JP2013095744A - Biocide composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve such problems that an agent using a carboxylic acid metal salt and a pyrethroid insecticidal and/or germicidal component has insufficient formulation stability and that a water dilution of the agent to be used in an immersion treatment for an industrial purpose has insufficient long-term stability.SOLUTION: Formulation or a water dilution of a biocide composition with long-term stability can be obtained by incorporating a carboxylic acid metal salt, a pyrethroid insecticidal and/or germicidal component, a solvent and a surfactant. The carboxylic acid metal salt is preferably a carboxylic acid metal salt synthesized from a monovalent carboxylic acid. The solvent is preferably at least one solvent selected from esters, ethers, and aromatic hydrocarbons. The surfactant preferably comprises a polyoxyethylene-hardened castor oil ether or polyoxyethylene castor oil ether, and at least one selected from a nonionic surfactant and an anionic surfactant.

Description

The present invention relates to a biocidal composition that is effective for use by diluting wood with water in order to prevent insect damage to the wood and deterioration and contamination by microorganisms.

Various insecticides and fungicides have been developed to protect wood from insect damage, microbial degradation and contamination, and methods of treating wood with biocidal compositions containing them have been employed. As a method of treating the biocidal composition, a method of applying a liquid diluted in water of the biocidal composition to wood, a method of spraying, a method of immersing wood in the diluted solution, a method of pressure injection treatment, etc. Has been done. The biocidal composition has good formulation stability, has excellent insecticidal effect, is easy to handle, and has a good water dilution stability. Especially, the biocidal composition for wood applications is a solution diluted in water. The thing whose stability is good for a long time is desired.

JP-A-11-207706 JP2008-81466

Provided is a biocidal composition for wood which has a long-term stability of a liquid diluted in water.

As a result of researches to achieve the above object, the present inventors have completed the present invention.
That is, the present invention
(1) It contains (A) a carboxylic acid metal salt, (B) a pyrethroid insecticide component and / or bactericidal component, (C) a solvent and (D) a surfactant, and can be used after diluted in water. A biocidal composition characterized in that it is.
(2) A biocidal composition wherein the carboxylic acid metal salt is a carboxylic acid metal salt synthesized from a monovalent carboxylic acid.
(3) A biocidal composition wherein the metal carboxylate is a salt of zinc and / or copper with at least one carboxylic acid selected from versatic acid, naphthenic acid and octylic acid.
(4) A biocidal composition characterized in that the bactericidal component is a triazole-based bactericidal component.
(5) A biocidal composition containing at least one solvent selected from esters, ethers and aromatic hydrocarbons as a solvent.
(6) Polyoxyethylene hydrogenated castor oil ether or polyoxyethylene castor oil ether as a surfactant and at least one compound selected from nonionic surfactants and anionic surfactants A biological composition is provided.

The biocidal composition of the present invention has good formulation stability, can be used after diluting in water, and the long-term stability of the water dilution is not caused by separation, sedimentation or crystal precipitation. to enable.

Examples of the carboxylic acid of the carboxylic acid metal salt of the composition of the present invention include saturated fatty acids, unsaturated fatty acids, dicarboxylic acids, hydroxy acids and the like, and monovalent carboxylic acids are particularly preferable, and further, versatic acid, naphthenic acid and Octyl acid is more preferred. These may be used alone or in combination of two or more.

Examples of the metal salt of the carboxylic acid metal salt of the composition of the present invention include zinc, copper, cobalt, nickel, tin, zirconium, titanium, chromium, manganese, iron, and the like. preferable. These may be used alone or in combination of two or more.

The pyrethroid insecticide of the composition of the present invention includes etofenprox, fenvalerate, esfenvalerate, fenpropatoline, cypermethrin, permethrin, cyhalothrin, deltamethrin, cycloprotorin, fulvalinate, bifenthrin, halfenprox, Tralomethrin, silafluophene, d-phenothrin, ciphenothrin, d-resmethrin, acrinaslin, cyfluthrin, tefluthrin, transfluthrin, tetramethrin, alletrin, praretrin, empentrin, imiproslin, d-flamethrin, phthalthrin and optical isomers and geometric isomers thereof Etc. They may be used alone or in combination of two or more. In particular, permethrin, bifenthrin, ciphenothrin, and etofenprox are preferable. The total amount of pyrethroid insecticide is 10% by weight or less, preferably 0.1 to 6% by weight of the preparation.

As the bactericidal component of the composition of the present invention, triazole compounds, organic iodine compounds, sulfamide compounds, bis quaternary ammonium salt compounds, quaternary ammonium salt compounds, dithiol compounds, thiophene compounds, thiocarbamate compounds Compounds, nitrile compounds, phthalimide compounds, pyridine compounds, pyrithione compounds, benzothiazole compounds, triazine compounds, guanidine compounds, urea compounds, imidazole compounds, isothiazoline compounds, nitroalcohol compounds, etc. It is done. Triazole compounds are particularly preferable. The total amount of the bactericidal component is 10% by weight or less, preferably 0.2 to 9% by weight of the preparation.

Examples of the triazole compounds include cyproconazole, hexaconazole, propiconazole, tebuconazole, ipconazole, azaconazole, epoxiconazole, metconazole, tetraconazole, penconazole, triadimethone, vitertanol, microbutanyl, diniconazole, difenoconazole, imi Benconazole, triadimenol, 2- (2,4-difluorophenyl) -1- (1H-1,2,4-triazol-1-yl) -3- (trimethylsilyl) propan-2-ol, etc. . These may be used alone or in combination of two or more. Cyproconazole, hexaconazole, 2- (2,4-difluorophenyl) -1- (1H-1,2,4-triazol-1-yl) -3- (trimethylsilyl) propan-2-ol are particularly preferred. .

Examples of the organic iodo compound include iodopropynyl butyl carbamate (IPBC), p-chlorophenyl-3-iodopropargyl formal, 1-[[(3-iodo-2-propynyl) oxy] methoxy] -4-methoxybenzene, 3 -Bromo-2,3-diiodo-2-propenyl ethyl carbonate and the like.

Examples of the sulfamide compounds include N-dichlorofluoromethylthio-N ′, N′-phenylsulfamide, N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-4-trisulfamide, N, N— Examples thereof include dimethyl-N ′-(fluorodichloromethylthio) -N ″ -phenylsulfamide, N-dimethylaminosulfonyl-N-tolyl-dichlorofluoromethanesulfamide and the like.

Examples of the bis-quaternary ammonium salt compound include N, N′-hexamethylene bis (4-carbamoyl-1-decylpyridinium bromide), N, N′-hexamethylene bis (4-carbamoyl-1-decylpyridinium acetate), Examples include 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide), 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium acetate), and the like.

Examples of the quaternary ammonium salt compound include di-n-decyl-dimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and benzalkonium chloride.

Examples of the dithiol-based compound include 4,5-dichloro-1,2-dithiol-3-one.

Examples of the thiophene compound include 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, and the like.

Examples of the thiocarbamate compound include tetramethylthiuram disulfide.

Examples of the nitrile compound include 2,4,5,6-tetrachloroisophthalonitrile.

Examples of the phthalimide-based compound include N-1,1,2,2-tetrachloroethylthio-tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-dichlorofluoromethylthiophthalimide, N-trichloromethylthiophthalimide and the like.

Examples of the pyridine compound include 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine.

Examples of the pyrithione compound include zinc pyrithione and sodium pyrithione.

Examples of the benzothiazole compound include 2- (4-thiocyanomethylthio) benzothiazole.

Examples of the triazine compound include 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, hexahydro-1,3,5-tris (hydroxyethyl) -s-triazine, and the like.

Examples of the guanidine-based compound include 1,6-di- (4'-chlorophenyldiguanide) -hexane, polyhexamethylene biguanidine hydrochloride and the like.

Examples of the urea compound include 3- (3,4-dichlorophenyl) -1,1-dimethylurea.

Examples of the imidazole compound include methyl-2-benzimidazole carbamate, methyl-2-benzimidazole carbamate hydrochloride, 2- (4-thiazolyl) -benzimidazole, and the like.

Examples of the isothiazoline-based compounds include 2-methyl-4-isothiazoline-3-one, 2-n-octyl-4-isothiazoline-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one, 5 -Chloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, 1,2-benzisothiazolin-3-one, N- and n-butyl-1,2-benzisothiazolin-3-one.

Examples of the nitroalcohol compound include 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitro-1-ethanol, and the like.

Solvents of the composition of the present invention include aromatic or aliphatic hydrocarbons (xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane, cyclohexane, etc.), halogenated hydrocarbons (chlorobenzene, dichloromethane) , Dichloroethane, trichloroethane, etc.), alcohols (methanol, ethanol, 2-propanol, butanol, hexanol, benzyl alcohol, ethylene glycol, etc.), ethers (diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene) Glycol monomethyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-pyrrolidone), alkylidene carbonates (such as propylene carbonate), vegetable oils (such as soybean oil, cottonseed oil), plant essential oils (such as orange oil, hyssop oil, lemon oil), and water. Aromatic hydrocarbons, ethers and esters are preferred. These may be used alone or in combination of two or more. In the present composition, the total amount of the solvent is 20% by weight or more.

As the surfactant in the composition of the present invention, a nonionic surfactant, an anionic surfactant, or the like can be used. Examples of the nonionic surfactant include polyoxyalkylene allyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene allyl phenyl ether, polyoxyethylene styryl phenyl ether. , Polyoxyethylene alkylphenyl ether formaldehyde condensate, polyoxyethylene-polyoxypropylene block polymer, polyoxyethylene-polyoxypropylene block polymer alkylphenyl ether, sorbitan fatty acid ester (eg, sorbitan monooleate, sorbitan monolaurate, sorbitan) Monostearate, sorbitan trioleate, etc.), polyoxyethylene fatty acid ester, Oxyethylene sorbitan fatty acid esters (eg, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate), polyoxyethylene castor oil ether, polyoxyethylene cured Castor oil ether, polyethylene glycol fatty acid ester and the like. Examples of the anionic surfactant include alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene benzyl (or styryl) phenyl ether sulfate, polyoxyethylene-poly Oxypropylene block polymer sulfate, alkyl sulfonate, dialkyl sulfosuccinate, alkyl benzene sulfonate, mono- or di-alkyl naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, lignin sulfonate, polyoxyethylene Alkyl phenyl ether sulfonate, polyoxyethylene alkyl ether sulfosuccinate, polyoxyethylene alkyl ether phosphate, polyoxyethylene, mono- or di- Le Kill phenyl ether phosphates, polyoxyethylene benzyl (or styryl) phenyl ether phosphates, polyoxyethylene benzyl (or styryl) phenyl ether phosphates or polyoxyethylene - polyoxypropylene block polymer phosphate.

In the composition of the present invention, the total amount of the surfactant is in the range of 7 to 15% by weight. In a more preferred embodiment, the amount of polyoxyethylene hydrogenated castor oil ether or polyoxyethylene castor oil ether is 1% by weight or more, nonionic The amount of the surfactant and / or anionic surfactant is 6% by weight or more.

In the biocidal composition of the present invention, stabilizers such as antioxidants and ultraviolet absorbers, rust preventives, colorants, fragrances, antifoaming agents and the like are added to the composition of the present invention as necessary. Also good.

The biocidal composition of the present invention can be treated at the time of use by diluting it twice or more with water on a weight basis and spraying, coating, spraying or immersing the wood in the diluted solution.

The possibility of water dilution in the biocidal composition of the present invention means that the water-diluted solution is stably and uniformly dissolved and / or emulsified and dispersed.

Next, although the test example of this invention is given and demonstrated, this invention is not limited to these. In addition, all% shown below are weight%.

Versatic acid (manufactured by Toei Kako Co., Ltd.) 153.92 g, zinc white (manufactured by Toei Kako Co., Ltd.) 39.36 g, and ion-exchanged water 39.26 g were added to the reaction vessel, mixed well, and then heated to 85 ° C. Reacted. After the reaction, the mixture was heated to 135 ° C. and dehydrated. Zinc versatic acid synthesized by this reaction was used in the preparation of Examples and Comparative Examples.

150 g of Versatic acid (manufactured by Toei Chemical Co., Ltd.) and 98 g of 38% sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) aqueous solution were added and reacted, and then heated to 80 ° C. After heating, 408.67 g of a 27% aqueous solution of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted at 80 ° C. After the reaction, the synthesized versatile copper of the oil layer was recovered and used for the production of Examples and Comparative Examples.

Octyl acid (Wako Pure Chemical Industries, Ltd.) 41.81 g and 38% sodium hydroxide (Wako Pure Chemical Industries, Ltd.) aqueous solution 32.43 g were added and reacted, and then heated to 80 ° C. After warming, 187.75 g of a 19% copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) solution was added and reacted at 80 ° C. After the reaction, the synthesized solid copper octylate was recovered and used for production of Examples and Comparative Examples.

Examples and Comparative Examples were prepared according to Tables 1 to 5 below.

(Formulation stability test)
Stability was evaluated by putting 100 ml of the biocidal compositions of the above Examples and Comparative Examples into glass bottles, conducting a storage test for 1 week to 1 month at 5 ° C. and room temperature, and observing the appearance. The evaluation criteria were as follows.
○ There is almost no separation or precipitation.
× Separation or precipitation occurs.

(Stability test of water dilution)
Evaluation was performed by diluting the above-mentioned Examples and Comparative Examples with tap water to double the weight, putting 100 ml of the prepared water dilution into a glass bottle, and observing the state of the water dilution after one week. The criteria for evaluation are as follows.
◎ There is almost no separation or precipitation in the water dilution.
○ Although the water dilution is separated, it can be dispersed again.
× Separation or precipitation occurs and cannot be dispersed again.

Table 4 shows the stability test results of the water dilutions of the biocidal compositions of Examples and Comparative Examples.

The biocidal composition of the present invention can be used for wood surface treatment and dipping treatment. By treating the wood-diluted water-diluted solution by spraying, coating, spraying or dipping on the wood, it is possible to protect the wood from insect damage, microbial degradation and contamination.

Claims (6)

(A) Carboxylic acid metal salt (B) Pyrethroid-based insecticidal component and / or bactericidal component (C) Solvent (D) Surfactant (A), (B), (C) and (D) are contained in water. Biocidal composition characterized in that it can be diluted. The biocidal composition according to claim 1, wherein the metal carboxylate is a metal carboxylate synthesized from a monovalent carboxylic acid. The biocidal composition according to claim 1 or 2, wherein the carboxylic acid metal salt is a salt of one or more carboxylic acids selected from Versatic acid, naphthenic acid and octylic acid and zinc and / or copper. . The biocidal composition according to any one of claims 1 to 3, wherein the bactericidal component is a triazole-based bactericidal component. The biocidal composition according to any one of claims 1 to 4, wherein the solvent contains at least one solvent selected from esters, ethers, and aromatic hydrocarbons. 6. A surfactant comprising at least one compound selected from polyoxyethylene hydrogenated castor oil ether or polyoxyethylene castor oil ether and a nonionic surfactant or an anionic surfactant. A biocidal composition according to any of the above.