JPS6197202A - Aqueous suspension composition of biocide - Google Patents

Abstract

PURPOSE:To provide an aqueous suspension composition of biocide, having high biocidal effect, storable stably for a long period without causing the bottom hard caking or thickening by the spontaneous precipitation of the biocide, by using a pulverized biocide having a specific particle diameter in combination with a specific adjuvant. CONSTITUTION:The objective aqueous suspension composition of biocide contains (A) a powdery biocide containing >=50wt% particles having a diameter of <=0.5mu (especially preferably containing >=70wt% particles having particle diameter of <=0.5mu and having an average particle diameter of <=0.4mu) and (B) a compound selected from (i) a polyoxyalkylene-type nonionic surfactant and (ii) a polyoxyalkylene alkyl(or alkylaryl) ether phosphate or their salts, as active components. The weight ratio of the components A:B is 1:(0.05-20), preferably 1:(0.5-15).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to aqueous suspension biocide compositions with significantly enhanced bioefficacy.

[Conventional technology]

Biocides such as insecticides, FF71M agents, herbicides, and acaricides are substantially insoluble in water, and have been put to practical use as fluid suspensions in which water forms a microscopic phase.

Compared to emulsions made by dissolving biocides in organic baths such as xylene or kerosene and dispersing them, fluidized suspensions are more effective in terms of product storage,
It is an advantageous formulation in terms of cost, environmental contamination, and phytotoxicity to crops, and it can be made into a liquid even when there is no suitable solvent for 1* and 2j1, and it is also suitable for aerial spraying. It is a type.

[Problem that the invention seeks to solve]

Although KfimM clouding agent has excellent properties as a biocide dosage form, and much research has been done to improve it, it also has the disadvantage of causing caking and thickening when stored for a long period of time, and is still not used. It wasn't quite satisfactory.

[Means O to solve all problems]

As a result of intensive research under such circumstances, the present inventor has found that if a dispersion of biocidal active substance is stirred with rigid media having a particle size of 0.5 mm or less, particles having a particle size of 0.5 μ or less can be obtained. Having found that a micronized biocidal drug substance with a concentration of 5 Q vt% or more can be obtained, and that the biological activity is significantly enhanced with micronization, the micronized biocidal drug product thus obtained can be used as an active ingredient. 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 request 1977
No. 9-185889).

As a result of further studies, the inventors of the present invention have discovered that the biological efficacy can be further enhanced when the micronized biocide thus obtained is used in combination with a specific azo2/scent, and the present invention has been further developed.

That is, in the present invention, particles having a particle size of 0.5 or less
A micronized biocide with vt% or more and the following (1) to (
The present invention provides an aqueous suspension biocide composition containing a compound selected from i) as an essential ingredient.

(1)? Lyoxyalkylene nonionic surfactant.

(i) de-lyoxyalkylene alkyl (or alkylaryl) ether phosphates or salts thereof.

In the micronized biocide used in the present invention, particles having a particle size of 0.5μ or less account for 50vt% or more, and further include 0.5μ or less particles.
Particles with a particle size of μ or less are 50vt% or more and the average particle size is 0
．． It is preferable that the particles have a particle diameter of 5 μm or less, and particularly preferably 7 Q vt% or more of particles with a particle size of 0.5 μm or less and an average particle size of 0.4 μm or less.

The biocide active material, which is the raw material for the micronized biocide used in the present invention, includes any biocide that is insoluble in water and solid or paste-like at a constant temperature, regardless of whether it belongs to Class 11. Any biocide can be made into microparticles according to the present invention and used in combination with azoupant to provide a biological effect unprecedented in the art. Moreover, the biocide active substance can also be used in combination of two or more types of biocides with different groove structures.

Biocides that are insoluble in water and are solid or paste-like at room temperature include copper agents, organic tin agents, 1 organic arsenic agent, sulfur, sulfur (zincified ethylene bis(dithiocarbamate)), Organic sulfur agents such as thiuram (bis(zomethylthiocarpamyl)ditylphite); organic chlorine agents such as Shiconyl (tetrachloroisophthalonitrile) and rubcide (4,5,6,7-titrachlor 7-thallide); others Cabtane (N-()lychloromethyltheo)-4-cyclohexene-1.2-S/cargoxiimide), difortan (N-(1,1,2,2-tetrachloroethylthio)-4-cyclohexene-1) ,2
-dicarboximide), acrizid (2-secondary-butyl-4,6-dinitrophenyl-3-methylflotoneate), Topsyn M (dimethyl 4.4'-〇-)unisine-3.3'- zothiozoallophanate),
Benlate (methyl-1-(7'tylcarbamoyl)-
2-benzimidazole carbamate), tacgalene (
Herbicides include nip (2,4-zochlorophenyl-p-nitrophenyl ether), MO (11-nido-t2phenyl-2,4,6-)di Diphenyl ether herbicides such as chlorphenyl ether); Stam (a/, 4/-
Acid amide herbicides such as Zochlorfa pionanilide) and Daimid (N-dimethyl-2,2-zophenylacetamide); Carbamate herbicides such as Suetsude (methyl-3,4-zochlorcarpanylate); Carmex D (3-(3,4-dichlorophenyl)-1,1-
Urea-based herbicides such as diethyl flare); Cymicin (2-
Chlor-4,6-bis(ethylamino)-1,3,5-
triazone herbicides such as DATENORIM (2-C!-4-ethylamino-6-isopropylamino-6-isopropylamino-1.3.5-) LYACIN); insecticides such as DDT (
Organochlorine insecticides such as 1,1,1-trichloro-2゜2-bis(para-chlorophenyl)-nitane), Kayaace (/e razomethylsulfamyl phenylzoethyl phosphorothionate), Guard side (2-chlor-1
Organophosphorus insecticides with aroma II such as -(2,4,5-)dichlorophenyl)-pinylzomethyl 7 phosphate); Dena? (1-naphthyl-methylcarbamate),
Tumaside (!, -)lyl methyl carbamate), Macpal (3,5-xylyl methyl carbamate), Mypsin (-cumenyl methyl carpamate), Sancide (0-isofo,/xyphenyl methyl carbamate) Bamate insecticides, metaldehyde (acetaldehyde tetramer), dinate (8-
/ Chiru N- (methylcarbamyloxy fragment-thioacetimide), etc.; acaricides such as Hasatsupitsun (p-arylphenyl P-chlorobenzene sulfonate), Tetheon (
p-Chlorphenyl-2$ 4@5-tri/l: I-ruphenylsulfone), Quer7ine (2,2,2-) IJ
/ 1.1-(p-/lorphenyl) ethanol), Omite (2-(p-tert-butylphenoxy)cyclohexyhf robinyl sulfite)
, Plictran (tricyclohexyl hydroxytin), etc.

The method for producing the imitative biocide according to the present invention is particularly specific.

Although not limited to K, it can be easily produced, for example, by stirring a dispersion of the biocidal active substance with rigid media having a particle diameter of 0.5 mm as described below.

The raw biocidal drug substance is used by dispersing a commercially available powder in water, but a commercially available dispersion may also be used.Also, the concentration of the dispersion liquid is such that the biocide drug product is in the range of S to iQw1%. Preferably, high 11K is particularly preferable considering production vehicles.

The preferred media are those with a particle size of 0.5I or less, particularly 0.05 to 0.5I. The material of this media can be a rigid body, such as Ottawa sand, glass, alumina, Zolcon, etc., but glass is preferable.A The biocidal substance and the media T-The equipment for stirring and making it into fine particles is a sand mill, a sand grinder, etc. However, the sand mill and sand grinder used in the present invention are generally known. Both vertical and horizontal types can be used, and commonly used types of disks can also be used.

The temperature during microparticulation is preferably 5 to 3 G'C, 3
If it exceeds 0'C, it is not preferable because it takes a long time to make the particles into particles, making it difficult to make them into particles.

Kitamoto describes the mixing of media and biocidal substance during atomization.
The volume ratio is in the range of 40/60 to 80/20, preferably 60/40 to 7G/30.

The biocidal active substance micronized as described above is subjected to pressure filtration and then centrifuged gi! It is obtained by separating the media and the biocide drug dispersion, and washing the media with water as needed.

In the above-mentioned microparticulation, if a suitable dispersant is added to the dispersion of the biocidal raw material, the microparticulation can be carried out more effectively.

Particularly preferred dispersants include the following compounds (1) to (3). These dispersants may be used alone or in combination.

(1) A water-bathable or water-dispersible electropolymer 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, derivatives thereof such as alkyl esters (such as methyl esters), alkali metal salts (such as soda salts), ammonium salts and organic amine salts (such as triethanolamine salts) of the above acids; There is a mixture. In addition to these monomers, copolymerizable monomers such as vinyl acetate, imbutylene, zoisoptylene, and styrene can also be added as copolymerization components.

These monomers can be formed into polymeric stones by conventionally known methods. Although there are no particular restrictions on the proportion of the j% polymer component and the degree of polymerization of the monomer, it is necessary that the monomer is 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 luic acid, copolymers of maleic acid and imbutylene, copolymers of maleic acid and styrene, and salts of these with alkali metals, ammonia, and organic 72 It is also possible to use two or more types of these polymer tubes.

(2) Polymer of styrene sulfonate Does a polymer of styrene sulfonate polymerize styrene sulfonate or? It can be easily produced by sulfonating listyrene. The polymer of styrene sulfonate has a skeleton represented by the following formula.

+io, M molecular weight is 1000 or more, preferably 10000 to 300
1M means Ll, alkali metal salts such as Na% IC, or NHl, alkylamine-alkanolamines, etc.

The polymer of styrene sulfonate may be an O copolymer of styrene sulfonate and other monomers. Such a copolymer can be easily produced by copolymerizing styrene sulfonate and other monomers or by converting a copolymer of styrene and other monomers into sulfonylamine! A can be built. In the case of copolymerization, it may be used as long as it does not have the effect tV of the present invention. The monomers to be copolymerized include hydrophobic monomers such as alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, propylene, butylene, putazoene, zoisoptylene, vinyl chloride, vinylidene chloride, acrylonitrile, and styrene; and acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, vinyl alcohol, acrylamide, methacrylamide, diacetone acrylamide,
R such as N-vinylpyrrolidone, 2-acrylamido-2-methylprono9nesulfonic acid, metaallylsulfonic acid, etc.
A water-based lid 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 sulfone dispersion derivatives, naphthalene sulfonic acid derivatives, etc. It is a formalin condensate.

The above compound (3) according to the present invention includes, for example, 7-talene,
It can be obtained by sulfonating alkyl-substituted 7-talene, anthracene, alkyl-substituted anthracene, lignin, those having aromatic 3J in petroleum residue, etc. by a general method, followed by kyc salt formation reaction, and then formalin condensation. . In this case, the degree of condensation is preferably □1
．． 2-30, more preferably 1.2-10. ζ
Here, when the degree of condensation is 1.2 or less, the effect of condensation is small, and when it exceeds 30, □ the molecular weight becomes high, which causes a problem in practical terms, rather than considering solubility.

As the polycyclic aromatic compound to be used, 15ate can be used, but it is preferable to use t11no, na7rivy, leg prime number 1-601, or lunaf Irene. <1 Of course, a mixture of these may also be used.

Salts include alkali metals such as sodium and potassium, and alkali salts such as calcium, as well as alkali salts such as alkali metals such as sodium and potassium. [KO,l
It is preferable to add K 0.5-10 w%%.

The micronized biocide thus obtained contained 5 Gtt% or more of particles having a particle size of 0.5 or less [particle size and its distribution were determined using a centrifugal automatic particle size distribution measuring device CAP Mu5oocs Factory. I did it. The dispersion containing this micronized biocide has conventionally been
Particle size 11 - Dispersion stability is significantly improved compared to a dispersion containing a biocide.

Since the biocide thus obtained for use in the present invention is micronized, its biological effects are already enhanced compared to the conventional dispersion 11K containing the main agent a, but the following compounds (r) to (10) By using it in combination, the biological effect is further enhanced.

(1) -Sao11? Dialkylene I11 Nonionic Surfactant The following compounds 1 to 2 are preferred.

■ A product obtained by adding renoxide in alcohol to a mixture of fatty acid tribrisepheids and polyhydric alcohols.

Fatty acid tri/9-9-ide is *Kll unspecified - triglycerides of higher fatty acids are generally used. Examples of higher fatty acids include behenic acid, stearic acid, oleic acid, linoleic acid, steric acid, thucric acid, caprylic acid, and the like. Also,
These higher fatty acids may be a single type or a mixture of two or more types; however, 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, can easily be used. It can be obtained as soon as it is obtained, and it is widely used for administering the original tSt*.

Such natural fats and oils include animal fats such as beef tallow, lard, and mutton fat; coconut oil, gnome oil, flattened oil, castor oil, rapeseed oil, coconut kernel oil, soybean oil, olive oil, and linseed oil. Examples include OS physical oils and fats such as oil, tokumo; and strawberry.

As a polyhydric alcohol, carbon number exceeds JL%/%2~
Compounds having 2 to 6 carbon atoms and having 6 hydroxyl groups are preferred, examples include ethylene glycol* fat'lengericol; dali heptaline; 1.2-, 1, 3-, and 2,3-
Detylene = 1-l 5l-2--1-3--
2-3--XO:Z, +-pentylene gelicol eL-
Examples include 2-, 1, 3-, 2, 3-, and 2,4-silene glycol; ltantriol: pentantriol; hexanetriol; pentaerythritol: norvint; mannit; xylit; dulcit. .

Among these polyhydric alcohols, those having 3 carbon atoms, especially glycerin, are most convenient for the purposes of the present invention. However, mixtures of these polyhydric alcohols can also be used @ the molar ratio of fatty acid triglyceride and polyhydric alcohol used is 1:0.1 to 5, preferably 1:0.
It is 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, teropylene oxide alone, and a combination of ethylene oxide and propylene oxide are preferred. When used in combination, it can be either random or block.

The alkylene oxide is added in an amount of 1 to 100 mol, preferably 5 to 60 mol, per 1 mol of the total of fatty acid triglyceride and polyhydric alcohol.

Addition reactions are not limited to addition reactions, but are generally performed to form alkylene ions to compounds having active hydrogen.
? The reaction can be carried out under the conditions of the id O addition reaction. That is,
A catalytic amount of an alkaline substance was added to the mixture of triglyceride and polyhydric alcohol charged in the above molar ratio, and alkylene oxide was introduced into the mixture at about 100 to 200'C11 to S'-1/♂ over several hours. This can be done by reacting.

The product obtained by this addition reaction is a mixture of various compounds, and although its composition is not clear, alkylene oxide is added between the fatty acid constituting the triglyceride and the polyhydric alcohol or glycerin derived from the triglyceride. It is estimated that the main component is a compound containing
ether.

The alkyl (or alkenyl) group has 4 to 22 carbon atoms, and the oxyalkylene is oxyethylene, oxypropylene, oxybutylene alone or in a mixture, and among them,
The proportion of oxyethylene is preferably 50% by weight or more based on oxyalkylene.

The number of moles of oxy or dialkylene added is 1 to 100 moles, preferably 3 to 50 moles.

■ ? Dioxyalkyle/mono- or sialkyl (also d-aryl) phenyl ethers.

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 ti OIF Diethylene, oxyalkylene, oxybutylene alone or in a mixture. Among them, the ratio of oxy1f1/7 to oxyalkylene is
The Qi amount is preferably at least %.

The number of moles of oxyalkylene added is 1 to 100, preferably 3 to 50 mol.

■ Oxyalkylene 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, oxybutylene-on combination is preferably 50% by weight or more based on oxyalkylene 7.

The number of moles of oxyalkylene added is 1 to 100 moles, preferably 3 to 50 moles.

■ Oxyalkylene Sorpitan fatty acid ester.

The fatty acid is a higher fatty acid with a carbon Xm of 8 to 22, and an ester degree of 1 to 4, preferably 1 to 3. The oxyalkylene is oxyethylene, oxy7'' robylene, or oxybutylene alone or in a mixture. Among them, the proportion of oxyethylene is preferably 50x amount % or more based on the kaoxyalkylene.

The number of moles of oxyalkylene added is 1 to 1O.

molar, preferably 3 to 50% molar.

■ ? Lyoxyalkylene norpitol 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 5. Oxyalkylene is oxyethylene, oxypropylene, oxybutylene alone or in mixtures. Among these, it is preferable that the proportion of oxyethylene is 50 Xk% or more based on the oxyalkylene.

The number of moles of oxyalkylene added is 1 to 100 moles, preferably 3 to 50 moles.

■ ? Lyoxyalkylene 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 at least % sox based on the oxyalkylene, and the number of moles of oxyalkylene added is 1 to 100 mol, preferably 3 to 50 mol.

■ Polyoxyalkylene alkyl (or alkenyl)
The amine alkyl (or alkenyl) group has 4 to 12 carbon atoms, and the oxyalkylene is oxyethylene, oxypropylene, oxybutylene alone or in mixtures. Among them,
It is preferable that the ratio of oxyalkylene f L/70 is 50% by weight or more based on oxyalkylene/.

Addition percentage of oxyalkylene is 1~ 100 mol, preferably 3 to 50 mol.

■ Plating oxyethylene/? Rioxy fa pyrene block d remer.

Those having a molecular weight of 1,000 to 10,000 are preferred.

■~■ can also be used in combination.

(i) $lioxyalkylene alkyl (or alkylaryl) ether phosphate esters or salts thereof.

The production method is not limited, and it can be produced by a generally known method, for example, by adding alkylene oxide to alcohol or alkylphenol, reacting it with phosphorus pentoxide, and neutralizing as necessary.

The starting material alcohol has a straight or branched alkyl group having 1 to 22 carbon atoms, or a double bond or water* in the chain.
It is an alcohol having an alkenyl group or a hydroxyalkyl group. It preferably has 4 to 18 carbon atoms, has 0 to 4 double bonds, preferably 0 to 2 double bonds, and has 0 to 4, preferably 0 to 2 hydroxyl groups. Butanol, 2-ethylhexanol, 5')
Illustrative examples include 9-alyl, stearyl-al, and oleyl-al. The alkylphenol preferably has an alkyl group having 4 to 18 carbon atoms.

7) Added to h call? Ethylene oxide f is an alkylene oxide that forms a lyoxyalkylene chain.
a) Pyrene oxide and butylene oxide are mentioned. These may be a single block, two or more types of blocks, or randomly added cells, and the number of added cells is 1 to 1.
100 moles, preferably 1 to 50%.

The addition reaction can be carried out using known methods, e.g. with acid or alkali catalysts.
This can be achieved by introducing and reacting alkylene oxide at 50 to 200° C. and 1 to 5 KF/- under cloth. There are various methods for phosphorylating polyoxyalkylene alkyl (or alkylphenol) ether. For example, 1 mole of phosphorus pentoxide is added to 3 liters of oxyalkylene alkyl ether to be oxidized, and the reaction is blinded at 80 to 100°C for about 6 hours. Disilicate esters can be easily obtained. The ridged oxyalkylene alkyl (or alkylphenol) ether phosphate obtained in this case is a mixture of approximately equal amounts of monoester and diester,
As an adjuvant in the present invention, both monoesters and diesters exhibit excellent effects, but monoesters, especially polyoxyalkylene alkyl ether phosphate monoesters or salts thereof, exhibit excellent effects. K s By neutralizing this phosphoric acid ester with a base, an oxyalkylene alkyl ether phosphoric acid ester salt is obtained from K.

This phosphoric acid ester salt also has a similar potency-enhancing effect. Examples of the salts include alkali metal salts, alkaline earth metal salts, monoethanolamine salts, jetanolamine salts, triethanolamine salts, and a/monicum salts.

In the present invention, the ratio by weight of the micronized biocide and the compound selected from (1) to (2) is preferably 1:0.055-20, more preferably 1:0.
S ~15.

In carrying out the present invention, in addition to the essential micronized biocide and compounds selected from (1) to (1), a dispersant, a water bath thickener, an antifoaming agent, an anti-decomposition agent, and an anti-aggregation agent are used. Agents etc. can be added as necessary.

As a dispersant, I have already mentioned the method of micronization. In addition to the remer-based compounds, one nonionic surfactant and/or anionic surfactant is used. Examples of these nonionic surfactants and/or anionic surfactants include: Lioxyethylene (hereinafter referred to as POE) alkyl (carbon number 6-22) ether, POE alkyl (
C4-18) Phenol ether, ? Lioxyzolobylene polyoxyethylene (block or random) alkyl ether, POE phenylphenol ether,
POE styrenated phenol ether ox) I
J pencil phenol ether nato nonionic surfactant, lignin sulfonate, alkylpe/zene sulfonate, alkyl sulfone (R salt, POL: alkyl sulfonate, POE alkylphenyl ether sulfonate, POE alkylphenyl ether phosphate) acid ester JLpoz phenylphenol ether sulfonate,
POE phenylphenol ether phosphate ester salt,
Examples include ionic surfactants such as naphthalene sulfonate, naphthalene sulfonic acid formalin condensate, and lipensol phenylphenol ether phosphate ester salt.These may be used alone or They can be used in combination.The content thereof in the composition is from 0 to 20 cents by weight, preferably from 1 to 10 cents 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, phosphorus 7a+, pectin derived from plants,
Gum arabic, guar gum, etc., semi-synthetic viscous substances include methylated products, carmexylalkylated products, hydroxyalkylated products (including methylcellulose, calgoxymethylcellulose, hydroxymethylcellulose, etc.) of cellulose or starch carriers, and synthetic viscous materials. So what about polyacrylates and polymaleates? Specific examples include ribinylpyrrolidone°. The water-soluble thickener is about 0 to 3.0 in the bottom material! Lid %, preferably about Q, 0
It is blended in an amount of 5 to 0.53i%.

Antifoaming agents may be added up to about 2% by weight to prevent foaming during formulation, and decomposition inhibitors may be added up to about 731.t% to prevent decomposition, especially during storage of organophosphorus biocides. It is preferable to include it.As the anti-foaming agent, any of them can be used, but specific examples include polypropylene glycol, silicone oil, etc.As the anti-decomposition agent, for example, Examples include epichlorohydrin, phenyl F/V ether, and allyl glycysol ether.In addition, depending on the type, and within a range that does not impair the effects of the present invention, agglomeration inhibitors for solid biocides (for example, ?lioxyethylene) may be used. lyoxyfcI pyrene block polymer), a drift inhibitor (for example, norbitol), etc. can be added.

To summarize the above, an example of the aqueous suspension biocide composition of the present invention is as follows.

a) Biocides 10-60. iii amount% (I
jl (1) “U) O compound 10-60’(
C) Dispersant 0-2oI (D) Water-soluble thickener 0-31 (E) Anti-foaming agent 0,21 (F) Decomposition inhibitor 0-7I (dJ water □0-8o
.

In addition, *ll! of the aqueous suspension biocide composition. The order in which each component is added is not limited.

The following margin [Function] Although the mechanism of how the aqueous suspension biocide composition of the present invention exerts its biological effect is not necessarily clear, it is possible that the biocide is present on the leaf surface as the biocide is made into fine particles. (9) Azoyupant, a compound selected from phantom, has a very strong solubilizing power for biocides; One possible reason is that the biocide is made into finer particles to facilitate its penetration from the plant surface or into insect and fungal bodies.

〔Effect of the invention〕

The aqueous suspension biocide composition of the present invention has a higher biological effect than the conventional biocide active substance with a large t2 diameter because the biocide is made into fine particles. The biological effect was further enhanced.

〔Example〕

Next, the present invention will be explained with reference to examples and reference examples, but the present invention is not limited to these actual proportions.

Reference example 1 Dogshin M powder 6? J? , a dispersant 4? represented by the formula (the molecular weight of the compound of the above formula is approximately 350,000). , water 559 and 0.1-0.2'H glass beads (media) 140? Mix (media/dispersion liquid volume ratio = 50750) L, internal volume 40Or! L
The disk was rotated at a circumferential speed of 6 m/sec for 12 hours in a sand grinder (manufactured by Igarashi Kikuzo). The temperature inside the sand grinder is 20-25C. Furthermore, after forming imitative particles, this is filtered under pressure to obtain a finely divided Dognon M dispersion of approximately 10 of. By washing the media twice with Makuhon 701, 97 wt % of Totsuzozone M can be recovered.

As shown in Table 1, this micronized Topnon M is 0
．． Particles having a diameter of 5 μ or less have a particle size distribution of 72 wt−.

Hereinafter,', : Mortar Table 1 Reference Example 2 Loveside (et, #1 agent) powder 46t1 200s Water-soluble copolymer salt represented by Iris (the molecular weight of the compound of the above formula is 680,000) 4 .5? , water 63F and 0.1-0.
20 colors x Heath (media) 187f 1 liter (media/dispersed liquid volume ratio = 63/37) L, same volume 400W
The disk was rotated for 12 hours at a circumferential speed of 6 per second in a sand grinder (manufactured by Igarashi Kikai). The bottom inside the sand grinder is 20-25C. Furthermore, when this is filtered under pressure, a micronized rubside dispersion liquid 601 is obtained. Also, by washing the media twice with 70 f of water, 98 wi- of love side can be recovered.

As shown in Table 2, this micronized rubside has a 0.0.
The particle size distribution consists of 100vt% of particles having a particle size of 5μ or less.

Reference Example 3 Simin (herbicide) 56f, water-soluble copolymer salt represented by the formula (the molecular weight of the compound of the above formula is 320,000) 4.5? , water 39.5f and 0.1~
0.20 Glass Peas (Media) 187rt Mixture (
Media/dispersed liquid volume ratio = 53/47) The disk was run for 12 hours at a peripheral speed of 6 m/sec for 1.21 cycles in a sand grinder (manufactured by Igarashi Kikai) with an internal volume of 400 L%. One degree in the sand grinder is 20-25°C. Furthermore, when this is filtered under pressure, it becomes imitative particles.
! L liquid 602 is obtained.

As shown in Table 2, this micronized Simin contains 88wt% of particles having a particle size of 0.5μ or less Reference Example 4 Carmex D (herbicide) 45.5F, naphthalenesulfonic acid formalin condensate (F7A degree 4) N & salt 4.5
fs Water Sat and 0.1 to 0-2 mm glass beads (media) were mixed at 180 rt (media/dispersed liquid volume ratio = 50/'50) and placed in a sand grinder (manufactured by Igarashi Kikai) with the same volume of 400 rt. Rotate the disk at a peripheral speed of 6 m/sec for 3 hours. The temperature inside the sand grinder is 20-25°C. Furthermore, when this is filtered under pressure, micronized Carmex D613 is obtained.

As shown in Table 2, this micronized Carmex D has 0.
Particles with a particle size of 5s or less consist of a 95 vrt 560 particle size distribution.

21st! ! Reference example 5 Tsumaside (R insect repellent) powder 45.5? 4. A water-soluble copolymer salt represented by the formula (the molecular weight of the compound of the above formula is 260,000). Sf, water 50f and glass beads (media) 187F of 0.1 to g-2 JLI were mixed (media/dispersed liquid volume ratio = 5015G) in a sand grinder (Isofu Kikaitenzo) with an internal volume of 400-L. , the disk is rotated for 8 hours at a circumferential speed of 6 m/sec.

One degree in the sand grinder is 20-25°C. Furthermore, by filtering this under pressure, a micronized lamicide dispersion liquid 70f is obtained.

This micronized Tsumaside is 0.5μ as shown in Table 3.
Particles having the following particle sizes consist of a 90vt-0 particle size distribution.

Reference Example 6 2/Nate (insecticide) #45. S? , a water-soluble copolymer salt having the formula (the molecular weight of the compound of the above formula is 220,000) 4.5? , 5 degrees of water and 187 tons of glass beads (media) of 0.1 to 0.2 N were mixed (media/dispersed liquid volume ratio = 5015 G) in a Nando grinder (manufactured by Igarashi Kikai) with a capacity of 61 L and 400 mm. The disk is d&ed for t-8 hours at a circumferential speed of 6 m and 1 second.

The temperature inside the sand grinder is 20-250°C. Then, when this is filtered under pressure, micronized raninate dispersion H
45t is obtained.

As shown in Table 3, this micronized runate has l'c0.
Particles having a particle size of 5μ or less consist of a particle size distribution of about 74vt.

Reference example 7 Plictran (acaricide) powder 45.5? .

Water-soluble copolymer salt represented by the formula (the molecular weight of the compound of the above formula is 180,000) 4.5F, water 50f and O,1~
Mix 187t of 0.2u glass beads (media) (
Media/dispersion liquid volume ratio = 50150) L, internal volume 4
In the 00- sand grinder (manufactured by Igarashi Kikai),
The disk is rotated at a rotation speed of 6 m/sec for 8 hours.

Inside the sand grinder! The temperature is 20-25°C. Furthermore, when this is filtered under pressure, it becomes a particulate Delictran dispersion liquid 70? is obtained.

This micronized Norictran is 0.5% as shown in Table 3.
Particles dllo having a particle size of less than μ.

It consists of a particle size distribution of wt%.

The following is a white example 1. To test the bioenhancing ability of various anojuvants for the Topsin M micronized sol shown in Reference Example 1, Chinese cabbage was inoculated with soft rot fungi, and after the onset of the disease (7th day) Topsin M!
Particulate sol and azoupant were sprayed at each concentration of a. Leave it under high temperature and high humidity for 7 days after treatment, measure the diameter of the lesion after disease onset and the diameter of the lesion after drug treatment, and evaluate the therapeutic efficacy by calculating the control value using the following formula. Note that the diameter of the lesion after onset of the disease was 1 OEl. The results are shown in Table 4.

Diameter of lesion area after disease onset Example 2 Rice plants at the 5-leaf stage were treated in advance with an aqueous suspension containing the Rubside micronized sol shown in Reference Example 2, and 6 hours later, the blast fungus spore suspension was sprayed. Processed. After being left under high temperature and high humidity for 10 days, the number of rice blast lesions was counted, and the control value t- relative to the untreated plot was calculated using the following formula. The results are shown in Table 5.

Below, Iz White Example 3 Testing the bioenhancing power of various anoepants against the Simasin value particulate sol shown in Reference Example 3.4, and the Carmex D imitative particulate sol, at the 9th, 5th to 6th leaf stage, plant height 12t: m 20 Mexican meshi A@grass plants were grown per plant and treated with spraying of Simin or Carmex D micronized sol and azoepant at various concentrations. 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. Fruit resistance is shown in Table 6.

The following All White Example 4 In order to test the bioenhancing ability of various asiepants on 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 azoepant at various concentrations. did. One day later, 30 adult insects were released, and the insecticides were determined after 7 days. - The results are shown in Table 7.

Below is a margin Example 5 To test the bioenhancing power of various azoyupants shown in Reference Example 6 7
I asked for the insect control department after the day. The results are shown in Table 8.

Below is a margin Example 6 To test the bioenhancing power of each Muku azoyuvant against the brictran value particulate sol shown in Reference Example 7, 10 to 1
Soybeans at the first leaf stage were sprayed with Plictran micronized sol and Azoepant at various concentrations. After leaving it for one day, adult female two-spotted spider mites (20 individuals) were added to it, and three days later, the total number of mite growls was counted, and the acaricidal rate was calculated using the following formula. Result t-
Shown in Table 9.

11, °Ding Zenshiro

Claims (1)

[Claims] 1. A micronized biocide containing 50 wt% or more of particles having a particle size of 0.5 μ or less, and a compound selected from the following (i) to (ii) as essential components. An aqueous suspension biocide composition. (i) Polyoxyalkylene type nonionic surfactant. (ii) Polyoxyalkylene alkyl (or alkylaryl) ether phosphates or salts thereof.