JPS6358802B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention relates to aqueous suspension biocide compositions with significantly enhanced bioefficacy. [Prior Art] Biocides such as insecticides, fungicides, herbicides, and acaricides are substantially insoluble in water and have been put to practical use as fluid suspensions with water as a continuous phase. Compared to emulsions made by dissolving biocides in organic solvents such as xylene and kerosene, fluid suspensions are
This dosage form is advantageous in terms of product storage, cost, environmental pollution, and phytotoxicity to crops, and can also be made into a liquid even when a suitable organic solvent is not available, making it suitable for aerial spraying. It is. [Problems to be Solved by the Invention] As described above, fluid suspensions have an excellent aspect as a biocide formulation, and although various improvement studies have been conducted, caking and caking occur when stored for a long period of time. It also has drawbacks such as thickening, and is not yet fully satisfactory. [Means for Solving the Problems] As a result of intensive research under such circumstances, the present inventor found that if a dispersion of biocidal drug substance is stirred with a rigid media having a particle size of 0.5 mm or less, particles with a particle size of 0.5 μ or less can be obtained. It was discovered that a micronized biocidal drug substance containing particles having a diameter of 50 wt% or more can be obtained, and that the biological activity is significantly enhanced as the particles are made into microparticles. It was discovered that if used, a suspended pesticide formulation with high biological effects and excellent long-term stability without hard caking at the bottom or thickening caused by natural sedimentation of the biocidal substance could be obtained, and a patent application has already been filed. (Special Application No. 59-185889). As a result of further investigation, the present inventor has determined that the thus obtained finely divided non-pyrethroid biocide (hereinafter, "biocide" refers to a non-pyrethroid biocide in this specification) and a specific The present invention was completed based on the discovery that the biological efficacy can be further enhanced when an adjuvant is used in combination. That is, in the present invention, particles having a particle size of 0.5μ or less
A micronized biocide that is 50wt% or more and the following (i)
The present invention provides an aqueous suspension biocide composition containing a compound selected from (ii) as an essential component. (i) Polyoxyalkylene type nonionic surfactant. (ii) Polyoxyalkylene alkyl (or alkylaryl) ether phosphates or salts thereof. The micronized biocide used in the present invention has 50 wt% or more of particles with a particle size of 0.5 μ or less, and 50 wt% or more of particles with a particle size of 0.5 μ or less and an average particle size of 0.5 μ or less. Preferably, particles with a particle size of 0.5μ or less are 70wt% or more, and the average particle size is 0.4μ.
The following are preferred. The raw material for the micronized biocide used in the present invention may be any type of biocide other than pyrethroid, which is insoluble in water and solid or paste at room temperature. Also includes. By making any biocide into fine particles according to the present invention and using it in combination with an adjuvant, an excellent biological effect that was previously unimaginable can be obtained. Also,
The active biocide can also be used in combination of two or more biocides with different structures. Biocides that are insoluble in water and solid or paste-like at room temperature include copper agents, organic tin agents, organic arsenic agents, sulfur, Daisen (zincified ethylene bis(dithiocarbamate)), and thiuram. Organic sulfur agents such as (bis(dimethylthiocarbamyl)disulfite); Daconyl (tetrachloroisophthalonitrile), Rubcide (4,5,
6,7-tetrachlorophthalide); other organic chlorine agents such as cabtan (N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide), difortan (N-(1,1,
2,2-tetrachloroethylthio)-4-cyclohexene-1,2-dicarboximide), acrycid (2-sec-butyl-4,6-dinitrophenyl-3-methylcrotonate),
Topudine M (dimethyl 4,4'-o-phenylene-3,3'-dithiodialophanate), Benlate (methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate), Takegalen (3-hydroxy-5 -methylisoxazole)
Herbicides include Nip (2,4-dichlorophenyl-p-nitrophenyl ether), MO (p-nitrophenyl ether),
Diphenyl ether herbicides such as nitrophenyl-2,4,6-trichlorophenyl ether); Stam (3',4'-dichloropropionanilide), Daimid (N,N-dimethyl-2,2-
Acid amide herbicides such as diphenylacetamide); Carbamate herbicides such as Sweep (methyl-3,4-dichlorocarbanilate); Carmex D (3-(3,4-dichlorophenyl)-1,
urea-based herbicides such as simazine (2-chloro-4,6-bis(ethylamino)-1,3,5-triazine), gesaprim (2-chloro-4,6-bis(ethylamino)-1,3,5-triazine);
Triazine herbicides such as -chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine); insecticides include DDT (1,1,1-trichlor-2,2-bis(para-chlorophenyl)); )-ethane), Kayaace (para-dimethylsulfamyl phenyl diethyl phosphorothionate), Guardside (2-
Chlor-1-(2,4,5-trichlorophenyl)
Organophosphorus insecticides with aromatic rings such as -vinyl dimethyl phosphate); Denapon (1-naphthyl-methyl carbamate), Tumaside (m-tolyl methyl carbamate), Macbal (3,5-
xylyl methyl carbamate), mypsin (o-
cumenyl methyl carbamate), sunside (o
-isopropoxyphenyl methyl carbamate)
Carbamate insecticides such as metaldehyde (acetaldehyde tetramer), raninate (S-methyl-N-(methylcarbamyloxy)-
thioacetimide); acaricides include satupiran (p-chlorophenyl p-chlorobenzenesulfonate), tedeon (p-chlorophenyl-2,
4,5-trichlorophenylsulfone), Kelsene (2,2,2-trichloro-1,1-bis(p
-chlorophenyl)ethanol), omite (2
-(p-tertiarybutylphenoxy)cyclohexylpropynyl sulfite), plictran (tricyclohexyl hydroxytin), and the like. The method for producing the micronized biocide according to the present invention is not particularly limited, but it can be easily produced, for example, by stirring a dispersion of the biocidal drug substance together with rigid media having a particle size of 0.5 mm or less, as described below. The raw biocidal active substance is used by dispersing a commercially available powder in water, but a commercially available dispersion may also be used. In addition, the concentration of the dispersion is 5 to 70 wt% of the biocidal active substance.
A range of 1 is preferable, and a high concentration is particularly preferable in consideration of production efficiency. Furthermore, the media preferably have a particle size of 0.5 mm or less, particularly 0.05 to 0.5 mm. The material of this media can be rigid, such as Ottawa sand, glass, alumina, zircon, etc.
Glass is preferred. Sand mills, sand grinders, etc. are known as devices for stirring the biocidal substance and media to make them into fine particles, but the sand mills and sand grinders used in the present invention may be of the generally known type, and may be of the vertical or horizontal type. Can be used together. Further, a commonly used type of disk can be used. The temperature during microparticulation is preferably 5 to 30°C. If the temperature exceeds 30°C, it is not preferable because it takes a long time to form fine particles and it becomes difficult to form fine particles. The mixing ratio of media and biocidal substance during atomization is in the range of 40/60 to 80/20 by volume.
Preferably it is 60/40 to 70/30. The biocidal drug substance micronized as described above is obtained by separating the media and the biocidal drug dispersion liquid by pressure filtration or centrifugation, and further washing the media with water as necessary. In the above-mentioned micronization, if an appropriate dispersant is added to the dispersion of the biocidal raw material, the micronization can be carried out even more efficiently. Particularly preferred dispersants include the following compounds (1) to (3).
These dispersants may be used alone or in combination of two or more. (1) A water-soluble or water-dispersible polymer containing as an essential component one or more monomers selected from the monomer group consisting of unsaturated carboxylic acids and their derivatives. Monomers used in the production of Polymer 1 include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as maleic acid, and derivatives thereof such as alkyl esters (methyl esters, etc.) of the above acids. ), alkali metal salts (such as soda salts), ammonium salts and organic amine salts (such as triethanolamine salts), and mixtures thereof. In addition to these monomers, copolymerizable monomers such as vinyl acetate, isobutylene, diisobutylene, and styrene can also be added as copolymerization components. The method of polymerizing these monomers is conventionally known. Although there are no particular restrictions on the ratio of monomer components and the degree of polymerization of the polymer, it is necessary that the polymer be at least water-soluble or water-dispersible. Specific examples include acrylic acid polymers, methacrylic acid polymers, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and acrylic acid methyl ester, and copolymers of acrylic acid and vinyl acetate. polymers, copolymers of acrylic acid and maleic acid, copolymers of maleic acid and isobutylene, copolymers of maleic acid and styrene, etc.
and salts of these with alkali metals, ammonia and organic amines. Two or more kinds of these polymers can also be used. (2) Polymer of styrene sulfonate A polymer of styrene sulfonate can be easily produced by polymerizing styrene sulfonate or by sulfonating polystyrene. The polymer of styrene sulfonate has a skeleton represented by the following formula. The molecular weight is 1,000 or more, preferably 10,000 to 3,000,000. M means an alkali metal salt such as Li, Na, or K, or NH ₃ , an alkylamine, an alkanolamine, or the like. Moreover, the polymer of styrene sulfonate may be a copolymer of styrene sulfonate and another monomer. Such a copolymer can be easily produced by copolymerizing styrene sulfonate and other monomers or by sulfonating a copolymer of styrene and other monomers. In the case of copolymerization, it may be used within a range that does not impair the effects of the present invention. The partner monomers for copolymerization include alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate,
Hydrophobic monomers such as ethylene, propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, acrylonitrile, styrene, and acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, vinyl alcohol, acrylamide, Hydrophilic monomers such as methacrylamide, diacetone acrylamide, N-vinylpyrrolidone, 2-acrylamido-2-methylpropanesulfonic acid, methalylsulfonic acid, etc. are used. (3) Formalin condensates of sulfonated polycyclic aromatic compounds that may have hydrocarbon groups as substituents or their salts, specifically petroleum sulfonic acid derivatives, lignin sulfonic acid derivatives, naphthalene sulfonic acid derivatives, etc. It is a formalin condensate. The above-mentioned compound (3) according to the present invention can be obtained by sulfonating, for example, naphthalene, alkyl-substituted naphthalene, anthracene, alkyl-substituted anthracene, lignin, aromatic ring-containing compounds in petroleum residue, etc., by a general method, followed by a salt-forming reaction. , and further formalin condensation. In this case, the degree of condensation is preferably from 1.2 to
30, more preferably 1.2-10. here,
When the degree of condensation is less than 1.2, the effect of condensation is small, and when it exceeds 30, the molecular weight becomes high, which causes practical problems in terms of solubility and the like. Various types of polycyclic aromatic compounds can be used, but preferably lignin, naphthalene, or alkylnaphthalene having 1 to 6 carbon atoms may be used, and of course, a mixture thereof may be used. . As salts, alkali metals such as sodium and potassium, alkaline earths such as calcium, amines, ammonium salts, etc. are also used. The above dispersants (1) to (3) are added in an amount of 0.1wt to the dispersion of the biocidal drug substance.
% or more, especially 0.5 to 10 wt%. The micronized biocide thus obtained contains 50 wt% or more of particles with a particle size of 0.5μ or less [particle size and its distribution were measured using a centrifugal automatic particle size distribution analyzer CAPA-
500 (Horiba, Ltd.). The same applies in Examples], and the dispersion containing this micronized biocide has significantly improved dispersion stability compared to the conventional dispersion containing a biocide with a large particle size. Since the biocide thus obtained for use in the present invention has been made into fine particles, its biological effects are already enhanced compared to dispersions containing conventional biocides.
By using the compounds (i) to (ii) in combination, the biological effects are further enhanced. (i) Polyoxyalkylene type nonionic surfactant The following compounds are listed as preferred. A product obtained by adding alkylene oxide to a mixture of fatty acid triglycerides and polyhydric alcohols. The fatty acid triglyceride is not particularly limited, and higher fatty acid triglycerides are generally used. Examples of higher fatty acids include behenic acid, stearic acid, oleic acid, linoleic acid, palmitic acid, myristic acid, lauric acid, and caprylic acid. Furthermore, these higher fatty acids may be used alone or in a mixture of two or more. Furthermore, it does not matter whether the fatty acid triglyceride is a natural product or a synthetic product. Natural fats and oils, which are natural fatty acid triglycerides, are also readily available and suitable for practicing the present invention. Such natural oils and fats include animal fats such as beef tallow, lard, and mutton tallow; coconut oil, palm oil, cottonseed oil, castor oil, rapeseed oil, coconut kernel oil, soybean oil, olive oil, linseed oil, corn oil, etc. Examples include vegetable oils and fats. As the polyhydric alcohol, compounds having 2 to 6 carbon atoms and having 2 to 6 hydroxyl groups not exceeding the number of carbon atoms are preferable, such as ethylene glycol; propylene glycol; glycerin;
1,2-, 1,3- and 2,3-butylene glycol; 1,2-, 1,3-, 2,3-,
and 2,4-pentylene glycol; 1,2
-, 1,3-, 2,3-, and 2,4-hexylene glycol; butanetriol; pentanetriol; hexanetriol; pentaerythritol; sorbit; mannit; xylit; dulcit; and the like. Among these polyhydric alcohols, those having 3 carbon atoms, especially glycerin, are most convenient for the purpose of the present invention. It is also possible to use mixtures of these polyhydric alcohols. The molar ratio of fatty acid triglyceride to polyhydric alcohol used is 1:0.1-5, preferably 1:0.2-2. As the alkylene oxide added to the mixture of fatty acid triglyceride and polyhydric alcohol, ethylene oxide, propylene oxide, or butylene oxide can be used alone or in combination. Among these, ethylene oxide alone, propylene oxide alone, and a combination of ethylene oxide and propylene oxide are preferred. When used in combination, it may be random or block. Alkylene oxide is 1 mole of fatty acid triglyceride and polyhydric alcohol.
~100 moles are added, preferably 5 to 60 moles. The addition reaction is not particularly limited,
The reaction can be carried out under the conditions of the commonly used addition reaction of alkylene oxide to a compound having active hydrogen. That is, a catalytic amount of an alkaline substance is added to a mixture of triglyceride and polyhydric alcohol charged at the above molar ratio, and alkylene oxide is introduced into the mixture at about 100 to 200°C at 1 to 5 kg/cm ² over several hours. This can be achieved by reacting with The product obtained by this addition reaction is a mixture of various compounds, and although the details of its composition are not clear, alkylene oxide is present between the fatty acid constituting the triglyceride and the polyhydric alcohol or glycerin derived from the triglyceride. It is estimated that the added compound is the main component. Polyoxyalkylene alkyl (or alkenyl) ether. Alkyl (or alkenyl) group has 4 carbon atoms
~22, and the oxyalkylene is oxyethylene, oxypropylene, or oxybutylene alone or in a mixture. Among these, it is preferable that the proportion of oxyethylene is 50% by weight or more based on the oxyalkylene. The number of moles of oxyalkylene added is 1 to 100
mol, preferably 3 to 50 mol. Polyoxyalkylene mono- or dialkyl (or aryl) phenyl ether. The alkyl group has 4 to 18 carbon atoms, and the aryl group includes a benzyl group, a phenyl group, and a styryl group. Oxyalkylene is oxyethylene, oxypropylene, oxybutylene alone or in mixtures. Among these, it is preferable that the proportion of oxyethylene is 50% by weight or more based on the oxyalkylene. The number of moles of oxyalkylene added is 1 to 100
Preferably it is 3 to 50 moles. Polyoxyalkylene fatty acid ester. The fatty acid is a higher fatty acid having 8 to 22 carbon atoms, and the oxyalkylene is oxyethylene, oxypropylene, or oxybutylene alone or in a mixture. Among these, it is preferable that the proportion of oxyethylene is 50% by weight or more based on the oxyalkylene. The number of moles of oxyalkylene added is 1 to 100
mol, preferably 3 to 50 mol. Polyoxyalkylene sorbitan fatty acid ester. The fatty acid is a higher fatty acid having 8 to 22 carbon atoms, and the ester degree is 1 to 4, preferably 1 to 3.
It is. xyalkylene is oxyethylene,
It is oxypropylene or oxybutylene alone or as a mixture. Among these, it is preferable that the proportion of oxyethylene is 50% by weight or more based on the oxyalkylene. The number of moles of oxyalkylene added is 1 to 100,
Preferably it is 3 to 50 moles. Polyoxyalkylene sorbitol fatty acid ester. The fatty acid is a higher fatty acid having 8 to 22 carbon atoms, and the degree of esterification is 1 to 6, preferably 3 to 22.
It is 5. Oxyalkylene is oxyethylene, oxypropylene, oxybutylene alone or in mixtures. Among them, the proportion of oxyethylene is 50% by weight relative to oxyalkylene.
The above is preferable. The number of moles of oxyalkylene added is 1 to 100
mol, preferably 3 to 50 mol. Polyoxyalkylene sorbitol alkyl ether. The alkyl group has 8 to 22 carbon atoms. The degree of etherification is 1-6, preferably 3-5.
Oxyalkylene is oxyethylene, oxypropylene, oxybutylene alone or in mixtures. Among these, it is preferable that the proportion of oxyethylene is 50% by weight or more based on the oxyalkylene. The number of moles of oxyalkylene added is 1 to 100
mol, preferably 3 to 50 mol. Polyoxyalkylene alkyl (or alkenyl) amine The alkyl (or alkenyl) group has 4 carbon atoms
~22, and the oxyalkylene is oxyethylene, oxypropylene, or oxybutylene alone or in a mixture. Among these, it is preferable that the proportion of oxyethylene is 50% by weight or more based on the oxyalkylene. The number of moles of oxyalkylene added is 1 to 100
mol, preferably 3 to 50 mol. Polyoxyethylene/polyoxypropylene block polymer. Those having a molecular weight of 1,000 to 10,000 are preferred. ~ can also be used in combination. (ii) Polyoxyalkylene alkyl (or alkylaryl) ether phosphates or salts thereof. There is no limitation on the manufacturing method, and it is manufactured by a generally known method. For example, it can be obtained by adding alkylene oxide to alcohol or alkylphenol, reacting it with phosphorus pentoxide, and neutralizing if necessary. The starting alcohol is an alcohol having a linear or branched alkyl group having 1 to 22 carbon atoms, an alkenyl group having a double bond or a hydroxyl group in the chain, or an alcohol having a hydroxyalkyl group. Preferably it has 4 to 18 carbon atoms and 0 to 18 double bonds.
4, preferably 0 to 2, 0 to 4 hydroxyl groups,
Preferably, the number is 0 to 2. Examples include butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, oleyl alcohol, and the like. The alkylphenol preferably has an alkyl group having 4 to 18 carbon atoms. Examples of alkylene oxides that are added to alcohols to form polyoxyalkylene chains include ethylene oxide, propylene oxide, and butylene oxide. These may be a single block, two or more types of blocks, or randomly added blocks. The number of moles added is 1 to 100 moles, preferably 1 to 50 moles. The addition reaction can be carried out by a known method, for example, by introducing and reacting alkylene oxide at 50 to 200° C. and 1 to 5 kg/cm ² in the presence of an acid or alkali catalyst. There are various methods for phosphorylating polyoxyalkylene alkyl (or alkyl phenol) ether, but for example, phosphorylation is achieved by adding 1 mole of phosphorus pentoxide to 3 moles of polyoxyalkylene alkyl ether and reacting at 80 to 100°C for about 6 hours. Acid esters can be easily obtained.
The polyoxyalkylene alkyl (or alkylphenol) ether phosphate ester obtained in this case is a mixture of approximately equal amounts of monoester and diester, and is used as an adjuvant in the present invention.
Although both monoesters and diesters exhibit excellent effects, monoesters, especially polyoxyalkylene alkyl ether phosphoric acid monoesters or salts thereof, exhibit particularly excellent effects. Furthermore, by neutralizing this phosphoric acid ester with a base, a polyoxyalkylene alkyl ether phosphoric acid ester salt can be obtained. This phosphoric acid ester salt also has an excellent potency-enhancing effect.
Examples of the salt include alkali metal salts, alkaline earth metal salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, and ammonium salts. In the present invention, the weight ratio of the micronized biocide and the compound selected from (i) to (ii) is 1:0.2 to 20,
More preferably, the ratio is 1:0.5 to 15. In carrying out the present invention, in addition to the essential components of the micronized biocide and the compounds selected from (i) to (ii), dispersants, water-soluble thickeners, anti-foaming agents, decomposition inhibitors, Anti-aggregation agents and the like can be added as necessary. As the dispersant, a nonionic surfactant and/or an anionic surfactant may be used in addition to the polymer compounds already described in the method of microparticulation. Examples of such nonionic surfactants and/or anionic surfactants include polyoxyethylene (hereinafter referred to as POE) alkyl (carbon number 6 to 22) ether, POE alkyl (carbon number 4
~18) Phenol ether, polyoxypropylene polyoxyethylene (block or random)
Alkyl ether, POE phenyl phenol ether, POE styrene phenol ether,
Nonionic surfactants such as POE tribenzyl phenol ether, lignin sulfonate, alkylbenzene sulfonate, alkyl sulfonate, POE alkyl sulfonate, POE alkyl phenyl ether sulfonate, POE alkyl phenyl ether phosphate Acid ester salt, POE phenyl phenol ether sulfonate, POE
phenylphenol ether phosphate ester salt,
Examples include anionic surfactants such as naphthalene sulfonate, naphthalene sulfonic acid formalin condensate, POE tribenzyl phenol ether sulfonate, and POE tribenzyl phenyl phenol ether phosphate ester salt. These can be used alone or in combination. Its content is 0-20% by weight in the composition, preferably 1-10% by weight. As the water-soluble thickener, any of natural, semi-synthetic and synthetic water-soluble thickeners can be used. Natural mucilages include xanthan gum derived from microorganisms, xanthuro,
Plant-derived pectin, gum arabic, guar gum, etc. are semi-synthetic viscous substances such as methylated products, carboxyalkylated products, hydroxyalkylated products (including methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, etc.) of cellulose or starch derivatives, and synthetic viscous products. Polyacrylates, polymaleates,
Specific examples include polyvinylpyrrolidone. The water-soluble thickener is incorporated in the composition in an amount of about 0 to 3.0% by weight, preferably about 0.05 to 0.5% by weight. Antifoaming agents may optionally be included up to about 2% by weight to prevent foaming during formulation, and antidegradants may be included up to about 7% by weight to prevent degradation, particularly during storage of organophosphorus biocides. is preferred. The anti-foaming agent is not particularly limited and any anti-foaming agent may be used, but specific examples include polypropylene glycol and silicone oil. Examples of the decomposition inhibitor include epichlorohydrin, phenyl glycidyl ether, allyl glycidyl ether, and the like. In addition, if desired, an anti-aggregation agent (e.g. polyoxyethylene-polyoxypropylene block polymer), an anti-drift agent (e.g. sorbitol), etc. for the solid biocide may be added within a range that does not impair the effects of the present invention. can. To summarize the above, an example of the aqueous suspension biocide composition of the present invention is as follows. (A) Biocide 10-60% by weight (B) Compounds (i)-(ii) 10-60 〃 (C) Dispersant 0-20 〃 (A) Water-soluble thickener 0-3 〃 (B) Anti-foaming agent 0 to 2 (C) Decomposition inhibitor 0 to 7 (G) Water 10 to 80 In the preparation of the aqueous suspension biocide composition, the order of addition of each component is not limited. [Effect] Although the mechanism of how the aqueous suspension biocide composition of the present invention exhibits excellent biological effects is not necessarily clear, it is possible that the stomata present on the leaf surface as the biocide is made into fine particles. Micronized particles can easily penetrate through pores such as cracks in the cuticular layer, and adjuvants, which are compounds selected from (i) to (ii), have a very strong solubilizing power for biocides. A possible reason is that it becomes finer particles and promotes penetration from the surface of plants or into insects and fungi. [Effects of the Invention] The aqueous suspension biocide composition of the present invention has a higher biological effect than conventional biocide active substances with large particle sizes because the biocide is made into fine particles. The biological effect was further enhanced by the effect of the adjuvant. [Examples] Next, the present invention will be explained with reference to Examples and Reference Examples, but the present invention is not limited to these Examples. Reference example 1 Topjin M powder 60g, formula (The molecular weight of the compound of the above formula is approximately 350,000), 55 g of water, and 140 g of glass beads (media) of 0.1 to 0.2 mm were mixed (media/
The disk was rotated at a peripheral speed of 6 m/sec for 12 hours in a sand grinder (manufactured by Igarashi Kikai) with an inner volume of 400 ml and a dispersion liquid volume ratio of 50/50. The temperature inside the sand grinder is 20-25 °C. Furthermore,
After micronization, this is filtered under pressure to obtain about 100 g of micronized Topjin M dispersion. Also 70g of water
If you wash the media twice with
90wt% can be recovered. As shown in Table 1, this micronized Topgin M has a particle size distribution of 72% by weight of particles having a particle size of 0.5μ or less.

[Table] Reference example 2 Loveside (bactericide) powder 46g, formula (The molecular weight of the above formula compound is 680,000) 4.5 g of water-soluble copolymer salt represented by, 63 g of water, and 187 g of glass beads (media) of 0.1 to 0.2 mm.
(media/dispersed liquid volume ratio = 63/37),
The disk was rotated at a circumferential speed of 6 m/sec for 12 hours in a sand grinder (manufactured by Igarashi Kikai) with an internal volume of 400 ml. The temperature inside the sand grinder is 20~
It is 25℃. Furthermore, this is filtered under pressure to obtain 60 g of a finely divided rubside dispersion. Also water 70
Washing the media twice with g will remove the love side.
98wt% can be recovered. As shown in Table 2, this micronized rubcide has a particle size distribution of 100 wt % of particles having a particle size of 0.5 μ or less. Reference example 3 Simazine (herbicide) 56g, formula (The molecular weight of the compound of the above formula is 320,000) 4.5 g of water-soluble copolymer salt, 39.5 g of water
and 0.1-0.2mm glass beads (media) 187
Mix g (media/dispersed liquid volume ratio = 53/47)
The disc was then heated at a circumferential speed of 6 m/min for 12 hours in a sand grinder with an internal volume of 400 ml (manufactured by Igarashi Kikai).
Rotate in seconds. The temperature inside the sand grinder is
The temperature is 20-25℃. Further, this is filtered under pressure to obtain 60 g of a micronized simazine dispersion. This micronized simazine is as shown in Table 2.
The particle size distribution consists of 88wt% particles having a particle size of 0.5μ or less. Reference example 4 Carmex D (herbicide) 45.5g, naphthalene sulfonic acid formalin condensate (degree of condensation 4) Na salt
Mix 4.5 g of water, 50 g of water, and 180 g of 0.1 to 0.2 mm glass beads (media) (media/dispersed liquid volume ratio = 50/50), and grind the disc in a sand grinder (manufactured by Igarashi Kikai) with an internal volume of 400 ml for 3 hours. , rotate at a circumferential speed of 6 m/sec. The temperature inside the sand grinder is 20-25 °C. Furthermore, by filtering this under pressure, micronized Carmex D68 is obtained. As shown in Table 2, this micronized Carmex D has a particle size distribution of 95% by weight of particles having a particle size of 0.5 μm or less.

[Table] Reference example 5 Tumaside (insecticide) powder 45.5g, formula (The molecular weight of the compound of the above formula is 260,000) 4.5 g of water-soluble copolymer salt, 50 g of water, and
187 g of glass beads (media) of 0.1 to 0.2 mm were mixed (media/dispersed liquid volume ratio = 50/50), and the disc was heated at a circumferential speed of 6 m/min for 8 hours in a sand grinder with an internal volume of 400 ml (manufactured by Igarashi Kikai). Rotate in seconds. The temperature inside the sand grinder is 20-25
It is ℃. Furthermore, this is filtered under pressure to obtain 70 g of a micronized Tumaside dispersion. This micronized Tsumaside is as shown in Table 3.
The particle size distribution consists of 90wt% of particles having a particle size of 0.5μ or less. Reference example 6 Rannate (insecticide) powder 45.5g, formula (The molecular weight of the compound of the above formula is 220,000) 4.5 g of water-soluble copolymer salt represented by, 50 g of water and
187 g of glass beads (media) of 0.1 to 0.2 mm were mixed (media/dispersed liquid volume ratio = 50/50), and the disc was heated at a circumferential speed of 6 m/min for 8 hours in a sand grinder with an internal volume of 400 ml (manufactured by Igarashi Kikai). Rotate in seconds. The temperature inside the sand grinder is 20-25
It is ℃. Furthermore, this is filtered under pressure to obtain 45 g of a micronized rannate dispersion. This micronized rannate is as shown in Table 3.
The particle size distribution consists of 74wt% particles having a particle size of 0.5μ or less. Reference example 7 Plictran (acaricide) powder 45.5g, formula (The molecular weight of the compound of the above formula is 180,000) 4.5 g of water-soluble copolymer salt represented by, 50 g of water and
187 g of glass beads (media) of 0.1 to 0.2 mm were mixed (media/dispersed liquid volume ratio = 50/50), and the disc was heated at a circumferential speed of 6 m/min for 8 hours in a sand grinder with an internal volume of 400 ml (manufactured by Igarashi Kikai). Rotate in seconds. The temperature inside the sand grinder is 20-25
It is ℃. Furthermore, this is filtered under pressure to obtain 70 g of a micronized plictran dispersion. As shown in Table 3, this micronized plictran has a particle size distribution in which 100 wt% of particles have a particle size of 0.5 μ or less.

[Table] Example 1 In order to test the bioenhancing ability of various adjuvants for the Topudin M micronized sol shown in Reference Example 1, Chinese cabbage was brought into contact with soft rot fungi, and after the onset of the disease (7
Day 1) Topjin M micronized sol and adjuvant were sprayed at various concentrations. After being left under high temperature and high humidity for 7 days after treatment, the diameter of the lesion after disease onset and the diameter of the lesion after treatment with the drug were measured, and the therapeutic efficacy was evaluated by calculating the control value using the following formula. Note that the diameter of the lesion after onset of the disease was 10 mm. The results are shown in Table 4. Control value: Diameter of lesion after disease onset - Diameter of lesion after drug treatment/Diameter of lesion after disease onset x 100

[Table] Example 2 Rice plants at the 5-leaf stage were treated in advance with an aqueous suspension containing the Rubcide micronized sol shown in Reference Example 2, and 6 hours later, the rice blast fungus spore suspension was sprayed. After leaving it under high temperature and high humidity for 10 days, the number of rice blast lesions was counted, and the control value was calculated with respect to the untreated plot using the following formula. The results are shown in Table 5. Control value: (1-number of lesions in chemical treated area/number of lesions in untreated area)
×100

[Table] Example 3 The simazine micronized sol shown in Reference Examples 3 and 4,
In order to test the bioenhancing ability of various adjuvants for Carmex D micronized sol, 20 crabgrass weeds at the 5-6 leaf stage and plant height of 12 cm were grown per pot, and simazine or Carmex D micronized sol and adjuvant were added at various concentrations. Sprayed. Thereafter, the plants were left in a greenhouse for 14 days, the weight of the above-ground parts was measured, and the percentage of weed killing compared to the untreated plot was calculated.
The results are shown in Table 6.

[Table] Example 4 In order to test the bioenhancing ability of various adjuvants for the Tumaside micronized sol shown in Reference Example 5, rice plants at the 7th to 6th leaf stage were sprayed with Tumaside micronized sol or adjuvant at various concentrations. .
One day later, adult leafhoppers (30 individuals) were released, and the killing rate was determined after 7 days. The results are shown in Table 7.

[Table] Example 5 In order to test the bioenhancing ability of various adjuvants on the raninate micronized sol shown in Reference Example 6, various diluted products were sprayed on armyworm larvae (20 individuals), and insecticidal after 7 days. I asked for the rate. The results are shown in Table 8.

【table】

[Table] Example 6 In order to test the bioenhancing ability of various adjuvants for the pulictran micronized sol shown in Reference Example 7, soybeans at the 10th to 11th leaf stage were sprayed with plictran micronized sol and adjuvant at various concentrations. . After leaving for 1 day, female adult red spider mites (20 individuals)
The total number of mites was counted after 3 days, and the mite killing rate was calculated using the following formula. The results are shown in Table 9. Acaricidal rate: (1 - total number of mites in treated area/total number of mites in untreated area) x 100

【table】

Claims (1)

[Scope of Claims] 1. Micronized non-pyrethroid biocide containing 50 wt% or more of particles having a particle size of 0.5 μ or less, and 20 to 2000 wt% of the following (i) to the biocide:
An aqueous suspension biocide composition characterized by containing a compound selected from (ii) as an essential component. (i) Polyoxyalkylene type nonionic surfactant. (ii) Polyoxyalkylene alkyl (or alkylaryl) ether phosphates or salts thereof.