JP7590832B2 - Stabilized aqueous suspension pesticide composition, its production method and application method - Google Patents

Description

The present invention relates to a new formulation technology in the field of agricultural chemicals, particularly in herbicides. More specifically, the present invention relates to an aqueous suspension-type agricultural chemical composition in which decomposition of the herbicidal active ingredient is suppressed, and a method for producing and applying the same.

In recent years, the demand for labor-saving spraying of pesticides has increased, leading to an increased demand for low-volume application formulations that reduce the amount of formulation applied, and formulations containing high concentrations of pesticide active ingredients have become mainstream. Against this background, the demand for stability of pesticide active ingredients has further increased in recent years.

Traditionally, the main formulations of pesticides have been wettable powders, water-soluble powders, emulsifiable concentrates, aqueous solutions, and granules. Of these, wettable powders and water-soluble powders have problems such as the impact on worker health due to dusting and diffusion into the environment, while emulsions have problems such as environmental pollution due to solvents and emulsifiers and fires due to organic solvents. In addition, many pesticide active ingredients are poorly soluble in water, making them difficult to formulate into water-soluble formulations. For these reasons, formulations in recent years are being replaced by aqueous suspension pesticide compositions and water-soluble granules, which have fewer such problems.

On the other hand, granules have traditionally been the main form of pesticide formulation for paddy fields. Previously, 3-4 kg of granules were typically applied per 10 ares, but in recent years, in response to the growing demand for labor-saving pesticide spraying, small-volume spray formulations, such as 1 kg granules, which reduce the amount of formulation applied, have become more common.

In the field of paddy field herbicides, aqueous suspension compositions have been developed with the aim of reducing labor and increasing efficiency during spraying. Unlike aqueous suspension compositions used in upland fields and non-agricultural land, this formulation is dripped or poured directly into paddy fields from a container without diluting the formulation, so no special spraying equipment is required. In addition, the treatment volume is small, about 100 milliliters to 1 liter per 10 ares, so it is light and easy to handle. Depending on the area of the field, aqueous suspension compositions can be applied by pouring them from the ridges (so-called frame treatment) or by simply pouring them from a water inlet when water is introduced into the field (so-called water inlet treatment), which is extremely labor-saving and has gained a certain share of the market.

Among pesticide active ingredients, for example, pyrazole-based active ingredients, triketone-based active ingredients, and sulfonylurea-based active ingredients have been widely used because they have control activity against many perennial weeds and broadleaf weeds. However, these active ingredients are relatively unstable in aqueous suspension compositions and often decompose during storage.

For this reason, several methods have been proposed for stabilizing pesticide active ingredients in pesticide formulations. That is, generally, as a measure to suppress the decomposition of pesticide active ingredients, a method of adding an inhibitor for the decomposition of pesticide active ingredients (for example, Patent Document 1) has been proposed. Patent Document 1 describes that in a pesticide composition containing (1) at least one salt selected from the group consisting of sodium sulfate, calcium acetate, and ammonium sulfate, (2) at least one anionic surfactant (wherein the pH at room temperature is 5 or less), (3) hydrochloric acid, and (4) a pesticide active ingredient, the decomposition of the pesticide active ingredient is suppressed in water and a stable suspension state is maintained.

JP 2017-149713 A

In formulations made from pesticide active ingredients that are unlikely to accumulate in the environment, i.e., have low stability, the pesticide active ingredients may decompose over time depending on environmental conditions such as temperature. If excessive decomposition occurs, the formulation may cause a decrease in efficacy or promote phytotoxicity due to the decomposition of the pesticide active ingredients. Furthermore, in formulations where decomposition is significant, it becomes difficult to guarantee the content of the pesticide active ingredients at the expiration date, making commercialization impossible or significantly reducing the commercial value. In particular, in formulations that require pesticide active ingredient content control by median value control, the control range becomes narrower as the pesticide active ingredient content increases, and a pesticide formulation with higher stability is required.

Among pesticide formulations for paddy fields, in the field of herbicides for paddy fields, aqueous suspension compositions are formulations in which pesticide active ingredients are dispersed or emulsified in water. Because these are formulations in which active ingredients that are easily decomposed in water are suspended in water, it is difficult to completely stabilize them, and these technologies cannot avoid a considerable degree of decomposition.

The composition described in Patent Document 1 contains hydrochloric acid and an anionic surfactant with a pH of 5 or less as essential ingredients, which makes the pH of the formulation acidic, posing issues in terms of safety and restrictions on the use of raw materials.
Therefore, an object of the present invention is to obtain an agrochemical composition which does not necessarily require an acidic component and which has excellent stability of the active ingredient.

The present inventors have conducted intensive research to solve the above problems, and as a result have found that in an aqueous suspension pesticide composition containing fine particles containing a herbicidal active ingredient and a salt of an alkylnaphthalenesulfonic acid-formaldehyde condensate and having a volume distribution integrated specific surface area of 80,000 ^cm2 / ^cm3 or more, the decomposition of the herbicidal active ingredient is suppressed and storage stability is improved. In particular, they have found that the storage stability of some herbicidal active ingredients can be improved to such an extent that the decomposition is completely suppressed, and have completed the present invention.
That is, the present invention is as follows.

[1] (1) A fine particle containing at least one herbicidal active ingredient;
(2) a salt of an alkylnaphthalenesulfonic acid-formaldehyde condensate;
Including,
1. An aqueous suspension concentrate pesticide composition having a volume distribution integrated specific surface area of 80,000 cm ² /cm ³ or more.
[2] The pesticidal aqueous suspension concentrate according to [1], wherein the specific surface area is 90,000 cm ² /cm ³ or more.
[3] The pesticidal aqueous suspension concentrate according to [1] or [2], wherein the specific surface area is 100,000 cm ² /cm ³ or more.
[4] The pesticidal aqueous suspension concentrate according to any one of [1] to [3], further comprising (3) a polyoxyethylene (mono-, di-, or tri)styrylphenyl ether phosphate mono- or diester.
[5] The pesticide composition according to any one of [1] to [4], wherein the herbicidal active ingredient is at least one selected from the group consisting of pyrazolate, cyclopyrimorate, pyraclonil, benzobicyclon, metazosulfuron, fentrazamide, and propyrisulfuron.
[6] The pesticide composition according to any one of [1] to [5], wherein the herbicidal active ingredient is pyrazolate.
[7] The aqueous suspension concentrate pesticide composition according to any one of [1] to [6], wherein the salt of the alkylnaphthalenesulfonic acid-formalin condensate is an alkali metal salt of an alkylnaphthalenesulfonic acid-formalin condensate, an alkaline earth metal salt of an alkylnaphthalenesulfonic acid-formalin condensate, an ammonium salt of an alkylnaphthalenesulfonic acid-formalin condensate, or an amine salt of an alkylnaphthalenesulfonic acid-formalin condensate.
[8] The pesticide composition according to [4], wherein the polyoxyethylene (mono-, di-, or tri-)styryl phenyl ether phosphate mono- or diester is polyoxyethylene (mono-, di-, or tri-)styryl phenyl ether phosphate monoester , or polyoxyethylene (mono-, di-, or tri-)styryl phenyl ether phosphate diester.
[9] The pesticide composition according to any one of [1] to [8], wherein the herbicidal active ingredient is contained in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the pesticide composition.
[10] (1) A fine particle containing at least one herbicidal active ingredient;
(2) a salt of an alkylnaphthalenesulfonic acid-formaldehyde condensate;
and adjusting the specific surface area of the mixture to 80,000 cm ² /cm ³ or more in terms of volume distribution integration.
[11] A method for applying an aqueous suspension concentrate pesticidal composition according to any one of [1] to [9] to a paddy field, comprising directly spraying the aqueous suspension concentrate pesticidal composition by hand or by using a pesticide sprayer.

The aqueous suspension pesticide composition of the present invention has excellent storage stability because the decomposition of the herbicidal active ingredient is suppressed.

Explain the various terms used in this specification.

The "herbicidal active ingredient" is not particularly limited as long as it can produce the effects of the present invention, but examples include bleaching herbicidal compounds or their salts, protoporphyrinogen oxidase (hereinafter referred to as PPO) inhibiting herbicidal compounds or their salts, very long chain fatty acid elongase (hereinafter referred to as VLCFAE) inhibiting herbicidal compounds or their salts, and acetolactate synthase (hereinafter referred to as ALS) inhibiting herbicidal compounds or their salts, with bleaching herbicidal compounds being preferred, and pyrazolate being even more preferred.

Bleaching herbicidal compounds are well-known herbicides that bleach weeds and cause them to die. Widely known bleaching herbicidal compounds include pyrazole herbicidal compounds and triketone herbicidal compounds.

Examples of pyrazole herbicidal compounds include pyrazolate, pyrazoxyfen, and benzofenap, which are described in The Pesticide Manual 13th Edition, pages 844-845, 848-849, and 81, respectively.

Examples of triketone herbicidal compounds include mesotrione, sulcotrione, and benzobicyclon, which are described in The Pesticide Manual 13th Edition, pages 631-632, 908-909, and 80, respectively. In addition, tefuryltrione (CAS No. 473278-76-1), fenquinotrion (CAS No. 1342891-70-6), lancotrione (CAS No. 1486617-22-4), and bicyclopyrone (CAS No. 352010-68-5) are also triketone herbicidal compounds.

In addition to pyrazole and triketone herbicidal compounds, clomazone (CAS No. 81777-89-1) and cyclopyrimorate (CAS No. 499231-24-2) are also bleaching herbicidal compounds.

PPO-inhibiting herbicidal compounds are well-known herbicidal compounds that inhibit PPO, causing browning symptoms and killing weeds. Examples of PPO-inhibiting herbicidal compounds are oxadiargyl, oxadiazon, and pentoxazone, which are described in The Pesticide Manual 13th Edition, pages 725-726, 727-728, and 757-758, respectively. Pyraclonil (CAS No. 158353-15-2) and cyclopyranyl (CAS No. 1651191-47-7) are also PPO-inhibiting herbicidal compounds.

VLCFAE-inhibiting herbicidal compounds are well-known herbicidal compounds that inhibit the synthesis of fatty acids by inhibiting VLCFAE, thereby killing weeds. Examples of VLCFAE-inhibiting herbicidal compounds include butachlor, pretilachlor, thenylchlor, and mefenacet, which are described in The Pesticide Manual 13th Edition, pages 118-120, 799-800, 956, and 621-622, respectively. In addition, cafenstrole (CAS No. 125306-83-4), fentrazamide (CAS No. 158237-07-1), fenoxasulfone (CAS No. 639826-16-7), and ipfencarbazone (CAS No. 212201-70-2) are also VLCFAE-inhibiting herbicidal compounds.

ALS-inhibiting herbicidal compounds are well-known herbicidal compounds that inhibit ALS, thereby inhibiting the synthesis of the essential amino acids valine, leucine, and isoleucine, and causing weed death. Widely known examples of ALS-inhibiting herbicidal compounds include sulfonylurea herbicidal compounds, pyrimidinylsalicylic acid herbicidal compounds, and triazolopyrimidine herbicidal compounds.

Examples of sulfonylurea herbicidal compounds include azimsulfuron, bensulfuron-methyl, cyclosulfamuron, halosulfuron-methyl, ethoxysulfuron, imazosulfuron, pyrazosulfuron-ethyl, chlorimuron-ethyl, cinosulfuron, and metsulfuron-methyl, which are described in The Pesticide Manual, 13th Edition, pages 46-47, 73-74, 222-223, 523-524, 386-387, 560-561, 847-848, 161-162, 184-185, and 677-678, respectively. Additionally, flucetosulfuron (CAS No. 412928-75-7), propyrisulfuron (CAS No. 570415-88-2), and metazosulfuron (CAS No. 868680-84-6) are also sulfonylurea herbicidal compounds.

Examples of pyrimidinylsalicylic acid herbicidal compounds include bispyribac, pyribenzoxim, pyriftalid, and pyriminobac-methyl, which are described in The Pesticide Manual 13th Edition, pages 96-97, 852-853, 860-861, and 863-864, respectively. In addition, pyrimisulfan (CAS No. 221205-90-9) and triafamone (CAS No. 874195-61-6) are also pyrimidinylsalicylic acid herbicidal compounds.

An example of a triazolopyrimidine herbicidal compound is penoxsulam, which is described in The Pesticide Manual, 13th Edition, pages 753-754.

The term "salt of alkylnaphthalenesulfonic acid formalin condensate" refers to, for example, a salt of a (mono- or di-)C1-C6 alkylnaphthalenesulfonic acid formalin condensate, such as a salt of a mono-C1-C6 alkylnaphthalenesulfonic acid formalin condensate or a salt of a di-C1-C6 alkylnaphthalenesulfonic acid formalin condensate. Specific examples include salts of formalin condensates of monoalkylnaphthalenesulfonic acids such as methylnaphthalenesulfonic acid, ethylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, or isobutylnaphthalenesulfonic acid; salts of formalin condensates of dialkylnaphthalenesulfonic acids such as dimethylnaphthalenesulfonic acid, diethylnaphthalenesulfonic acid, diisopropylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, or diisobutylnaphthalenesulfonic acid; or salts of formalin condensates of methylnonylnaphthalenesulfonic acid.
Examples of the salt of the formalin condensate include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, ammonium salts, and amine salts. Among these, alkali metal salts are preferred, and sodium salts are particularly preferred. In particular, sodium salts of alkylnaphthalenesulfonic acid-formalin condensates are preferred.

Specific examples of salts of alkylnaphthalenesulfonic acid formalin condensates include, for example, sodium salts of (mono- or di-)C1-C6 alkylnaphthalenesulfonic acid formalin condensates. Representative examples of commonly used salts of alkylnaphthalenesulfonic acid formalin condensates include, for example, Supragil (registered trademark) MNS90, Supragil (registered trademark) RM/210EI (manufactured by Rhodia Nicca), Demol (registered trademark) RN, Demol (registered trademark) SNB (manufactured by Kao Corporation), preferably Labellin (registered trademark) FA-N (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and particularly preferably Morwet (registered trademark) D-425 Powder (manufactured by Lion Specialty Chemicals).

"Polyoxyethylene (mono-, di-, or tri-)styrylphenyl ether" refers to polyoxyethylene styrylphenyl ether having 1 to 3 aryl groups. Specific examples include polyoxyethylene monostyrylphenyl ether, polyoxyethylene distyrylphenyl ether, and polyoxyethylene tristyrylphenyl ether, and particularly preferred is polyoxyethylene distyrylphenyl ether.

The term "mono- or di-phosphate ester" refers to a phosphate ester having one or two organic groups. Specific examples include mono- or di-phosphate esters.
The content of the herbicidal active ingredient in the pesticide composition of the present invention may be any amount that allows the formulation of a suspension formulation, and is usually 0.1 to 30 parts by weight based on 100 parts by weight of the composition of the present invention.

The aqueous suspension pesticide composition of the present invention contains water, (1) fine particles containing at least one herbicidal active ingredient, (2) a salt of an alkylnaphthalenesulfonic acid formalin condensate, and, if necessary, (3) a polyoxyethylene (mono-, di-, or tri-)styrylphenyl ether phosphate mono- or diester, and may further contain other adjuvants for various purposes. Examples of other adjuvants that may be added include wetting agents, dispersants, thickeners, defoamers, fungicides, solvents, or stabilizers, i.e., colorants, bulking agents, preservatives, pH regulators, and other adjuvant components. In addition, the composition may contain, for example, hydrochloric acid in an amount that can be formulated.

The wetting agent or dispersing agent used in the aqueous suspension pesticide composition of the present invention is not particularly limited as long as it is one used in ordinary pesticides, and any surfactant such as anionic surfactants, nonionic surfactants, cationic surfactants, or zwitterionic surfactants can be used, and one or more of these can be used.

Examples of anionic surfactants include alkyl phosphate ester salts, alkyl sulfate ester salts, polyoxyalkylene alkyl ether phosphate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alkylaryl phosphate ester salts, alkylaryl sulfate ester salts, polyoxyalkylene alkylaryl ether phosphate ester salts, polyoxyalkylene alkylaryl ether sulfate ester salts, alkylphenol phosphate salts, alkylphenol phosphate ester salts, alkylphenol sulfate salts, alkylphenol sulfate ester salts, polyoxyalkylene alkylphenol phosphate salts, polyoxyalkylene alkylphenol phosphate salts, polyoxyalkylene alkylphenol phosphate ester salts, polyoxyalkylene alkylphenol sulfate salts, polyoxyalkylene Alkylphenol sulfate, styrylphenol phosphate, styrylphenol phosphate salt, styrylphenol sulfate, styrylphenol sulfate, polyoxyalkylenestyrylphenol phosphate, polyoxyalkylenestyrylphenol phosphate, polyoxyalkylenestyrylphenol sulfate, polyoxyalkylenestyrylphenol sulfate, distyrylphenol phosphate, distyrylphenol phosphate salt, distyrylphenol sulfate, distyrylphenol sulfate, polyoxyalkylenedistyrylphenol phosphate, polyoxyalkylenedistyrylphenol phosphate, polyoxyalkylenedistyrylphenol sulfate, polyoxyalkylenedistyrylphenol sulfate tristyrylphenol sulfate, tristyrylphenol phosphate, tristyrylphenol phosphate salt, tristyrylphenol sulfate, tristyrylphenol sulfate, polyoxyalkylene tristyrylphenol phosphate, polyoxyalkylene tristyrylphenol phosphate, polyoxyalkylene tristyrylphenol sulfate, polyoxyalkylene tristyrylphenol sulfate, alkyl succinate sulfonate, dialkyl succinate sulfonate, polyoxyalkylene dialkyl succinate sulfonate, monoalkyl sulfosuccinate, dialkyl sulfosuccinate, or polyoxyethylene alkyl sulfosuccinate, and preferably alkyl phosphate ester. salts, polyoxyalkylene alkyl ether phosphate salts, alkylaryl phosphate salts, polyoxyalkylene alkylaryl ether phosphate salts, alkylphenol phosphate salts, styrylphenol phosphate salts, polyoxyalkylene styrylphenol phosphate salts, distyrylphenol phosphate salts, distyrylphenol phosphate salts, polyoxyalkylene distyrylphenol phosphate salts, polyoxyalkylene distyrylphenol phosphate salts, tristyrylphenol phosphate salts, tristyrylphenol phosphate salts, polyoxyalkylene tristyrylphenol phosphate salts, polyoxyalkylene tristyrylphenol phosphate salts, and dialkyl sulfosuccinate salts.

Examples of nonionic surfactants include aliphatic alcohol alkylene oxide adducts, polyalkyleneoxy fatty acid esters, sorbitan surfactants or their alkylene oxide adducts, polyglycerol fatty acid esters, alkyl polysaccharide surfactants, sucroglycerides, polyoxyalkylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyalkylene alkyl aryl ethers, polyoxyalkylene alkyl phenol ethers, polyoxyalkylene styryl phenol ethers, polyoxyalkylenedistyryl phenol ethers, and polyoxyalkylene tristyryl phenol ethers. Preferred examples include polyoxyalkylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyalkylene alkyl aryl ethers, polyoxyalkylene alkyl phenol ethers, polyoxyalkylene styryl phenol ethers, polyoxyalkylenedistyryl phenol ethers, and polyoxyalkylene tristyryl phenol ethers.
These surfactants containing ethylene oxide may contain propylene oxide as a part thereof.

Examples of cationic surfactants include aliphatic tertiary amines or their salts, aliphatic tertiary amine-aliphatic amine alkylene oxide adducts or their salts, and aliphatic quaternary amine salts.

Examples of amphoteric surfactants include amino acid amphoteric surfactants such as sodium laurylaminopropionate; carboxylate amphoteric surfactants such as betaine amphoteric surfactants such as lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine; sulfate ester salt amphoteric surfactants; sulfonate salt amphoteric surfactants; and phosphate ester salt amphoteric surfactants.

The amount of surfactant used in one embodiment of the aqueous suspension pesticide composition of the present invention is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight, in the pesticide composition.

There are no particular limitations on the thickening agent, so long as it is one that is normally used in pesticide formulations. Examples include minerals such as white carbon, aluminosilicates, bentonite, montmorillonite, hectorite, and attapulgite; and polymeric thickening agents such as gum arabic, gum tragacanth, xanthan gum, guar gum, roasted bean gum, casein, alginic acid, cellulose polysaccharides, ethyl cellulose, polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose. Polymeric thickening agents are preferred, and xanthan gum is more preferred.

The defoaming agent is not particularly limited as long as it is one that is normally used in pesticide formulations, but examples include lower alcohol-based defoaming agents such as methanol, ethanol, isopropanol, sec-butanol, and butanol; organic polar compound-based defoaming agents such as amyl alcohol, diisobutyl carbitol, tributyl phosphate, oleic acid, tall oil, metal soap, surfactants with low HLB (e.g., sorbitan laurate monoester, sorbitan laurate triester, polyethylene glycol fatty acid ester, acetylene glycol derivatives, Pluronic-type nonionic surfactants, etc.), and acetylene glycol derivatives; mineral oil-based defoaming agents such as mineral oil surfactant blends and mineral oil and fatty acid metal salt surfactant blends; silicone resin-based defoaming agents such as silicone resin, silicone resin surfactant blends, and silicone resin inorganic powder blends.

There are no particular limitations on the fungicides that are normally used in agricultural chemical formulations, but examples include parachlorometaxylenol, polyhexamethylene biguanidide hydrochloride, 1,2-benzoisothiazolin-3-one, methyl parahydroxybenzoate, ethyl parahydroxybenzoate, propyl parahydroxybenzoate, butyl parahydroxybenzoate, heptyl parahydroxybenzoate, benzyl parahydroxybenzoate, paraoxybenzoic acid esters, sorbic acid, orthophenylphenol, sodium orthophenylphenate, glutaric dialdehyde, quaternary ammonium compounds, tri-(N -chlorohexyldiazeniumdioxy)-aluminum, tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thione, 2,5-dimethoxytetrahydrofuran, dimethylol urea, sodium N-methyldithiocarbamate, phenoxyethanol, glyoxal, glutaraldehyde, 1,3,5-tris(2-hydroxyethyl)-1,3,5-hexahydrotriazine, benzalkonium chloride, phenoxypropanol, tetramethylacetylenediurea, povidone iodine, potassium sorbate, 2-bromo-2-nitropropane-1,3-diol, or thiazolone.

There are no particular limitations on the solvent as long as it is one that is normally used in pesticides, but it is preferable for it to have a flash point of Class 2 petroleum or higher. Examples of such fatty acids include alkylbenzene, methylnaphthalene, liquid paraffin, ligroin, kerosene, kerosene, n-decane, isododecane, tetralin, decalin, turpentine oil, pine oil, adipic acid, gluconic acid, maleic acid, lactic acid, benzoic acid, phthalic acid, malic acid, fumaric acid, succinic acid, tartaric acid, citric acid, lauric acid, oleic acid, coconut oil fatty acid, cyclohexanone, cyclohexenylcyclohexanone, acetylacetone, acetophenone, methylbutyl ketone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, epichlorhydrin, diglycidyl ether, dioxane, triethyl phosphate, tributyl phosphate, soybean oil, rapeseed oil, sesame oil, rice oil, coconut oil, sunflower oil, sardine oil, whale oil, dimethyl sulfoxide, N,N-dimethylacetamide, and N-methylpyrrolidone.

There are no particular limitations on the coloring agent, so long as it is one that is normally used in pesticides, and examples include dyes, and preferably Brilliant Blue FCF, Cyanine Green G, or Eriogreen G. The amount of coloring agent used is usually 0.05 to 0.5% by weight, and preferably 0.1 to 0.3% by weight, in the aqueous suspension pesticide composition.

There are no particular limitations on the preservatives, so long as they are those normally used in pesticides, and preferred are sorbic acid, potassium sorbate, parachlorometaxylenol, butyl paraoxybenzoate, or sodium dehydroacetate. The amount of preservative used is usually 0.1 to 3% by weight, and preferably 0.2 to 2% by weight, in the aqueous suspension pesticide composition.

There are no particular limitations on the pH regulator, so long as it is one that is normally used in agricultural chemicals. For example, inorganic acids such as phosphoric acid; organic acids such as citric acid, phthalic acid, and succinic acid; organic metal salts such as sodium citrate and potassium hydrogen phthalate; inorganic metal salts such as disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium carbonate, potassium carbonate, and sodium borate; hydroxides such as sodium hydroxide and potassium hydroxide; or organic amines such as triethanolamine. Preferred are inorganic acids, inorganic metal salts, or hydroxides, and more preferred are hydrochloric acid, citric acid, succinic acid, sodium hydroxide, potassium hydroxide, or sodium carbonate. The pH regulators used can be used alone or in combination of two or more.

The aqueous suspension concentrate pesticide composition of the present invention comprises:
(1) A fine particle containing at least one herbicidal active ingredient;
(2) a salt of an alkylnaphthalenesulfonic acid-formaldehyde condensate;
Includes.
Furthermore, from the viewpoint of the effects of the present invention, it is also preferable to contain (3) polyoxyethylene (mono-, di-, or tri-)styrylphenyl ether phosphate mono- or diester.
If necessary, the above-mentioned other components or fine particles thereof may be contained.

The herbicidal active ingredient is not particularly limited as long as it can exert the effect of the present invention, and can be appropriately selected from the above-mentioned herbicidal active ingredients, but in the present invention, from the viewpoint of the effect of the present invention, it is preferable that it is at least one selected from the group consisting of pyrazolate, cyclopyrimorate, pyraclonil, benzobicyclone, fentrazamide, metazosulfuron and propyrisulfuron, and it is more preferable that it contains pyrazolate.

In the present invention, the specific surface area of the fine particles contained in the aqueous suspension pesticide composition is 80,000 ^cm2 / ^cm3 or more in terms of volume distribution. By setting the specific surface area of the fine particles in this range, there is an effect that decomposition of the herbicidal active ingredient is suppressed and storage stability is improved. The specific surface area is more preferably 90,000 ^cm2 /cm3 or ^more , and particularly preferably 100,000 ^cm2 /cm3 or ^more .

In general, if the specific surface area of the fine particles containing a herbicidal active ingredient contained in an aqueous suspension pesticide composition is increased, the herbicidal effect is improved, but the area in contact with water, oxygen, etc. is increased, which promotes the decomposition of the herbicidal active ingredient and reduces storage stability. In other words, in an aqueous suspension pesticide composition, there is a trade-off between the improvement of the herbicidal effect of the herbicidal active ingredient and the storage stability. However, the present inventors have discovered that in an aqueous suspension pesticide composition containing (1) fine particles containing a herbicidal active ingredient and (2) a salt of an alkylnaphthalenesulfonic acid formalin condensate, by setting the specific surface area of the fine particles contained in the composition to a predetermined value or more, the decomposition of the herbicidal active ingredient contained in the fine particles (1) is suppressed and the herbicidal effect is more effectively expressed, thereby completing the present invention.

The specific surface area of the fine particles (1) calculated as volume distribution is 80,000 ^cm2 /cm3 or ^more , preferably 90,000 ^cm2 /cm3 or ^more , and more preferably 100,000 ^cm2 / ^cm3 or more. This effectively inhibits the decomposition of the herbicidal active ingredient contained in the fine particles (1) by the action of component (2), and further improves the storage stability.

"Specific surface area converted into volume distribution" refers to the specific surface area calculated by integrating the volume distribution obtained using a laser diffraction/scattering particle size distribution measuring device (LA-960 manufactured by Horiba, Ltd.).

Next, a method for producing the aqueous suspension pesticide composition of the present invention will be described. The aqueous suspension pesticide composition of the present invention can be produced by known formulation processes such as mixing and grinding used in the production of ordinary pesticide formulations. For example, when wet grinding the pesticide active ingredient, the pesticide active ingredient, surfactant and defoamer are added to water and mixed and suspended, then wet-ground to a predetermined particle size using a wet grinder as described below, and then the previously added, mixed, dispersed and dissolved ingredients are added and homogenized, and the pH of the composition is further adjusted with a pH adjuster to obtain the aqueous suspension pesticide composition of the present invention.

Examples of wet grinding machines include attrition mills such as Attritor (registered trademark) (Mitsui Mining Co., Ltd.); bead mills such as Dyno Mill (registered trademark) (Shinmaru Enterprises Co., Ltd.), Research Lab TM (Shinmaru Enterprises Co., Ltd.), Sand Grinder (registered trademark) (Igarashi Machinery Co., Ltd.), Apex Mill (registered trademark) (Kotobuki Engineering Co., Ltd.), Super Apex Mill (registered trademark) (Kotobuki Engineering Co., Ltd.), Ultra Apex Mill (registered trademark) (Kotobuki Engineering Co., Ltd.), Diamond Fine Mill (registered trademark) (Mitsubishi Heavy Industries, Ltd.), Koball Mill (registered trademark) (Shinko Pantech Co., Ltd.), and Dreiswerke Pearl Mill (Nihon Eirich Co., Ltd.); and hammer mills such as Colloid Mill (registered trademark) (Tokushu Kika Kogyo Co., Ltd.) and Wet Atomizer (registered trademark) (Fuji Paudal Co., Ltd.).

The grinding of the active ingredient is not limited to wet grinding. For example, the active ingredient can be mixed with a mineral carrier or other auxiliary agents, if necessary, and ground to a predetermined particle size using a dry grinder. The resulting ground product can be added to water together with a surfactant, antifoaming agent, thickener, antifreeze agent, antibacterial agent and other auxiliary agents, suspended and dispersed, and mixed and homogenized to obtain the aqueous suspension pesticide composition of the present invention.

Examples of dry grinding machines include jet mills such as SK-Jet-O-Mill (registered trademark) (Seishin Enterprise Co., Ltd.) and Single Track Jet Mill (registered trademark) (Seishin Enterprise Co., Ltd.); hammer mills such as ACM Pulperizer (registered trademark) (Hosokawa Micron Co., Ltd.) and Sample Mill TM (Fuji Paudal Co., Ltd.); pin mills (registered trademark); ball mills (registered trademark); turbo mills (registered trademark); etc.

Furthermore, the grinding of the pesticide active ingredient can be performed by appropriately combining grinding with each of these grinders. For example, it is possible to pre-grind the active ingredient with a wet grinder such as a Colloid Mill TM or Wet Atomizer (registered trademark), and then finely grind it with a bead mill, or it is possible to suspend and disperse the active ingredient that has been dry-ground in advance in water together with a surfactant and an antifoaming agent, and then further finely grind it with the above-mentioned wet grinder. It is also possible to pre-grind the active ingredient with a batch grinder such as Attritor (registered trademark), and then finely grind it with a continuous bead mill.

Regarding the degree of grinding of the pesticide active ingredient, whether wet grinding or dry grinding is used, the majority of the active ingredient is usually ground to a size of 10 μm or less, preferably to a weight median diameter of 0.1 to 5 μm.

The aqueous suspension pesticide composition of the present invention is preferably prepared by wet grinding a mixture containing (1) fine particles containing at least one herbicidal active ingredient, (2) a salt of an alkylnaphthalenesulfonic acid formalin condensate, and, if necessary, (3) a polyoxyethylene (mono-, di-, or tri-)styrylphenyl ether phosphate mono- or diester. In this grinding step, the specific surface area of the fine particles contained in the mixture is adjusted to 80,000 cm ² /cm ³ or more in terms of volume distribution. By setting the specific surface area of the fine particles in this range, the decomposition of the herbicidal active ingredient is suppressed and the storage stability is improved. The specific surface area is more preferably 90,000 cm ² /cm ³ or more, and particularly preferably 100,000 cm ² /cm ³ or more.

The aqueous suspension pesticide composition of the present invention can usually be used as a direct spray. When diluting the prepared aqueous suspension pesticide composition to produce an aqueous composition containing the pesticide composition, in addition to the above water, agricultural water, industrial water, well water, tap water, etc. can be used as long as they do not inhibit the function and performance of the pesticide composition. The dilution ratio when preparing the aqueous composition can be appropriately selected depending on the crops, soil, etc. to be used, and can be 10 to 5,000 times, preferably 50 to 2,000 times.

When used for direct spraying, the aqueous suspension pesticide composition can be placed in a 100-1000 mL plastic bottle with a hole in the inner stopper and can be manually poured into the bottle without dilution, or mechanically sprayed using a chemical ejection device, pesticide sprayer, etc., but is not limited to these methods. The application amount and application time of the aqueous suspension pesticide composition and the aqueous composition containing the aqueous suspension pesticide composition can be appropriately determined depending on the pesticide active ingredient to be blended.

The above "pesticide sprayer" refers to devices that are powered by an engine or motor, such as unmanned helicopters, drones, and powered sprayers.

The composition and control method of the present invention are effective against, for example, the following types of weeds:
Weeds include various weeds that are problematic in paddy fields, for example, grass weeds such as barnyard grass; broadleaf weeds such as burdock, burdock, Chinese burdock, water chickweed, water hyacinth, sedge, and Japanese knotweed; Cyperaceae weeds such as Cyperus punctatus, bulrush, pine bait, serotinus serrata, and kuroguwai; and Saltaceae weeds such as Sagittaria pygmaea, arrowhead, and arrowhead weed; non-agricultural weeds such as Sagittaria pygmaea, arrowhead, and arrowhead weed; Various weeds that are problematic in arable land, field land and orchards, for example, solanaceae weeds such as day cherries and Datura stramonium, mallow weeds such as velvetleaf and American sedge, convolvulaceae weeds such as morning glory and field bindweed, amaranthaceae weeds such as black burdock and redroot pigweed, Asteraceae weeds such as cocklebur, ragweed, ground daisy and fleabane, mustard and shepherd's purse Brassicaceae weeds such as Lamium orchid, Chenopodiaceae weeds such as Chenopodium album and Chenopodium album, Violaceae weeds such as field pansy, Caryophyllaceae weeds such as chickweed, Legume weeds such as white clover, Solanum pratense and Calendula officinalis, Portulacaceae weeds such as Purslane, Scrophulariaceae weeds such as Veronica persica, Lamiaceae weeds such as Lamium amplexicaule, Euphorbiaceae weeds such as Cornus officinalis, Dogweed Examples of weeds that can be used include, but are not limited to, grass weeds such as sorghum, crabgrass, goosegrass, annual grass, annual foxtail, oat, ryegrass, green foxtail, and Chinese dwarf grass; sedge weeds such as Japanese laurel and yellow sedge; dayflower weeds such as dayflower and round dayflower; and horsetail weeds such as horsetail.

The following are examples of formulations of the pesticide composition used in the present invention, but the present invention is not limited to these. In the following formulation examples, "%" indicates % by mass, and "parts" indicates parts by weight.

Example 1
128.57 parts of pyrazolate raw material (purity 94.5%), 59.83 parts of cyclopyrimorate raw material (purity 98.50%), 3.00 parts of Morwet (registered trademark) D-425 Powder (manufactured by Lion Specialty Chemicals, sodium salt of alkylnaphthalenesulfonic acid formalin condensate), 4.50 parts of Newcol (registered trademark) 607-PDE (manufactured by Nippon Nyukazai Co., Ltd., polyoxyethylene mono-, di-, or tristyrylphenyl ether phosphate mono- or diester), 0.60 parts of Surfynol (registered trademark) 104PG50 (manufactured by Evonik Japan, alkylene diol), 0.60 parts of AF (registered formulation)-128 (10% aqueous solution) (manufactured by Asahi Chemical Industry Co., Ltd., silicone defoamer) and 102.90 parts of tap water were mixed, and the mixture was diluted with Attritor (registered trademark) 0.1S. Wet pulverization was performed using a mold (manufactured by Mitsui Mining & Metals Co., Ltd.) to obtain a pyrazolate/cyclopyrimorate premix slurry. Next, 1.50 parts of ammonium sulfate, 45.00 parts of Agrisol G-200 (manufactured by Kao Corporation, anionic special polymer surfactant), 4.50 parts of Newcol PB60 (manufactured by Nippon Nyukazai Co., Ltd., polystyrylphenyl ether-formalin condensate), 30.00 parts of Morwet (registered trademark) D-425 Powder, and 219.00 parts of tap water were mixed and dissolved to obtain a dispersant mixture. In addition, 11.20 parts of bentonite (Kunipia (registered trademark) F, manufactured by Kunimine Kogyo Co., Ltd.), 2.80 parts of xanthan gum (Roadpole (registered trademark) 23, manufactured by Rhodia Nikka Co., Ltd.), 186.64 parts of propylene glycol, and 599.36 parts of tap water were added and mixed to obtain a thickener mixture. 280.00 parts of pyrazolate/cyclopyrimorate premix slurry, 200.00 parts of dispersant mixture, 300.00 parts of thickener mixture, 62.59 parts of fentrazamide bulk powder (purity 71.90%), 2.0 parts of Proxel (registered trademark) GXL-S (Arch Chemicals Japan) and 155.41 parts of tap water were added and mixed to obtain an aqueous suspension pesticide composition having a specific surface area of 94,400 ^cm2 / ^cm3 .

Example 2
Pyrazolate technical substance (purity 94.5%) 105.79 parts, cyclopyrimorate technical substance (purity 98.40%) 49.59 parts, propyrisulfuron technical substance (purity 98.3%) 16.16 parts, Morwet (registered trademark) D-425 Powder (manufactured by Lion Specialty Chemicals, sodium salt of alkylnaphthalenesulfonic acid formalin condensate) 3.60 parts, VEEGUM R (registered trademark) (manufactured by Vanderbilt Minerals, magnesium aluminum silicate) 0.60 parts, Newcoal (registered trademark) 607-PDE (manufactured by Nippon Nyukazai Co., Ltd., polyoxyethylene mono-, di- or tristyrylphenyl ether phosphate mono- or diester) 4.50 parts, Newcoal (registered trademark) 291-PG 0.15 parts of (manufactured by Nippon Nyukazai Co., Ltd., sodium dialkyl sulfosuccinate), 3.00 parts of AF (registered formulation)-128 (10% aqueous solution) (manufactured by Asahi Chemical Industry Co., Ltd., silicone antifoaming agent), and 116.61 parts of tap water were mixed and wet-pulverized using an Attritor (registered trademark) 0.1S type (manufactured by Mitsui Mining & Smelting Co., Ltd.) to obtain a pyrazolate/cyclopyrimorate/propyrisulfuron premix slurry. Then, 6.00 parts of ammonium sulfate, 60.00 parts of Polity (registered trademark) A540 (manufactured by Lion Co., Ltd., polyacrylate) and 234.00 parts of tap water were added and mixed to dissolve, to obtain a dispersant mixture. In addition, 5.50 parts of bentonite (Kunipia (registered trademark) F, Kunimine Kogyo Co., Ltd.), 2.00 parts of xanthan gum (Rodepol (registered trademark) 23, Rhodia Nikka Co., Ltd.), 133.35 parts of propylene glycol, and 359.15 parts of tap water were added and mixed to obtain a thickener mixture. 272.00 parts of pyrazolate/cyclopyrimorate/propyrisulfuron premix slurry, 200.00 parts of dispersant mixture, 240.00 parts of thickener mixture, 1.60 parts of Proxel (registered trademark) GXL-S (Arch Chemicals Japan Co., Ltd.), and 86.40 parts of tap water were added and mixed to obtain an aqueous suspension pesticide composition with a specific surface area of 93,600 cm ² /cm ³ .

Example 3
177.18 parts of pyrazolate technical substance (purity 94.2%), 10.05 parts of propyrisulfuron technical substance (purity 98.2%), 2.40 parts of Morwet (registered trademark) D-425 Powder (manufactured by Lion Specialty Chemicals, sodium salt of alkylnaphthalenesulfonic acid formalin condensate), 3.00 parts of Newcol (registered trademark) 607-PDE (manufactured by Nippon Nyukazai Co., Ltd., polyoxyethylene mono-, di-, or tristyrylphenyl ether phosphate mono- or diester), 0.30 parts of Surfynol (registered trademark) 104PG50 (manufactured by Evonik Japan, alkylene diol), 0.30 parts of KM (registered formulation)-68-1F (10% aqueous solution) (manufactured by Shin-Etsu Chemical Co., Ltd., sorbitan fatty acid ester) and 106.77 parts of tap water were mixed, and the mixture was diluted with Attritor (registered trademark) 0.1S. Wet pulverization was performed using a mold (manufactured by Mitsui Mining & Metals Co., Ltd.) to obtain a pyrazolate/propyrisulfuron premix slurry. Then, 3.99 parts of ammonium sulfate, 80.01 parts of Agrisol G-200 (manufactured by Kao Corporation, anionic special polymer surfactant), 60.00 parts of Morwet (registered trademark) D-425 Powder, and 156.00 parts of tap water were added and mixed to obtain a dispersant mixture. In addition, 3.96 parts of bentonite (Kunipia (registered trademark) F, manufactured by Kunimine Kogyo Co., Ltd.), 1.44 parts of xanthan gum (Rodepole (registered trademark) 23, manufactured by Rhodia Nikka Co., Ltd.), 55.56 parts of propylene glycol, and 239.04 parts of tap water were added and mixed to obtain a thickener mixture. 148.20 parts of pyrazolate/propyrisulfuron premix slurry, 22.50 parts of dispersant mixture, 81.00 parts of thickener mixture, 0.60 parts of Proxel (registered trademark) GXL-S (Arch Chemicals Japan) and 47.70 parts of tap water were added and mixed to obtain an aqueous suspension pesticide composition having a specific surface area of 135,200 ^cm2 / ^cm3 .

Example 4
Pyrazolate raw material (purity 94.0%) 131.61 parts, pyraclonil raw material (purity 97.5%) 22.35 parts, benzobicyclon raw material (purity 98.0%) 24.66 parts, Morwet (registered trademark) D-425 Powder (manufactured by Lion Specialty Chemicals, sodium salt of alkylnaphthalenesulfonic acid formalin condensate) 3.00 parts, KP (registered trademark) -1436 (25) (manufactured by Kao Corporation, polyoxyethylene styrenated phenol phosphate ester salt) 3.00 parts, Surfynol (registered trademark) 104E (manufactured by Evonik Japan, alkylene diol) 0.30 parts, AF (registered formulation) -128 (10% aqueous solution) (manufactured by Asahi Chemical Industry Co., Ltd., silicone defoamer) 0.30 parts, VEEGUM R (registered trademark) (Vanderbilt 0.60 parts of 1,2-diamino-1,2-diphenyl-2,3-dimethyl-2,4-dimethyl-1,5-dimethyl-2,6-dimethyl-1,7-dimethyl-2,8-dimethyl-1,9 ... In addition, 3.15 parts of bentonite (Kunipia (registered trademark) F, Kunimine Kogyo Co., Ltd.), 1.14 parts of xanthan gum (Rodepole (registered trademark) 23, Rhodia Nikka Co., Ltd.), 63.15 parts of propylene glycol, 5.04 parts of VEEGUM R (registered trademark) (Vanderbilt Minerals, magnesium aluminum silicate) and 227.55 parts of tap water were added and mixed to obtain a thickener mixture. 150.00 parts of pyrazolate / pyraclonil / benzovidichron premix slurry, 30.00 parts of dispersant mixture, 71.25 parts of thickener mixture, 0.60 parts of Proxel (registered trademark) GXL-S (Arch Chemicals Japan Co., Ltd.) and 48.15 parts of tap water were added and mixed to obtain an aqueous suspension-type pesticide composition with a specific surface area of 105,000 cm ² /cm ³ .

Example 5
Pyrazolate raw material (purity 94.5%) 186.18 parts, Newcoal (registered trademark) 607-PDE (manufactured by Nippon Nyukazai Co., Ltd., polyoxyethylene mono-, di- or tristyrylphenyl ether phosphate mono- or diester) 7.50 parts, AF (registered formulation)-128 (10% aqueous solution) (manufactured by Asahi Chemical Industry Co., Ltd., silicone antifoaming agent) 2.25 parts and tap water 104.07 parts were mixed and wet ground with Attritor (registered trademark) 0.1S type (manufactured by Mitsui Mining & Metals Co., Ltd.) to obtain a pyrazolate slurry (1). Next, Morwet (registered trademark) D-425 Powder 30.00 parts and tap water 270.00 parts were added and mixed and dissolved to obtain a dispersant mixture. In addition, 3.99 parts of bentonite (Kunipia (registered trademark) F, Kunimine Industries Co., Ltd.), 1.11 parts of xanthan gum (Rodepol (registered trademark) 23, Rhodia Nikka Co., Ltd.), 69.99 parts of propylene glycol, and 224.91 parts of tap water were added and mixed to obtain a thickener mixture. 119.70 parts of pyrazolate slurry (1), 90.00 parts of the dispersant mixture, 90.00 parts of the thickener mixture, and 0.30 parts of Proxel (registered trademark) GXL-S (Arch Chemicals Japan Co., Ltd.) were added and mixed to obtain an aqueous suspension pesticide composition with a specific surface area of 101,800 ^cm2 / ^cm3 .

Example 6
The formulation was the same as in Example 5, but the wet-grinding time was adjusted to obtain an aqueous suspension concentrate pesticidal composition having a specific surface area of 91,300 cm ² /cm ³ .

(Example 7)
The formulation was the same as in Examples 5 and 6, but the wet-grinding time was adjusted to obtain an aqueous suspension concentrate pesticidal composition having a specific surface area of 81,200 cm ² /cm ³ .

(Example 8)
Pyrazolate technical substance (purity 94.2%) 149.28 parts, benzobicyclon technical substance (purity 99.5%) 27.14 parts, metazosulfuron technical substance (purity 93.7%) 9.86 parts, Morwet (registered trademark) D-425 Powder (manufactured by Lion Specialty Chemicals, sodium salt of alkylnaphthalenesulfonic acid formalin condensate) 3.00 parts, Newcol (registered trademark) 607-PDE (manufactured by Nippon Nyukazai Co., Ltd., polyoxyethylene mono-, di- or tristyrylphenyl ether phosphate mono- or diester) 3.00 parts, Newcol (registered trademark) 291-PG (manufactured by Nippon Nyukazai Co., Ltd., dialkylsulfosuccinic acid sodium salt) 0.15 parts, VEEGUM R (registered trademark) (Vanderbilt 0.60 parts of aluminum magnesium silicate (manufactured by Minerals Co., Ltd.), 0.30 parts of Surfynol (registered trademark) 104PG50 (manufactured by Evonik Japan Co., Ltd., alkylene diol), 0.30 parts of AF (registered formulation)-128 (10% aqueous solution) (manufactured by Asahi Chemical Industry Co., Ltd., silicone defoamer) and 106.37 parts of tap water were mixed and wet-pulverized with Attritor (registered trademark) 0.1S type (manufactured by Mitsui Mining & Smelting Co., Ltd.) to obtain a pyrazolate/benzobicyclone/metazosulfuron premix slurry. Then, 0.66 parts of ammonium sulfate, 13.30 parts of neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd., sodium sulfate), 33.22 parts of Polity (registered trademark) A540 (manufactured by Lion Co., Ltd., polyacrylate), 0.72 parts of 3N hydrochloric acid and 152.10 parts of tap water were added and mixed to dissolve, and a dispersant mixture was obtained. Also, 0.78 parts of KERZAN AP (xanthan gum, manufactured by CP Kelco), 0.78 parts of xanthan gum (Rodepol (registered trademark) 23, manufactured by Rhodia Nikka), 33.33 parts of propylene glycol, and 265.11 parts of tap water were added and mixed to obtain a thickener mixture. 200.00 parts of pyrazolate/benzobicyclone/metazosulfuron premix slurry, 150.50 parts of dispersant mixture, 135.00 parts of thickener mixture, 1.00 part of Proxel (registered trademark) GXL-S (manufactured by Arch Chemicals Japan), and 13.50 parts of tap water were added and mixed to obtain an aqueous suspension-type pesticide composition having a specific surface area of 95,000 cm ² /cm ³ .

(Comparative Example 1)
The formulation was the same as in Example 3, but the wet-grinding time was adjusted to obtain an aqueous suspension concentrate pesticide composition having a specific surface area of 78,000 cm ² /cm ³ .

(Comparative Example 2)
The formulation was the same as in Examples 5, 6 and 7, but the wet-grinding time was adjusted to obtain an aqueous suspension concentrate pesticidal composition having a specific surface area of 52,900 cm ² /cm ³ .

(Comparative Example 3)
The formulation was the same as in Examples 5, 6 and 7 and Comparative Example 2, but the wet-grinding time was adjusted to obtain an aqueous suspension concentrate pesticidal composition having a specific surface area of 40,600 cm ² /cm ³ .

(Comparative Example 4)
186.18 parts of pyrazolate raw material (purity 94.5%), 7.50 parts of Newcoal (registered trademark) 607-PDE (manufactured by Nippon Nyukazai Co., Ltd., polyoxyethylene mono-, di-, or tristyrylphenyl ether phosphate mono- or diester), 2.25 parts of AF (registered formulation)-128 (10% aqueous solution) (manufactured by Asahi Chemical Industry Co., Ltd., silicone antifoaming agent), and 104.07 parts of tap water were mixed and wet-pulverized with Attritor (registered trademark) 0.1S type (manufactured by Mitsui Mining & Metals Co., Ltd.) to obtain a pyrazolate slurry (1). Next, 3.99 parts of bentonite (Kunipia (registered trademark) F, manufactured by Kunimine Kogyo Co., Ltd.), 1.11 parts of xanthan gum (Rodepol (registered trademark) 23, manufactured by Rhodia Nikka Co., Ltd.), 69.99 parts of propylene glycol, and 224.91 parts of tap water were added and mixed to obtain a thickener mixture. 119.70 parts of pyrazolate slurry (1), 90.00 parts of tap water, 90.00 parts of thickener mixture, and 0.30 parts of Proxel (registered trademark) GXL-S (manufactured by Arch Chemicals Japan) were added and mixed to obtain an aqueous suspension pesticide composition having a specific surface area of 90,100 ^cm2 / ^cm3 .

(Comparative Example 5)
The formulation was the same as in Comparative Example 4, but the wet-grinding time was adjusted to obtain an aqueous suspension concentrate pesticide composition having a specific surface area of 80,600 cm ² /cm ³ .

(Comparative Example 6)
The formulation was the same as in Comparative Examples 4 and 5, but the wet-grinding time was adjusted to obtain an aqueous suspension concentrate pesticidal composition having a specific surface area of 56,500 cm ² /cm ³ .

(Comparative Example 7)
The formulation was the same as in Comparative Examples 4, 5 and 6, but the wet-grinding time was adjusted to obtain aqueous suspension concentrate pesticidal compositions having a specific surface area of 35,700 cm ² /cm ³ .

(Test Example)
The aqueous suspension pesticide compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 7 were sealed in plastic bottles and stored in a thermostat at 40°C for 90 days. The active ingredient contents (pyrazolate, cyclopyrimorate, fentrazamide, propyrisulfuron, pyraclonil, benzobicyclon, metazosulfuron) of the aqueous suspension pesticide compositions before and after the aging test were quantified by liquid chromatography to evaluate the change over time. The results were calculated from the active ingredient decomposition rate after aging (the following formula). The results are shown in Table 1.
Formula: Active ingredient decomposition rate (%)
= [1 - (active ingredient content after storage)/(active ingredient content before storage)] x 100

As is clear from the results of the test examples, the aqueous suspension pesticide composition of the present invention is able to achieve stabilization of pesticide active ingredients, which was difficult to achieve with formulations using the known techniques listed as comparative examples, and a highly practical aqueous suspension pesticide composition was obtained.

The aqueous suspension pesticide composition of the present invention inhibits the decomposition of the herbicidal active ingredient, has excellent storage stability, and is a useful formulation as an agricultural material.

Claims (12)

(1) Fine particles containing a herbicidal active ingredient;
(2) a salt of an alkylnaphthalenesulfonic acid-formaldehyde condensate;
Including,
The herbicidal active ingredient comprises pyrazolate,
1. An aqueous suspension concentrate pesticidal composition having a volume distribution integrated specific surface area of 80,000 cm ² /cm ³ or more. 2. The pesticidal aqueous suspension concentrate according to claim 1, wherein the specific surface area is 90,000 ^{cm 2} /cm ³ or more. 3. The pesticidal aqueous suspension concentrate according to claim 1, wherein the specific surface area is 100,000 ^{cm 2} /cm ³ or more. The aqueous suspension pesticide composition according to any one of claims 1 to 3, further comprising (3) polyoxyethylene (mono-, di-, or tri-)styryl phenyl ether phosphate mono- or diester. The aqueous suspension pesticide composition according to any one of claims 1 to 4, wherein the herbicidal active ingredient further comprises at least one selected from the group consisting of cyclopyrimorate, pyraclonil, benzobicyclon, metazosulfuron, fentrazamide and propyrisulfuron. 5. The agricultural chemical composition according to claim 1 , wherein the herbicidal active ingredient is pyrazolate. The aqueous suspension pesticide composition according to any one of claims 1 to 6, wherein the salt of the alkylnaphthalenesulfonic acid-formalin condensate is an alkali metal salt of an alkylnaphthalenesulfonic acid-formalin condensate, an alkaline earth metal salt of an alkylnaphthalenesulfonic acid-formalin condensate, an ammonium salt of an alkylnaphthalenesulfonic acid-formalin condensate, or an amine salt of an alkylnaphthalenesulfonic acid-formalin condensate. The aqueous suspension pesticide composition according to claim 4, wherein the polyoxyethylene (mono-, di-, or tri-)styryl phenyl ether phosphate mono- or diester is polyoxyethylene (mono-, di-, or tri-)styryl phenyl ether phosphate monoester or polyoxyethylene (mono-, di-, or tri-)styryl phenyl ether phosphate diester. The aqueous suspension concentrate pesticide composition according to any one of claims 1 to 8, which contains the herbicidal active ingredient in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the aqueous suspension concentrate pesticide composition. (1) Fine particles containing a herbicidal active ingredient;
(2) a salt of an alkylnaphthalenesulfonic acid-formaldehyde condensate;
and adjusting the specific surface area of the mixture to 80,000 cm ² /cm ³ or more in terms of volume distribution integration,
The method for producing an aqueous suspension concentrate pesticide composition, wherein the herbicidal active ingredient comprises pyrazolate. The method for producing an aqueous suspension pesticide composition according to claim 10, wherein the herbicidal active ingredient further comprises at least one selected from the group consisting of cyclopyrimorate, pyraclonil, benzobicyclon, metazosulfuron, fentrazamide and propyrisulfuron. A method for applying an aqueous suspension pesticide composition according to any one of claims 1 to 9 to a paddy field by directly spraying the aqueous suspension pesticide composition by hand or by using a pesticide sprayer.