispersion containing the liquid agricultural chemical composition according to any one of claims 1 to 7,
(A) particles containing an agrochemical active ingredient are 20 nm or less,
Aqueous dispersion.