JPS647041B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a micronized biocidal active ingredient for agricultural chemicals with significantly enhanced biological efficacy, a method for producing the same, and a suspension agricultural chemical formulation containing the same. [Prior Art] Agrochemical biocides (hereinafter simply referred to as "biocides"), such as insecticides, fungicides, herbicides, and acaricides, are substantially insoluble in water, and require water as a continuous phase. It is put into practical use as a fluid suspension agent. 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 dosage form, and although various improvement studies have been conducted, caking occurs when stored for a long period of time. However, it also has the drawbacks of increased viscosity, and is not yet fully satisfactory. [Means for Solving the Problems] As a result of intensive research under such circumstances, the present inventor has determined that a dispersion of a biocidal active substance for agricultural chemicals (hereinafter simply referred to as "biocidal active substance") has a particle size of 0.5 mm. It has been found that by stirring with the following rigid media, a micronized biocidal drug substance containing 50 wt % or more of particles with a particle size of 0.5 μ or less can be obtained, and that the biological activity is significantly enhanced as the micronization is performed. Furthermore, if the micronized biocidal drug substance obtained in this way is used as an active ingredient, it will have a high biological effect and will have excellent long-term stability without hard caking at the bottom or thickening caused by natural sedimentation of the biocidal drug substance. The present invention was completed by discovering that a cloudy agricultural chemical formulation can be obtained. That is, the present invention uses particles having a particle size of 0.5μ or less.
The present invention provides a biocidal active substance having a concentration of 50 wt% or more, a method for producing the same, and a suspension agricultural chemical formulation containing the same. In the micronized biocidal active substance of the present invention, particles having a particle size of 0.5μ or less account for 50wt% or more, and furthermore, particles with a particle size of 0.5μ or less are present.
If the following particle sizes are 50wt% or more, the average particle size is
It is preferably 0.5μ or less, and particularly preferably 70wt% or more of particles with a particle diameter of 0.5 or less and an average particle size of 0.4μ or less. The active biocide according to the present invention includes any biocide, regardless of its type, that is insoluble in water and is solid or pasty at room temperature. Furthermore, by making any of the biocides into microparticles according to the present invention, excellent biological effects that were previously unimaginable can be obtained. Moreover, the biocide active substance can also be used in combination of two or more types of biocides having 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-secondary-butyl-4,6-dinitrophenyl-3-methylcrotonate),
Topudin M (dimethyl 4,4'-o-phenylene-3,3'-dithiodialophanate), benlate (methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate), takegalen (3
herbicides such as nip (2,4-dichlorophenyl-p-nitrophenyl ether) and MO (p-nitrophenyl-2,4,6-trichlorophenyl ether). Diphenyl ether herbicide;
Stam (3′,4′-dichloropropionanilide),
Acid amide herbicides such as Daimid (N,N-dimethyl-2,2-diphenylacetamide); Carbamate herbicides such as Swep (methyl-3,4-dichlorocarbanilate); Carmex D (3- (3,4-dichlorophenyl)-1,1-
Urea herbicides such as simazine (2-chloro-4,6-bis(ethylamino)-
Triazine herbicides such as DDT (1,3,5-triazine) and Gesaprim (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine); -Trichlor-2,2-bis(para-chlorophenyl)-
Organochlorine insecticides such as ethane), Kayaace (para-dimethylsulfamyl phenyl diethyl phosphorothionate), Guardside (2-chloro-1-(2,4,5-trichlorophenyl)-vinyldimethylphos) Organophosphorus insecticides with aromatic rings such as denapon (1-naphthyl-methyl carbamate), Tumaside (m-tolyl methyl carbamate), Macbal (3,5-xylyl methyl carbamate), and mypsin (o- Carbamate insecticides such as menyl methyl carbamate), Sancide (o-isopropoxyphenyl methyl carbamate), metaldehyde (acetaldehyde tetramer), and lannate (S-
Methyl-N-(methylcarbamyloxy)-thioacetimide), etc.; acaricides such as satupyran (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 micronized biocidal drug substance of the present invention is produced by stirring a dispersion of the biocidal drug product with a rigid medium having a particle size of 0.5 mm or less. 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, and the like are known as devices for stirring the biocidal drug substance and media to make them into fine particles, but the sand mills and sand grinders used in the present invention may be of a generally known type, and may be of vertical type 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 micronized biocidal drug substance of the present invention is obtained by micronizing the biocidal drug substance in a sand mill, 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, derivatives thereof such as alkyl esters (such as methyl esters) 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,
Examples include copolymers of maleic acid and isobutylene, copolymers of maleic acid and styrene, 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 is an alkali metal such as Li, Na, K, or
It means NH ₃ , alkylamine, alkanolamine, etc. 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 monomers to be copolymerized include alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, propylene,
Hydrophobic monomers such as butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, acrylonitrile, styrene, and acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, vinyl alcohol, acrylamide, methacrylamide, Hydrophilic monomers such as 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 1.2-30, 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 0.1w to the biocide drug dispersion.
% or more, especially 0.5 to 10 wt%. The micronized biocidal active substance obtained in this way contains 50 wt% or more of particles with a particle size of 0.5 μ or less [particle size and its distribution were measured using a centrifugal automatic particle size distribution analyzer CAPA
-500 (Horiba, Ltd.) was used. The same applies in Examples], and the dispersion liquid containing this micronized biocidal active substance has significantly improved dispersion stability compared to the conventional dispersion containing a biocidal active substance with a large particle size. Furthermore, since the biological effect is further enhanced compared to dispersions containing conventional biocidal substances, it is extremely advantageous to use it as an agricultural chemical formulation. Although the suspension agricultural chemical formulation of the present invention has good dispersion stability, a thickener such as cellulose or xanthan gum can be added if necessary. [Operation] Although the mechanism of biological efficacy enhancement by the micronized biocidal active substance of the present invention has not been fully clarified, the micronized particles are released through fine pores such as stomata on the leaf surface and cracks in the cuticle layer due to the micronization. This is thought to be due to the increased ease of invasion and the marked increase in biological activity. [Effect of the invention] According to the present invention, particles having a particle size of 0.5μ or less can be produced.
It has become possible to produce extremely fine biocidal active ingredients with a concentration of 50wt% or more. This micronized biocidal active ingredient has a higher biological effect than conventional biocidal active ingredients with large particle sizes, and a suspension agricultural chemical formulation containing this as an active ingredient has good dispersion stability and excellent biological effectiveness. [Example] Next, the present invention will be explained with reference to Examples. Example 1 Topjin M powder 60g, formula (The molecular weight of the compound of the above formula is approximately 350,000) 4 g of dispersant represented by, 55 g of water and 0.1 to 0.2 mm
Mix 140 g of glass beads (media) (media/dispersed liquid volume ratio = 50/50) and rotate the disc at a peripheral speed of 6 m/s for 12 hours in a sand grinder (manufactured by Igarashi Kikai) with an internal volume of 40 ml. . 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. water again
If you wash the media twice with 70g, Topjin M
97wt% of the total amount 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 0.5 μ or less.

[Table] Example 2 Loveside (sterilizing agent) 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/dispersion liquid volume ratio 63/37), and the disc was rotated at a peripheral 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 20-25
It is ℃. Furthermore, this is filtered under pressure to obtain 60 g of a finely divided rubside dispersion. Also 70g of water
If you wash the media twice with
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. 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 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℃. 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. Example 4 Carmex D (herbicide) 45.5 g, 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] 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. 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. 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
Mix 0.1 to 0.2 mm glass beads (187 g of media (media/dispersed liquid volume ratio = 50/50) and use a sand grinder with an internal volume of 400 ml (manufactured by Igarashi Kikai).
The disk was rotated at a circumferential speed of 6 m/sec for 8 hours. The temperature inside the sand grinder is 20-25 °C. 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 8 Using the Topjin M dispersion obtained in Example 1 (product of the present invention) and the Topjin M dispersion (conventional product) having the particle size distribution shown in Table 4 below, a biological test was conducted by the following method. I did this. The results are shown in Table 5.

[Table] (Test method) Satsuma mandarin oranges were immersed in Botrytis spore suspension.
After 6 hours, add 1 tangerine of the present invention or the conventional product to this.
After spraying 1 ml per individual at various concentrations, they were stored at 27°C for 2 weeks, and the pesticidal effects of the products of the present invention and conventional products were examined. In addition, the control effect was evaluated using the following evaluation criteria. Evaluation criteria:

【table】

[Table] Example 9 Rubside dispersion obtained in Example 2 (product of the present invention)
A biological test was conducted using the following method using 20% cloable agent (conventional product) and Rabside. The results are shown in Table 6. (Test method) Spray treated rice (Nipponbare) with a plant height of 13 cm and 4-leaf stage with blast spore suspension. After 6 hours, the product of the present invention or the conventional product was sprayed at various concentrations, and the rice was heated at 27°C. , and left for two weeks at a relative humidity of 90%. Thereafter, the number of lesions was counted and the control percentage was calculated relative to the untreated area.

[Table] Example 10 Using the herbicide dispersions (products of the present invention) obtained in Examples 3 and 4 and the corresponding commercial products, Simazine 50% hydrating powder and Carmex D 50% hydrating powder, the following method was used. Biological tests were conducted. The result is the 7th
Shown in the table. (Test method) The weed grass was grown to a height of 7 cm and the 3-4 leaf stage, and the products of the present invention and commercially available products were sprayed thereon to examine their herbicidal efficacy. Evaluation was carried out by measuring the above-ground fresh weight and calculating the percentage of weed killing compared to the untreated plot. The amount of dilution water sprayed was 20 per Al.

[Table] Example 11 Using the insecticide dispersions (products of the present invention) obtained in Examples 5 and 6 and the corresponding commercial products, Tumaside 30% emulsion and Rannate 45% hydrating powder, biological tests were conducted by the following method. I did this. The results are shown in Table 8. (Test method) Rice (Nipponbare) was grown to a plant height of 25 cm and the 7-leaf stage, and the products of the present invention and commercially available products were diluted to various concentrations and sprayed at 10 ml per plant. After 6 hours, 50 black leaf flies were released, and the insect killing rate was measured on the 7th day after release compared to the untreated area.

[Table] Example 12 A biological test was conducted using the Plictran dispersion (product of the present invention) obtained in Example 7 and the Plictran 50% hydrating powder (commercial product) according to the following method. The results are shown in Table 9. (Test method) 30 adult female two-spotted spider mites were planted on a 5cm x 5cm bean leaf desk, and left at 25℃ for one day.
Various concentration solutions of the present invention and commercially available products are applied to the desk.
Sprayed 0.3ml (repeated 10 times). On the third day after spraying, the mite killing rate was determined for the untreated area.

【table】

Claims (1)

[Scope of Claims] 1. A micronized biocidal active ingredient for agricultural chemicals, comprising 50 wt% or more of particles having a particle size of 0.5 μ or less. 2. A dispersion of biocidal active ingredient for agricultural chemicals is stirred together with rigid media having a particle size of 0.5 mm or less.
A method for producing a micronized biocidal active ingredient for agricultural chemicals, in which the proportion of particles having a particle size of 0.5μ or less is 50wt% or more. 3. Particle size of 0.5 μ or less as described in claim 2, wherein the dispersion of the biocidal active ingredient for agricultural chemicals contains one or more dispersants selected from the following (1) to (3). A method for producing a micronized biocidal active ingredient for agricultural chemicals having a particle content of 50 wt% 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. (2) Polymer of styrene sulfonate. (3) A formalin condensate of a sulfonated polycyclic aromatic compound or a salt thereof, which may have a hydrocarbon group as a substituent. 4. A suspension agricultural chemical formulation containing as an active ingredient a micronized biocidal active ingredient for agricultural chemicals, in which particles having a particle size of 0.5 μ or less account for 50 wt% or more.