CN1856247A - Uniformly diffusible granular pesticide composition - Google Patents

Abstract

The purpose of the present invention is to provide the granular pesticide preparation that can be prepared in a simple way, and while exerting the drug effect of the active ingredient of the pesticide for a long time, can reduce the environmental burden, reduce or prevent the drug hazard caused by the active ingredient of the pesticide, which is a granular pesticide preparation that can A uniformly diffusible granular pesticide formulation that spreads uniformly over the entire paddy field by a simple spraying method. As a uniformly diffusible granular pesticide formulation, there is provided a non-disintegrating granular pesticide composition containing an acidic pesticide active ingredient, a cationic surfactant, and an alkaline substance that does not disintegrate in water within 30 minutes or less, and provides a granular A granular composition whose mass ratio of particles having a diameter of 3 mm or more is 80% by mass or more and which has a particle size distribution and the property of floating on the water surface immediately after being charged, but disintegrates on the water surface within 30 minutes or less . The acidic pesticide active ingredient has a pKa of 2 to 7, and the cationic surfactant is preferably gelled or swellable in water.

Description

Uniform diffusing granular pesticide formulation

technical field

The present invention relates to a uniform diffusible granular pesticide preparation that can reduce or prevent drug hazards and reduce environmental burdens while exhibiting the efficacy of pesticide active ingredients for a long time.

Background technique

For a long time, in order to reduce the drug hazard and maintain the efficacy of granular pesticide preparations containing pesticide active ingredients, various preparation methods that can inhibit the dissolution of pesticide active ingredients have been studied. For example, a method for slow release by combining paraffin, thermoplastic resin or activated carbon, granular foam, and clay minerals has been proposed (refer to Japanese Patent Application Publication No. 63-35504, Japanese Patent Application Publication No. 63-45201 and Japanese Patent Application Laid-Open No. 2-288803).

However, such conventional slow-release methods are not necessarily effective, and the preparation method of granular pesticide preparations is complicated, and due to insufficient release of the pesticide composition, most of the active ingredients of the pesticide are not effectively utilized and remain in the pesticide composition. Moderate problems, such that more than necessary pesticide active ingredients are released into the environment, and as a result, the burden on the environment becomes large.

In addition, for the purpose of stabilizing different active ingredients, after preparing the inner core, a preparation method of a granular pesticide preparation coated with an active ingredient different from the inner core is provided (refer to Japanese Patent Application Laid-Open No. 9-315903), but The technique of labor-saving formulations for uniformly spreading the granular pesticide formulations exhibiting sustained release properties from the edge of the paddy fields has not been established yet.

Contents of the invention

Under such circumstances, the present invention will provide the following as a problem: it can be formulated in a simple method that overcomes the problems associated with conventional granular pesticide preparations, and can reduce the environmental A granular pesticide formulation that burdens, reduces or prevents drug hazards caused by pesticide active ingredients. The granular pesticide formulation is a uniformly diffusible granular pesticide formulation that can be uniformly spread throughout the paddy fields by a simple spreading method.

As a result of earnest research by the present inventors on uniform diffusible granular pesticide formulations, it was found that by making the composition into a non-disintegrating granular pesticide containing an acidic pesticide active ingredient, a cationic surfactant, and an alkaline substance, it has a particle diameter of 3mm Or 3mm or more particles mass ratio of 80% by mass or more of the particle size distribution and the properties of floating on the water surface, and disintegration in the water surface within 30 minutes or less, can solve the aforementioned problems, found that Based on this, the present invention has been accomplished.

That is, the present invention provides:

(1) A uniformly diffusible granular pesticide preparation, characterized in that it includes non-disintegrating pesticide granules, surfactants and floating components, and the non-disintegrating pesticide granules contain acidic pesticide active ingredients, cationic surfactants agent and alkaline substance, and non-disintegrating pesticide granules that do not disintegrate in water within 30 minutes or within 30 minutes; The particle size distribution of 80% by mass or more and the property of floating on the water surface immediately after being put into the water surface, but disintegrating on the water surface within 30 minutes or less,

(2) The uniformly diffusible granular pesticide formulation as described in (1) above, wherein the active ingredient of the acidic pesticide is a component with a pKa of 2 to 7,

(3) The uniformly diffusible granular pesticide formulation as described in (1) above, wherein the acidic pesticide active ingredient is a herbicide,

(4) The uniformly diffusible granular pesticide formulation as described in (3) above, wherein the herbicide is a sulfonylurea compound,

(5) The uniformly diffusible granular pesticide formulation described in (3) above, wherein the herbicide is the general formula (I)

[chemical 1]

( ^R in the formula is hydrogen atom, alkyl or alkoxyalkyl)

Represented difluoromethanesulfonyl anilide derivatives or salts thereof,

(6) The uniformly diffusible granular pesticide formulation as described in (1) above, wherein the cationic surfactant gels in water or exhibits swelling properties,

(7) The uniformly diffusible granular pesticide formulation as described in (1) above, wherein the basic substance is sodium bicarbonate, sodium carbonate, calcium hydroxide, calcium carbonate, basic white carbon black or basic acid clay,

(8) The uniformly diffusible granular pesticide formulation as described in (1) above, wherein the floating component is an inorganic hollow body or a plastic hollow body,

(9) A method for preparing a uniformly diffusible granular pesticide preparation, which is characterized in that the non-disintegrating pesticide granules, surfactants and floating components are granulated together to form spherical or short pellets with a particle diameter of 1 to 20 mm. A horizontally long shape with a diameter of 1 to 20 mm and a long diameter of 3 to 40 mm, the non-disintegrating pesticide granules contain acidic pesticide active ingredients, cationic surfactants and alkaline substances, and dissolve within 30 minutes or less Non-disintegrating pesticide granules that do not disintegrate in water,

(10) The production method described in (9) above, wherein the granulation treatment is carried out by extrusion granulation with a sieve with a mesh diameter (mesh opening diameter) larger than the particle diameter or particle size of the non-disintegrating pesticide granules ,

(11) A method for preparing a uniformly diffusible granular pesticide preparation, characterized in that the non-disintegrating pesticide granules, pesticide active ingredients, surfactants, and floating ingredients are granulated together to form a particle size of 1 to 20 mm spherical or horizontally long with a short diameter of 1-20 mm and a long diameter of 3-40 mm. The non-disintegrating pesticide granules contain acidic active ingredients of pesticides, cationic surfactants and alkaline substances, and dissolve in 30 minutes or 30 minutes. non-disintegrating pesticide granules that do not disintegrate in water, and

(12) The production method described in (11) above, wherein the granulation treatment is carried out by extrusion granulation with a sieve having a particle diameter or a larger mesh diameter than the non-disintegrating pesticide granules.

A brief description of the drawings

FIG. 1 is an explanatory diagram of a paddy field field to which a pesticide formulation is applied in Test Example 2. FIG.

The best way to practice the invention

The present invention will be described in detail below.

The non-disintegrating pesticide granules contained in the granular pesticide formulation of the present invention do not disintegrate in water for 30 minutes or less, and retain the granular prototype.

There is no particular limitation on the acidic pesticide active ingredients used in the non-disintegrating granules, but they are usually herbicides, plant growth regulators, fungicides, insecticides, etc., preferably within the range of pKa2～7, In addition, geometric isomers and optical isomers are also included.

As herbicide, there is no special limitation, but it is preferably pKa 2～7, especially by sulfonylurea compound or by following general formula (I)

[Chem 2]

(wherein R ¹ is a hydrogen atom, an alkyl group or an alkoxyalkyl group) represented by a difluoromethanesulfonyl anilide derivative or a salt thereof is particularly preferred.

As an example of a sulfonylurea compound, 1-(4,6-dimethoxypyrimidin-2-yl)-3-[1-methyl-4-(2-methyl-2H-tetrazole- 5-yl)pyrazol-5-ylsulfonyl]urea (Aim sulfron), 1-(2-chloroimidazo[1,2-a]pyridin-3-ylsulfonyl)-3-(4,6-di Methoxypyrimidin-2-yl)urea (Imazosulflon), 5-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-1-methylpyrazole-4-carboxylic acid ethyl Esters (Pyrazosulfuron (Pyrazosulfuron)), α-(4,6-dimethoxypyrimidin-2-ylcarbamoylaminosulfonyl)-O-Trol Ato methyl ester (Pyrazosulfuron (ベンスルフロンテチル)), 1-(4,6-dimethoxypyrimidin-2-yl)-3-(2-ethoxyphenoxysulfonyl)urea (ethoxysulfone (Etokisisulflon) ), 1-[2-(cyclopropylcarbonyl)anilinosulfonyl]-3-(4,6-dimethoxypyrimidin-2-yl)urea (cyclosulfonamide (Cyclosulfamuron)), 1 -(4,6-dimethoxy-1,3,5-triazin-2-yl)-3-[2-(2-methoxyethoxy)phenylsulfonyl]urea (Sinosolflon), 3-(4-Methoxy-6-methyl-1,3,5-triazin-2-ylformylaminosulfonyl)-2-thiophenic acid methyl ester (Chiphensul frontmechl), 2-(4 , 6-dimethoxypyrimidin-2-ylcarbamoylaminosulfonyl)-N,N-dimethylnicotinamide (Nicosolflon), 3-chloro-5-(4,6-dimethoxypyrimidine -2-ylcarbamoylaminosulfonyl)-1-methylpyrazole-4-carboxylic acid methyl ester (Harosul Fronmechl), 1-(4,6-dimethoxypyrimidin-2-yl)-3 -(3-trifluoromethyl-2-pyridylsulfonyl)urea (Frasasulflon), 1-(4,6-dimethoxypyrimidin-2-yl)-3-(3-ethylsulfonyl - 2-pyridylsulfonyl) urea (rim sulfon) and the like.

In addition, examples of difluoromethanesulfonyl anilide derivatives or salts thereof include compounds described in JP-A-2000-44546, such as 2-[(4,6-dimethoxypyrimidine-2- Base) hydroxymethyl]-N-difluoromethanesulfonylaniline, 2-[(4,6-dimethoxypyrimidin-2-yl)hydroxymethyl]-6-methoxymethyl-N- Difluoromethanesulfonylanilide, 2-[(4,6-dimethoxypyrimidin-2-yl)hydroxymethyl]-6-ethyl-N-difluoromethanesulfonylanilide and the like.

As examples of other herbicides, 2-methyl-4-chlorophenoxythioacetic acid-S-ethyl (phenolthiophene), α-(2-naphthyloxy) propionyl benzene (naproanilid ), 5-(2,4-dichlorophenoxy)-2-nitrobenzoic acid methyl ester (biferox), S-(4-chlorobenzyl)-N,N-diethylthiocarbamic acid Ester (Bentiocarb), 1,2-Dimethylpropyl (ethyl) S-benzyl thiocarbamate (Esporocalbu), S-Ethylhexahydro-1H-azepine-1-thiocarboxylate Ester (カボチオエト) (Morine ト), piperidine-1-thiocarboxylic acid-S-1-methyl-1-phenylethyl ester (シメピペルト), 6-methoxy- 2-Pyridine (methyl) thiocarbamate O-3-tert-butylphenyl ester (piribicalbu), 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetyl Anilide (butacrol), 2-chloro-2', 6'-diethyl-N-(2-propoxyethyl) acetylanilide (purchracrol), (RS)-2-bromo- N-α,α-dimethylbenzyl)-3,3-dimethylbutylamide (bromobutid), 2-benzothiazol-2-yloxy-N-methylacetanilide (Mefenaset), 1-(α, α-dimethylbenzyl)-3-(p-tolyl)urea (Dimron), 2-methylthio-4,6-bis(ethylamine)-s-triazine ( Simetrin), 2-methylthio-4,6-bis(isopropylamine)-s-triazine (Prometrin), 2-methylthio-4 ethylamine-6-(1,2-di Methylpropylamine)-s-triazine (ヅメタメトリン), 2,4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether (crometkisinil), 5-tert-butyl- 3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4,-oxyoxadiazol-2(3H)-one (Oxadiazol), 4-(2,4-di Chlorobenzoyl)-1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate (ヒラゾレ一ト), 2-[4-(2,4-dichlorobenzoyl)-1,3 -Dimethylpyrazol-5-yloxy]acetophenone (ヒラゾキシフエン), (RS)-2-(2,4-dichloro-m-tolyloxy)propionanilide (chromeprotop), 2 -[4-[2,4-Dichloro-m-tolyl]-1,3-dimethylpyrazol-5-yloxy]-4'-methylacetophenone Fluoromethane-4-isobutyl-6-trifluoromethylpyridine-3,5-dicarboxylic acid S, S'-dimethyl ester (ヅチオヒル), 2-chloro-N-(3-methoxy-2 - Thienyl-2', 6'-dimethylacetanilide (Tenylcrol), (R)-2-[4-(4-cyano-2fluorophenoxy)phenoxy]propanoic acid Butyl ester (shiharohopbuchol), 3-[1-(3,5-dichlorophenyl)-1-methylethyl]-2,3-dihydro-6-methyl-5-phenyl- 4H-1,3-oxazin-4-one (Oxazin-4-one), 3-(4-chloro-5-cyclopentyloxy-2-fluorophenyl)-5-isopropylidene-1,3-oxazolidine -2,4-diketone (Pentokisazon), 1-(diethylcarbamoyl)-3-(2,4,6-trimethylphenylsulfonyl)-1,2,4-triazole (カフエンストロOne lu), 2-[(4,6-dimethoxypyrimidin-2-yl)oxy]-6-[(E)-1-(methoxyimino)ethyl]benzoic acid methyl ester ( piriminovacmechol) and so on.

The plant growth regulator is not particularly limited, and 4'-chloro-2'-(α-hydroxybenzyl)isonicotinamide (Inabenfid), (2RS, 3RS)-1-(4-chlorobenzene Base)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-alcohol (Pacrobutra 1-ol), (E)-(S)-1- (4-Chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol (ウニコナゾ-1-ol), 3 - Calcium oxo-5-oxo-4-propionylcyclohex-3-enecarboxylate (prohekysazion calcium salt), choline maleic acid hydrazide, and the like. Of these, those with a pKa of 2 to 7 are particularly suitable.

The fungicide is not particularly limited, and O, O-diisopropyl-S benzyl phosphorothioate (チオホスフエト) (IBP), 3'-isopropoxy-2-methylbenzyl Anilide (Mepronil), α,α,α-Trifluoro-3'-isopropoxy-O-trianiline (Flutranil), 3,4,5,6-tetrachloro-N-(2,3- Dichlorophenyl) phthalic acid (Tecroftaram), 1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea (Penceclon), 6-(3,5-dichloro-4-methyl N-(2-methoxyacetyl)-N-(2,6-methylbenzyl)-DL-alanine methyl ester (Metalakisil), (E)-4-chloro-α,α,α-trifluoro-N-(1-imidazol-1-yl-2-propoxyethylene)-o-toluidine ), kasugamycin, validamycin, 3-aryloxy-1,2-benzisothiazole-1,1-dioxide (probenazol), diisopropyl-1,3-two tetra Hydrothiophene-2-iriden-malonate (inprothiolan), 5-methyl-1,2,4-triazolo[3,4-b]benzothiazole (tricyclazole) ), 1,2,5,6-tetrahydropyrrolo[3,2,1-ij]quinolin-4-one (Hirokilon), 5-ethyl-5,8-dihydro-8-oxo[ 1,3]dioxo[4,5-g]quinoline-7-carboxylic acid (okinlinkic acid), 4,6-dimethylpyrimidin-2-ylhydrazone-4,5,6,7-tetra Chlorophthalone (Z)-2'-Methylacetophenone (Ferimon), 3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1- Carboxamide (iprogion) and the like. Of these, those with a pKa of 2 to 7 are particularly suitable.

As an insecticide, there is no particular limitation, and O, O-dimethyl-O-(3-methyl-4-nitrophenyl) phosphorothioate (MEP), (2-isopropyl- 4-methylpyrimidinyl-6)-diethylphosphorothioate (Diajinon), 1-naphthyl-N-methylcarbamate (NAC), O, O-diethyl-O-(3 -Oxo-2-phenyl-2H-pyridazin-6-yl)phosphorylsulfuryl (Hosohorochioet) (Piridafenchin), O, O-dimethyl-O-3,5,6-tri Chloro-2-pyridyl phosphorothioate (crolpirihorsmechl), dimethyldiethoxyformylethyl phosphorodithioate (malason), O, O-dimethyl-S-(N-methylaminomethyl Acylmethyl) phosphorodithioate (jimetoet), O, O-dipropyl-O-4-methylthiophene phosphate (Prophathos), O, S-dimethyl-N-acetylphosphoric acid Amide (ホスホロアミドチオエエト) (アスフエトト), ethyl p-nitrophenylthiocarbon (チオノ) phenylphosphonate (EPN), 2-sec-butylphenyl-N-methylamino Formate (BPMC), 2,3-dihydro-2,2-dimethyl-7-benzo[b]furyl N-dibutylaminothio-N-methylcarbamate ), N-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio]-N-isopropyl-β-alanine ethyl ester (Benfracalbu), (RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropionic acid (RS)-α-amino-3-phenoxybenzyl ester (Sicuroprotolin ), 2-(4-ethoxyphenyl)-2-methylpropyl=3-phenoxybenzyl=ether (Etofenprox), 1,3-bis(carbamoylthio)-2- (N,N-Dimethylamino)propane hydrochloride (Caltap), 5-Dimethylamino-1,2,3-trithiane bromide (Choosiclam), S,S'-2-dimethyl Amino trimethylene = bis(phenylthiophosphonate) (Bensultap), 2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5,6-tetrahydro- 2H-1,3,5-thiadiazin-4-one (buprofen) and the like. Of these, those with a pKa of 2 to 7 are particularly suitable.

In the case of using an acidic pesticide active ingredient with the pKa specified above, the pKa of the ingredient is, for example, given in Experimental Chemistry Lecture 5 (thermal measurement and equilibrium) p469-p474 issued by Maruzen Co., Ltd. on January 20, 1933. determined by the method described above.

The cationic surfactant used in the present invention is not particularly limited, and preferred examples thereof include amine salts, pyridinium salts, and quaternary ammonium salts.

Examples of amine salt cationic surfactants include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine Acetate etc.

Examples of the pyridinium salt-based cationic surfactant include laurylpyridinium chloride, myristylpyridinium chloride, cetylpyridinium chloride, and the like.

Examples of quaternary ammonium cationic surfactants include alkyl dimethyl benzyl ammonium chloride, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, and stearyl trimethyl ammonium chloride. Ammonium Chloride, Dilauryl Dimethyl Ammonium Chloride, Dioleyl Dimethyl Ammonium Chloride, Dicocoyl Dimethyl Ammonium Chloride, Distearyl Dimethyl Ammonium Chloride, Lauryl Dimethyl Ammonium Chloride Dihydroxyethyl methyl ammonium chloride, oleyl dipolyoxyethane methyl ammonium chloride, stearyl hydroxyethyl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, lauryl di Methylbenzylammonium Chloride, Lauroyl Aminopropyl Dimethyl Ethyl Ammonium Ethosulfate wait.

Cationic surfactants are especially suitable for gelling in water, or showing swelling properties, for example: dialkyl dimethyl ammonium chloride, the alkyl part of which is C ₈ -C ₂₂ , of which dilauryl di Methyl ammonium chloride, dioleyl dimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, etc. These surfactants may be used alone or in combination of two or more.

The alkaline substance used in the present invention is not particularly limited, preferably when the 1% by mass aqueous solution or 1% by mass aqueous suspension has a pH of 7.5 or above, preferably pH 9-12. Examples of such a base include hydroxides of alkali metals or alkaline earth metals, salts of alkali metals or alkaline earth metals, compounds or minerals containing these, and the like. More specifically, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, calcium hydroxide, calcium carbonate, calcium oxide, basic white carbon black, basic acid clay, etc., especially sodium bicarbonate , sodium carbonate, calcium hydroxide, calcium carbonate, basic silica and basic acid clay are preferred. These basic substances may be used alone or in combination of two or more.

The surfactant used in the present invention is not particularly limited, and examples thereof include polyoxyalkylene diol higher fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylaryl ethers, polyoxyalkylene alkylaryl Nonionic surfactants such as phenyl ether, sorbitan monoalkylate, acetylene glycol, polyoxyethylene acetylene glycol, etc.; alkylaryl sulfonate, dialkyl sulfonate, alkyl sulfate salt, Alkyl phosphates, alkylaryl phosphates, alkylaryl phosphates, polyoxyalkylene alkyl ether sulfates, naphthalene sulfonates and their condensates, alkylnaphthalene sulfonates and their condensates , lignosulfonate, acrylic acid-itaconic acid copolymer, methacrylic acid-itaconic acid copolymer, maleic acid-styrene copolymer, maleic acid-isobutylene copolymer, and alkali metal salts of these, etc. Polycarboxylic acid polymer surfactants; anionic surfactants such as polyoxyalkylene aryl phenyl ether sulfate salts. These may be used alone or in combination of two or more.

The buoyant substance used in the present invention is not particularly limited as long as it floats on the water surface when it is thrown into the water surface, and it can be listed respectively: as inorganic substances, such as glassy hollow bodies, foamed beads, foamed Foam fly ash, vermiculite, burnt vermiculite, tendril balls (Silas balone), microspheres, hollow microspheres and other inorganic hollow bodies, as well as organic matter, plastic hollow bodies, waxes, solid paraffins, foam-containing Starch, cork, wood chips, corncobs and other plant chips, organic solvents with light specific gravity such as polybutene, etc. In particular, glass-made hollow bodies and inorganic hollow bodies such as shilas heating foams, and plastic hollow bodies such as vinylidene chloride-acrylonitrile copolymer plastic balls and acrylonitrile-based plastic balls are preferable. These may be used alone or in combination of two or more.

The uniformly dispersed granular agrochemical formulation of the present invention may contain additive components generally used in agrochemical formulations as necessary. As this additional component, an extender, an auxiliary component, etc. can be used.

As the bulking agent, solid carriers such as mineral carriers, or water-soluble salts, etc. can be used, and specific examples include: clay, calcium carbonate, bentonite, talc, diatomaceous earth, acid clay, silica sand, granular calcium carbonate, granular diatom Soil, calcium stearate, white carbon black, potassium chloride, anhydrous sodium sulfate, potassium sulfate, urea, ammonium sulfate, sodium benzoate, etc. These may be used alone or in combination of two or more.

As an auxiliary component, for example, a binder when preparing a granular composition, specifically, carboxymethylcellulose sodium salt, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinylpyrrolidone, polyvinylpyrrolidone, Ethylene glycol, sodium polyacrylate, polyethylene glycol with an average molecular weight of 6,000 to 20,000, polyethylene oxide with an average molecular weight of 100,000 to 5 million, etc. In addition, when dissolving acidic pesticide components and cationic surfactants and adsorbing them on the carrier, specific examples of organic solvents used include alkylnaphthalene, dimethylformamide, dimethylsulfoxide, N-methyl- 2-pyrrolidone, N-octylpyrrolidone, polyol, silicone oil, etc. In addition, a stabilizer etc. can also be used as needed. These may be used alone or in combination of two or more.

In the uniformly diffusible granular pesticide formulation of the present invention, the composition ratio of the non-disintegrating pesticide granular material is usually 0.1 to 40% by mass of an acidic pesticide component, 1 to 40% by mass of a cationic surfactant, and 0.1% by mass of an alkaline substance. It is selected within the range of ~95% by mass, and preferably the pH of a 1% by mass aqueous suspension of the non-disintegrating pesticide granules is usually adjusted to 5 or more, preferably 7 or more, more preferably 7.5 to 11.5.

In addition, the composition ratio of the uniformly diffusible granular pesticide preparation of the present invention is usually 1 to 70% by mass of the non-disintegrating pesticide granular product, 0 to 50% by mass of the active ingredient of the pesticide, and 0.1 to 30% by mass of the surfactant. 0.1 to 50% by mass of floating components, 0 to 95% by mass of bulking agents, preferably 5 to 70% by mass, 0 to 50% by mass of auxiliary components, preferably 0.1 to 30% by mass, more preferably 1 capsule The specific gravity is less than 1, so choose within the range that is sufficient to float on the water surface.

The uniform diffusible granular pesticide preparation of the present invention disintegrates within 30 minutes or less after being treated in the nursery, and the non-disintegrating pesticide granules contained in it are slowly disintegrated in the nursery during the disintegration Uniform sedimentation enables the release of the pesticide active ingredient contained in the pesticide granules to be dissolved and released slowly. It is a labor-saving type of release-controlled pesticide preparation, but by including the pesticide active ingredient that does not want to be released slowly, it is different from the non-disintegrating type. Uniformly diffusible granular pesticide formulations of pesticide granules can also be designed to suit the dissolution properties of each pesticide active ingredient.

In addition, the present invention also includes a mixed pesticide preparation obtained by mixing the uniform diffusible granular pesticide formulation and the uniform diffusible granular pesticide formulation free of cationic surfactants and alkaline substances at a mass ratio of 1:9 to 9:1. .

In the uniformly diffusible granular pesticide formulation of the present invention, it is good if the size itself is as follows: in the case of a spherical shape, usually a particle diameter of 1 to 20 mm, preferably 3 to 10 mm; 20 mm, preferably 3 to 10 mm, long diameter 3 to 40 mm, preferably 5 to 30 mm; the size of the non-disintegrating pesticide granules contained in the pesticide preparation is good when the size is as follows: spherical, usually a particle size of 0.01 to 5 mm, preferably 0.1 to 3 mm; in the case of a horizontally long shape, usually the short diameter is 0.1 to 10 mm, preferably 0.5 to 7 mm, and the long diameter is 0.3 to 30 mm, preferably 1.5 to 20 mm.

There are no particular limitations on the method of preparing the uniformly diffusible granular pesticide formulation of the present invention and the non-disintegrating pesticide granules contained in the formulation, for example, using the known tumbling granulation method, extrusion granulation method , coating granulation method, etc.

As a method for preparing the uniformly diffusible granular pesticide preparation of the present invention, the following method can preferably be mentioned: a method that contains an acidic pesticide active ingredient, a cationic surfactant, and an alkaline substance, and does not disintegrate in water within 30 minutes or less. The non-disintegrating pesticide granules are granulated together with surfactants and floating components to form a spherical shape with a particle diameter of 1-20 mm or a horizontally long shape with a short diameter of 1-20 mm and a long diameter of 3-40 mm.

(Preparation of non-disintegrating pesticide granules)

The tumbling granulation method is formed by the following process: adding acidic pesticide active ingredients, cationic surfactants and alkaline substances, together with auxiliary ingredients such as binders or extenders, into the tumbling granulator to prepare powdery raw materials The process; slowly adding an appropriate amount of water or an aqueous solution in which a binder is dissolved to the powdery raw material to prepare a granular composition with a target particle size or grain length; and coating the granular composition on its surface as necessary The film-forming substance is dried and then sieved.

The extrusion granulation method is formed by the following process: the acidic pesticide active ingredients, cationic surfactants and alkaline substances are subjected to jet milling (Eamil) or mechanochemical milling together with auxiliary components such as binders or extenders, A process of preparing a powdery raw material; kneading a mixture obtained by adding an appropriate amount of water to the powdery raw material with a kneader such as a biaxial kneader, an extrusion granulator, etc., and then setting it to have a target particle size or particle size A step of extruding and granulating through a sieve with a long mesh to prepare a granular composition; and a step of coating the surface of the granular composition with a film-forming substance as necessary, drying, and then sieving.

The coating granulation method is formed by the following process: the acidic pesticide active ingredients, alkaline substances and cationic surfactants used as necessary, together with auxiliary ingredients such as extenders, are subjected to airflow or mechanochemical pulverization to prepare powder The process of raw materials; the oil-absorbing granules with the target particle size or particle length are added to the conical screw type mixer, and the auxiliary components such as the cationic surfactant diluted with the solvent and the binder used if necessary are sprayed at the same time. The step of coating the powdered material obtained in the preceding step on the oil-absorbing granules obtained by mixing to prepare a granular composition; and the step of sieving the granular composition after drying if necessary.

(Preparation of Granular Pesticide Formulation)

The extrusion granulation method is formed by the following process: the non-disintegrating pesticide granules obtained according to the previous method, surfactants and floating components, and extenders, binders or stabilizers used as necessary Auxiliary components and pesticide active ingredients are used such as a kneader such as a two-shaft kneader, an extrusion granulator, etc., and an appropriate amount of water is added to knead, and the resulting mixture is reduced from the particle size of the non-disintegrating pesticide granules. Or a process of extruding granulation through a sieve with a larger particle size to prepare a granular composition; and a process of coating the surface of the granular composition with a film-forming substance as necessary, drying, and then sieving.

The tumbling granulation method is formed by the following process: the non-disintegrating pesticide granules obtained according to the previous method, surfactants and floating components, and bulking agents, binders or stabilizers used as necessary Auxiliary ingredients and pesticide active ingredients are added to the rotary granulator to prepare powdery raw materials; slowly add an appropriate amount of water or an aqueous solution in which the binder is dissolved to the powdery raw materials to prepare granular materials with the target particle size or particle length. a composition step; and a step of coating the surface of the granular composition with a film-forming substance as necessary, drying, and then sieving.

In these production methods, the drying treatment may be performed with an appropriate drying device such as a fluidized bed drying device or a vacuum drying device.

In the uniformly diffusible granular pesticide formulation of the present invention, as the active ingredient of the acidic pesticide, a substance with a pKa of 2 to 7 is preferably used, wherein the herbicide is, for example, a herbicide formed by a sulfonylurea compound, especially the aforementioned general formula (I) The difluoromethanesulfonanilide derivative or its salt shown above is preferably used as a cationic surfactant that gels in water or exhibits swelling properties.

Hereinafter, the present invention will be described in detail in examples and test examples, but the present invention is not limited by these examples in any way. In addition, the part in each example shows a mass part.

Each of the pesticide active ingredients used in the examples has a pKa of 2 to 7, each of the alkaline substances is a 1% by mass aqueous solution or a 1% by mass aqueous suspension with a pKa of 7.5 or more, and is non-disintegrating The pesticide granules were each a 1% by mass aqueous suspension and had a pKa of 5 or more.

In addition, each of the cationic surfactants used in Examples 1, 7, and 9 to 10 gelled in water.

Furthermore, the uniformly diffusible granular pesticide preparations obtained in each of the examples floated on the water surface immediately after being put into the water surface, but disintegrated within 30 minutes or less, and the non-disintegrating pesticide granules settled.

Example 1

6.25 parts of benzsulfuron (pKa 5.03), 6.25 parts of distearoyl dimethyl ammonium chloride, 6.25 parts of dilauryl dimethyl ammonium chloride, 68.75 parts of calcium carbonate, 6.25 parts of polyvinyl alcohol, α The uniformly mixed mixture of 6.25 parts of starch was pulverized with an impact mill. Add appropriate amount of water to the obtained powder in a high-speed mixer for kneading, use a dome granulator, extrude and granulate with a sieve with a mesh diameter of 0.5mm, and dry the granules at 60°C. , to obtain the pesticide granules containing benzsulfuron 6.25% by mass, with a diameter of 0.4-0.6 mm and a length of 1-6 mm. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 32 parts of non-disintegrating pesticide granules, 3 parts of polyoxyethylene acetylene glycol, 2 parts of enzyme-modified dextrin, and vinylidene chloride-acrylonitrile copolymer plastic balls [Mazumoto Microcross] as plastic hollow bodies Feia-F-30E (trade name), Matsumoto Yushi Pharmaceutical Co., Ltd.] 14 parts, 20 parts of anhydrous sodium sulfate, and 40.9 parts of urea were mixed with an appropriate amount of water. After kneading with a two-shaft kneader, use an extrusion out of the granulator, extrude and granulate with a sieve with a mesh diameter of 5mm, and then granulate into the target size, then dry it through a fluidized bed dryer at a product temperature of 60°C, and sieve to obtain a uniform diffusible granular pesticide preparation with a diameter of 3-7mm, length 3-20mm, containing 2% by mass of bensulfuron-uron granular. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Example 2

6.25 parts of benzsulfuron (pKa 5.03), 12.5 parts of dioleyl dimethyl ammonium chloride, 62.5 parts of calcium carbonate, and 12.5 parts of bentonite were homogeneously mixed, and pulverized by an impact mill. After adding 12.5 parts of acrylic emulsion containing 50% solid content and an appropriate amount of water to the obtained powder in a high-speed mixer and kneading, use a dome granulator to extrude and granulate with a sieve with a mesh diameter of 0.5 mm. Standing and drying at 60° C., pesticide granules containing 6.25% by mass of bensulfuron-uron, 0.4 to 0.6 mm in diameter and 1 to 6 mm in length were obtained. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 32 parts of the non-disintegrating pesticide granules, 32 parts of Mefenaset, finely pulverized by jet milling, 1 part of dioctyl sulfosuccinate, 2 parts of polyoxyethylene acetylene glycol, enzyme-modified 3 parts of dextrin, 12 parts of plastic hollow bodies used in Example 1, 5 parts of bentonite, 10 parts of anhydrous sodium sulfate, and 13.2 parts of urea were mixed with an appropriate amount of water. After kneading with a two-shaft kneader, Use an extrusion granulator to extrude and granulate with a sieve with a mesh diameter of 5mm. After sizing the granules into the target size, they are dried by a fluidized bed dryer at a product temperature of 60°C and sieved to obtain a uniform diffusible granular pesticide preparation. A granular material containing 2% by mass of benzsulfuron and 32% by mass of Mefenaset with a diameter of 3 to 7 mm and a length of 3 to 20 mm. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Example 3

In the general formula (I), R ¹ is an ethyl compound (hereinafter referred to as compound A. pKa 6.17) 10 parts, basic white carbon black 1.7 parts are uniformly mixed, and the powder containing compound A is prepared by jet milling for fine pulverization.

Add 75 parts of diatomite with a particle size of 16 to 35 mesh (1000 to 425 μm) into the conical screw mixer, and add 10 parts of dilauryl dimethyl ammonium chloride, propylene glycol 2 parts, 1.3 parts of polypropylene glycol (molecular weight: 1000) and a cationic surfactant solution prepared by heating and mixing. Immediately after the addition, the above-mentioned powder containing Compound A was added, uniformly mixed to form granules, and the granules were aged in a tray (shelf section) dryer at 60°C to obtain pesticide granules with a particle size of 0.4-1.1 mm. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 30 parts of the non-disintegrating pesticide granules, 3 parts of sodium dibutylnaphthalene sulfonate, 2 parts of lauryl sulfate, 3 parts of polyoxyethylene acetylene glycol, 2 parts of enzyme-modified dextrin, poly 1 part of sodium acrylate, 2 parts of white carbon black, 14 parts of the plastic hollow body used in Example 1, 20 parts of anhydrous sodium sulfate, and 34.9 parts of urea are mixed with an appropriate amount of water, and kneaded with a two-axis kneader After that, use an extrusion granulator to carry out extrusion granulation with a sieve with a mesh diameter of 5mm. After sizing the granules into the target size, they are dried by a fluidized bed dryer at a product temperature of 60°C and sieved to obtain uniform diffusible granules. Pesticide preparations are granules containing 3% by mass of Compound A with a diameter of 3 to 7 mm and a length of 3 to 20 mm. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Example 4

Mix 7.5 parts of compound A (pKa 6.17), 10 parts of N-methyl-2-pyrrolidone, and 10 parts of dioleyl dimethyl ammonium chloride with a propeller mixer to prepare a solution containing compound A. The obtained solution is adsorbed on 75 parts of alkaline acid clay with a particle size of 16 to 35 mesh (1000 to 425 μm) at a pH of 7 to 10 in a 1% aqueous suspension to obtain pesticide granules with a particle size of 0.4 to 1.1 mm . The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 40 parts of the non-disintegrating pesticide granules, 3 parts of sodium dibutylnaphthalene sulfonate, 2 parts of lauryl sulfate, 2 parts of polyoxyethylene acetylene glycol, 0.7 parts of sodium polyacrylate, ring-shaped insulating glass [Fuji Balone (trade name) Fuji Silysia Chemical Co., Ltd.] 20 parts, 15 parts of anhydrous sodium sulfate, and 17.3 parts of urea were uniformly mixed with a high-speed mixer, and after adding an appropriate amount of water for kneading, the resulting mixture was molded in a basket The granulator uses a sieve with a mesh diameter of 5mm to carry out extrusion granulation. After the granulation is sized to the target size, it is dried by a fluidized bed dryer at a product temperature of 60°C and sieved to obtain a uniform diffusible granular pesticide preparation with a diameter of 3-7mm. , A granular material containing 3% by mass of Compound A having a length of 3 to 20 mm. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Example 5

In general formula (I), R ¹ is methoxymethyl compound (hereinafter referred to as compound B. pKa5.75) 10 parts, distearyl dimethyl ammonium chloride 6.7 parts, dilauryl dimethyl The uniformly mixed mixture of 6.7 parts of ammonium chloride, 63.2 parts of calcium carbonate, 6.7 parts of polyvinyl alcohol and 6.7 parts of pregelatinized starch was pulverized with an impact mill. After kneading the mixture obtained by adding an appropriate amount of water to the obtained powder with a high-speed mixer, use a dome granulator to extrude and granulate with a sieve with a mesh diameter of 0.5mm, and dry the granules at 60°C to obtain Compound B 10% by mass, a pesticide granule with a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm. The obtained pesticide granules were poured into water, and the disintegration state of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 30 parts of the non-disintegrating pesticide granules, 1 part of polyoxyethylene acetylene glycol, 2 parts of polyoxyethylene polyoxypropylene block polymer, 3 parts of polyoxyethylene styrene phenyl ether phosphate amine salt , 3 parts of enzyme-modified dextrins, 14 parts of plastic hollow bodies used in Example 1, 5 parts of bentonite, 20 parts of anhydrous sodium sulfate, 30.9 parts of urea, the mixture of adding an appropriate amount of water, carried out with a two-axis kneader After kneading, use an extrusion granulator to carry out extrusion granulation with a sieve with a mesh diameter of 5mm. After sizing the granules into the target size, they are dried by a fluidized bed dryer at a product temperature of 60°C and sieved to obtain a uniform diffusion A granular pesticide preparation with a diameter of 3 to 7 mm and a length of 3 to 20 mm containing 3% by mass of Compound B. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Example 6

6.25 parts of compound B (pKa 5.75), 12.5 parts of distearyl dimethyl ammonium chloride, 62.5 parts of calcium carbonate, and 12.5 parts of bentonite were uniformly mixed and pulverized by an impact mill. After adding 6.25 parts of acrylic acid emulsion and an appropriate amount of water to the obtained powder, knead with a high-speed mixer, use a dome granulator, extrude and granulate with a sieve with a mesh diameter of 0.5 mm, and statically place the granulated material at 60 ° C. Set to dry, obtain the pesticide granule containing compound B 6.25 mass %, diameter 0.4～0.6mm, length 1～6mm. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 32 parts of the non-disintegrating pesticide granules, 1 part of compound B finely pulverized by jet milling, 1 part of polyoxyethylene acetylene glycol, 2 parts of polyoxyethylene polyoxypropylene block polymer, poly 3 parts of oxyethylene styrene phenyl ether amine phosphate salts, 3 parts of enzyme-modified dextrins, 14 parts of plastic hollow bodies used in Example 1, 5 parts of bentonite, 20 parts of anhydrous sodium sulfate, 30.9 parts of urea, add an appropriate amount of After kneading the water mixture with a two-axis kneader, use an extrusion granulator to extrude and granulate with a sieve with a mesh diameter of 5mm. After the granules are sized to the target size, they pass through the fluidized layer at a product temperature of 60°C. Dried in a drier and sieved to obtain a granular product containing 3% by mass of Compound B as a uniform diffusible granular pesticide preparation with a diameter of 3 to 7 mm and a length of 3 to 20 mm. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Example 7

10 parts of compound B (pKa 5.75), 13.3 parts of distearyl dimethyl ammonium chloride, 56.9 parts of calcium carbonate, and 13.3 parts of bentonite were homogeneously mixed and pulverized with an impact mill. After adding 13 parts of acrylic emulsion containing 50% solids and an appropriate amount of water to the obtained powder and kneading with a high-speed mixer, use a dome granulator to extrude and granulate with a sieve with a mesh diameter of 0.5 mm. The granulated product was left standing and dried at 60° C. to obtain a pesticide granulated product containing 10% by mass of Compound B, having a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 30 parts of the non-disintegrating pesticide granules, 8 parts of fuentrazamide finely pulverized by jet milling, 5 parts of sodium dibutylnaphthalene sulfonate, 1 part of lauryl sulfate, polyoxyethylene acetylene glycol 3 parts, 2 parts of enzyme-modified dextrins, 0.5 parts of sodium polyacrylate, 14 parts of plastic hollow bodies used in Example 1, 20 parts of anhydrous sodium sulfate, 28.4 parts of urea, the mixture of adding an appropriate amount of water, using a two-axis After kneading by a type kneader, use an extrusion granulator to extrude and granulate with a sieve with a mesh diameter of 5 mm. After the granules are sized to the target size, they are dried by a fluidized bed dryer at a product temperature of 60 ° C, and sieved. A granular product containing 3% by mass of Compound B and 8% by mass of Funtrazamid with a diameter of 3 to 7 mm and a length of 3 to 20 mm was obtained as a uniform diffusible granular pesticide preparation. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Example 8

Uniformly mix 6.25 parts of pyrazosulfuron (pKa 3.91), 6.25 parts of cetyltrimethylammonium chloride, 68.75 parts of calcium carbonate, and 18.75 parts of polyvinyl alcohol, and pulverize it with an impact mill. After adding an appropriate amount of water to the obtained powder and kneading with a high-speed mixer, use a dome granulator to extrude and granulate with a sieve with a mesh diameter of 0.5 mm, and dry the granules at 60 ° C to obtain Pesticide granules with 6.25% by mass, 0.4 to 0.6 mm in diameter, and 1 to 6 mm in length. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, in 16 parts of the non-disintegrating pesticide granules, 5 parts of butyl naphthalene sulfonic acid formalin condensate sodium salt, 1 part of polyoxyethylene acetylene glycol, 0.5 parts of sodium polyacrylate, in Example 1 A mixture of 14 parts of plastic hollow bodies, 20 parts of anhydrous sodium sulfate, and 55.4 parts of urea with an appropriate amount of water added, kneaded with a high-speed mixer, and then extruded through a sieve with a mesh diameter of 5 mm using an extrusion granulator After granulation and granulation into the target size, the product temperature is 60° C., dried by fluidized bed dryer, and sieved to obtain a uniform diffusible granular pesticide preparation with a diameter of 3 to 7 mm and a length of 3 to 20 mm containing 1% by mass. Granules of pyrazosulfuron. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Example 9

20 parts of tricyclazole (pKa 1.6), 15 parts of distearyl dimethyl ammonium chloride, 55 parts of calcium carbonate, and 10 parts of polyvinyl alcohol were homogeneously mixed and pulverized with an impact mill. After adding an appropriate amount of water to the obtained powder and kneading with a high-speed mixer, use a dome granulator to extrude and granulate with a sieve with a mesh diameter of 0.7mm, and dry the granulated material at 60°C to obtain tricyclazole-containing 20% by mass, a pesticide granule with a diameter of 0.6 to 0.8 mm and a length of 2 to 9 mm. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 40 parts of the non-disintegrating pesticide granules, 5 parts of butyl naphthalene sulfonic acid formalin condensate sodium salt, 1 part of polyoxyethylene acetylene glycol, and 0.5 parts of sodium polyacrylate were used as plastic hollow bodies. The acrylonitrile plastic ball [Mazumotomaicrossfea-F-80E (trade name), Matsumoto Yuyu Pharmaceutical Co., Ltd.] 14 parts, anhydrous sodium sulfate 20 parts, urea 31.4 parts, add the mixture of an appropriate amount of water, with a high-speed mixer After kneading, use an extrusion granulator to extrude and granulate with a sieve with a mesh diameter of 5mm. After sizing the granules into the target size, they are dried by a fluidized bed dryer at a product temperature of 60°C and sieved to obtain a homogeneous The diffusible granular pesticide formulation is a granular product containing 8% by mass of tricyclazole with a diameter of 3 to 7 mm and a length of 3 to 20 mm. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Example 10

20 parts of PHC (pKa 11.6), 15 parts of distearyl dimethyl ammonium chloride, 55 parts of calcium carbonate, and 10 parts of polyvinyl alcohol were homogeneously mixed and pulverized with an impact mill. After adding an appropriate amount of water to the obtained powder and kneading with a high-speed mixer, use a dome granulator to extrude and granulate with a sieve with a mesh diameter of 0.7mm, and dry the granules at 60°C to obtain PHC-containing 20% by mass, a pesticide granule with a diameter of 0.6 to 0.8 mm and a length of 2 to 9 mm. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, in 40 parts of the non-disintegrating pesticide granules, 5 parts of butyl naphthalene sulfonic acid formalin condensate sodium salt, 1 part of polyoxyethylene acetylene glycol, 0.5 parts of sodium polyacrylate, Example 9 A mixture of 14 parts of plastic hollow body, 20 parts of anhydrous sodium sulfate, and 31.4 parts of urea is added with an appropriate amount of water. After kneading with a high-speed mixer, use an extrusion granulator to extrude through a sieve with a mesh diameter of 5 mm. After granulating and sizing into the target size, the product temperature is 60° C., dried by fluidized bed dryer, and sieved to obtain a uniform diffusible granular pesticide preparation with a diameter of 3 to 7 mm and a length of 3 to 20 mm containing 8% by mass. Granular matter of PHC. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Comparative example 1

6.25 parts of benzsulfuron (pKa 5.03), 81.25 parts of calcium carbonate, 6.25 parts of polyvinyl alcohol, and 6.25 parts of α-starch were homogeneously mixed, and pulverized by an impact mill. After adding an appropriate amount of water to the obtained powder and kneading with a high-speed mixer, use a dome granulator to extrude and granulate with a sieve with a mesh diameter of 0.5mm, and dry the granules at 60°C to obtain 6.25% by mass of rimsulfuron, pesticide granules with a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 32 parts of non-disintegrating pesticide granules, 3 parts of polyoxyethylene acetylene glycol, 2 parts of enzyme-modified dextrin, 14 parts of plastic hollow bodies used in Example 1, and 20 parts of anhydrous sodium sulfate , 40.9 parts of urea, the mixture of adding an appropriate amount of water, after kneading with a two-shaft kneader, use an extrusion granulator to extrude and granulate with a sieve with a mesh diameter of 5mm. After the granules are sized into the target size, The product is dried by a fluidized bed dryer at a temperature of 60° C., and sieved to obtain a uniform diffusible granular pesticide preparation with a diameter of 3-7 mm and a length of 3-20 mm containing 2% by mass of bensulfuron-methyl. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Comparative example 2

10 parts of compound A (pKa 6.17) and 1.7 parts of basic silica were uniformly mixed, and a compound A-containing powder finely pulverized by jet milling was prepared.

Add 75 parts of diatomite particles with a particle size of 16 to 35 mesh (1000 to 425 μm) into the conical screw mixer, and add 12 parts of propylene glycol and 1.3 parts of polypropylene glycol (molecular weight: 1000) with a propeller mixer while mixing. Warm and mix the prepared solution. Immediately after the addition, the powder containing the above compound A was added, uniformly mixed to form granules, and the granules were aged in a tray dryer at 60°C to obtain pesticide granules with a particle size of 0.4-1.1 mm. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 30 parts of the non-disintegrating pesticide granules, 3 parts of sodium dibutylnaphthalene sulfonate, 2 parts of lauryl sulfate, 3 parts of polyoxyethylene acetylene glycol, 2 parts of enzyme-modified dextrin, poly 1 part of sodium acrylate, 2 parts of white carbon black, 14 parts of the plastic hollow body used in Example 1, 20 parts of anhydrous sodium sulfate, and 34.9 parts of urea are mixed with an appropriate amount of water, and kneaded with a two-axis kneader After that, use an extrusion granulator to carry out extrusion granulation with a sieve with a mesh diameter of 5mm. After sizing the granules into the target size, they are dried by a fluidized bed dryer at a product temperature of 60°C and sieved to obtain uniform diffusible granules. Pesticide preparations are granules containing 3% by mass of Compound A with a diameter of 3 to 7 mm and a length of 3 to 20 mm. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Comparative example 3

10 parts of compound B (pKa 5.75), 6.7 parts of distearyl dimethyl ammonium chloride, 6.7 parts of dilauryl dimethyl ammonium chloride, 63.2 parts of clay (クレ一), 6.7 parts of polyvinyl alcohol, alpha The uniformly mixed mixture of 6.7 parts of starch was pulverized with an impact mill. After kneading the mixture obtained by adding an appropriate amount of water to the obtained powder with a high-speed mixer, use a dome granulator to extrude and granulate with a sieve with a mesh diameter of 0.5mm, and dry the granules at 60°C to obtain Compound B 10% by mass, pesticide granules with a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, 30 parts of the non-disintegrating pesticide granules, 1 part of polyoxyethylene acetylene glycol, 2 parts of polyoxyethylene polyoxypropylene block polymer, 3 parts of polyoxyethylene styrene phenyl ether phosphate amine salt , 3 parts of enzyme-modified dextrins, 14 parts of plastic hollow bodies used in Example 1, 20 parts of anhydrous sodium sulfate, and 38.9 parts of urea are mixed with an appropriate amount of water, and after kneading with a two-axis kneader, Use an extrusion granulator to extrude and granulate with a sieve with a mesh diameter of 5mm. After sizing the granules into the target size, they are dried by a fluidized bed dryer at a product temperature of 60°C and sieved to obtain a uniform diffusible granular pesticide preparation. A granular material containing 3% by mass of Compound B with a diameter of 3 to 7 mm and a length of 3 to 20 mm. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Comparative example 4

The mixture uniformly mixed with 6.25 parts of pyrazosulfuron (pKa 3.91), 12 parts of paraffin (melting point 68-70°C), 63.75 parts of calcium carbonate, and 18 parts of polyvinyl alcohol was pulverized by an impact mill. After adding an appropriate amount of water to the obtained powder and kneading with a high-speed mixer, use a dome granulator to extrude and granulate with a sieve with a mesh diameter of 0.5mm, and dry the granulated material at 70°C to obtain Pesticide granules with 6.25% by mass of rimsulfuron, a diameter of 0.4 to 0.6 mm, and a length of 1 to 6 mm. The obtained pesticide granules were poured into water, and the state of disintegration of the particles was observed after 30 minutes. There were no disintegrated particles, and it was judged as non-disintegrated.

Then, in 16 parts of the non-disintegrating pesticide granules, 5 parts of butyl naphthalene sulfonic acid formalin condensate sodium salt, 1 part of polyoxyethylene acetylene glycol, 0.5 parts of sodium polyacrylate, in Example 1 A mixture of 14 parts of plastic hollow bodies, 20 parts of anhydrous sodium sulfate, and 55.4 parts of urea with an appropriate amount of water added, kneaded with a high-speed mixer, and then extruded through a sieve with a mesh diameter of 5 mm using an extrusion granulator After granulation and granulation into the target size, the product temperature is 60° C., dried by fluidized bed dryer, and sieved to obtain a uniform diffusible granular pesticide preparation with a diameter of 3 to 7 mm and a length of 3 to 20 mm containing 1% by mass. Granules of pyrazosulfuron. The obtained uniformly diffusible granular pesticide preparation was poured into water. As a result of observation, the particles of the preparation disintegrated and the non-disintegrating pesticide granules settled within 30 minutes or less.

Test example 1 (dissolution test in water)

8 liters of tap water were added to a hollow container made of vertically 50 cm and horizontally 40 cm to make the water depth 4 cm. In this container, 250 g per 10 ares of uniformly diffusible granular pesticide formulations of Examples 1-10 and Comparative Examples 1-4 were applied and treated. Water was collected after 1, 3, 7, 21, and 35 days of treatment, and the concentration of components in water was determined by HPLC analysis as the dissolution rate in water. The results are shown in Table 1.

[Table 1] Herbicidal Active Ingredients 1 day 3 days 7 days 21 days 35 days Example 1 benzsulfuron 52 63 74 81 87 Example 2 benzsulfuron 54 66 71 87 96 MEFENA SETSUTTO 85 92 100 97 93 Example 3 Compound A 34 41 56 59 73 Example 4 Compound A 42 54 67 82 91 Example 5 Compound B 19 twenty one 32 47 69 Example 6 Compound B 29 38 42 53 68 Example 7 Compound B 19 twenty four 37 49 56 Funtrazamid 95 100 98 94 96 Example 8 pyrazosulfuron 56 59 71 83 86 Example 9 Tricyclazole 69 72 86 95 93 Example 10 PHC 59 63 72 80 83 Comparative example 1 benzsulfuron 100 100 100 100 100 Comparative example 2 Compound A 100 96 98 100 96 Comparative example 3 Compound B 79 95 100 99 100 Comparative example 4 pyrazosulfuron 6 8 3 5 7

According to Table 1, the uniform diffusible granular pesticide formulations of Examples 1 to 7, with regard to the sulfonylurea compound or difluoromethanesulfonylanilide derivative or its salt of the pesticide active ingredient herbicide, after 1 day of treatment to In the test after 35 days, the dissolution rate in water was lower than that of Comparative Examples 1 to 3, indicating that sustained release was performed.

In addition, comparing Example 8 with Comparative Example 4, the concentration of the latter in water is lower than that of the former, and the dissolution of the pesticide active ingredient stagnates in only a small part of the initial stage and does not continue. Therefore, the pesticide in the uniformly diffusible granular pesticide formulation It is obviously not good in that most of the active ingredient remains unused.

In addition, comparing Example 5 with Comparative Example 3, the concentration of the latter in water is higher than that of the former, and it can be seen that the sustained release of the active ingredient of the pesticide is low due to the absence of alkaline substances.

Test example 2 (field diffusivity)

As shown in Fig. 1, the uniform diffusible granular pesticide formulation of Example 5 was sprinkled by hand from two sides in the upwind direction of a water field nursery with a short side of 20 m, a long side of 50 m, and a water depth of 5 cm. After 48 hours after spreading, water was collected from the points (A-L) shown in Figure 1 for analysis, and the ratio when the concentration in water under the theoretically uniform dispersion of the pesticide active ingredient was taken as 100% was obtained, and the average value was divided by each point. The standard deviation of the concentration in the water is used to calculate the rate of change. The results are shown in Table 2.

[Table 2] Place Concentration of Compound B (%) A 35 B 37 C 39 D. 31 E. 29 f 25 G 29 h 31 I 35 J 27 K 26 L twenty four average 30.8 rate of change 16.2

As can be seen from Table 2, when the uniformly diffusible granular pesticide formulation was applied, the uniformity of the pesticide active ingredient in water was good.

Possibility of industrial use

The uniformly diffusible granular pesticide preparation of the present invention can be prepared in a simple and convenient way, and the dissolution of the active ingredient of the pesticide can be moderately slow-released, thereby exerting the drug effect of the active ingredient of the pesticide for a long time, due to the release of the active ingredient in the environment. The reduction of the active ingredients of the pesticide reduces the environmental burden, reduces or prevents the drug hazards caused by the active ingredients of the pesticide, such as the drug hazards to the target crops, etc., and the granular pesticide preparation can be spread uniformly in the entire paddy field by a simple spreading method, which is helpful for agricultural production. Remarkable effect of labor saving.

Claims (12)

1. uniformly diffusible granular pesticide composition, it is characterized in that comprising non-disintegration-type agricultural chemicals shot-like particle, surfactant and floatability composition, this non-disintegration-type agricultural chemicals shot-like particle is to contain acid agrichemical active component, cationic surfactant and alkaline matter, and at 30 minutes or 30 minutes non-disintegration-type agricultural chemicals shot-like particles with interior not disintegration in water; Described pesticidal preparations have particle diameter the mass ratio of 3mm and the particle more than the 3mm be 80 quality % or the size distribution more than the 80 quality % and drop into the water surface after swim immediately character on the water surface, but 30 minutes or 30 minutes with interior disintegration on the water surface.

2. the described uniformly diffusible granular pesticide composition of claim 1, wherein the pKa of acid agrichemical active component is 2～7.

3. the described described uniformly diffusible granular pesticide composition of claim 1, wherein the acid agrichemical active component is a weed killer herbicide.

4. the described described uniformly diffusible granular pesticide composition of claim 3, wherein weed killer herbicide is a sulfonyl urea compound.

5. the described uniformly diffusible granular pesticide composition of claim 3, wherein weed killer herbicide is a general expression

[changing 1]

(the R in the formula ¹Being hydrogen atom, alkyl or alkoxyalkyl) represented difluoromethane sulfonyl is for anil or its salt.

6. the described uniformly diffusible granular pesticide composition of claim 1, wherein cationic surfactant gelation or show swellability in water.

7. the described uniformly diffusible granular pesticide composition of claim 1, wherein alkaline matter is a sodium bicarbonate, sodium carbonate, slaked lime, calcium carbonate, the Emathlite of alkaline white carbon or alkalescence.

8. the described uniformly diffusible granular pesticide composition of claim 1, wherein the floatability composition is inorganic hollow body or plastic hollow body.

9. the preparation method of a uniformly diffusible granular pesticide composition, it is characterized in that non-disintegration-type agricultural chemicals shot-like particle, surfactant are carried out granulation with the floatability composition to be handled, form spherical or minor axis 1～20mm of particle diameter 1～20mm, the shape of growing crosswise of major diameter 3～40mm, described non-disintegration-type agricultural chemicals shot-like particle be contain acid agrichemical active component and cationic surfactant and alkaline matter and at 30 minutes or 30 minutes non-disintegration-type agricultural chemicals shot-like particles with interior not disintegration in water.

10. the described preparation method of claim 9 wherein carries out granulation with the sieve extruder grain of using the order footpath bigger than the particle diameter of non-disintegration-type agricultural chemicals shot-like particle or grain length and handles.

11. the preparation method of a uniformly diffusible granular pesticide composition, it is characterized in that non-disintegration-type agricultural chemicals shot-like particle, pesticide activity component are carried out granulation with surfactant and floatability composition to be handled, form spherical or minor axis 1～20mm of particle diameter 1～20mm, the shape of growing crosswise of major diameter 3～40mm, this non-disintegration-type agricultural chemicals shot-like particle is to contain acid agrichemical active component, cationic surfactant and alkaline matter, and at 30 minutes or 30 minutes non-disintegration-type agricultural chemicals shot-like particles with interior not disintegration in water.

12. the described preparation method of claim 11 is wherein to use particle diameter or the big order sieve extruder grain directly of grain length than non-disintegration-type agricultural chemicals shot-like particle to carry out the granulation processing.