JPS6320202B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention combines 2-(4-thiazolyl)benzimidazole (hereinafter abbreviated as TBZ) and 4-chlorophenyl-3'-iodopropargyl formal (hereinafter referred to as CIF).
It relates to an anti-mildew composition characterized in that it is used in combination with Until now, various antifungal agents have been used for general houses, furniture, household goods, and various industrial products and raw materials, but most of them have limited potency, residual effect, or limited range of use, and are toxic to humans and livestock. There was a tendency to neglect the aspects of environmental pollution and pollution, and this was never satisfactory. In order to solve this problem, the present inventor conducted various studies on a large number of compounds and their combinations, and found that when a mixture of TBZ and CIF was used as an active ingredient, the efficacy was enhanced due to a synergistic effect and it could be widely applied. We have obtained the knowledge that it is a household and industrial antifungal composition that can be used. That is, TBZ constituting the composition of the present invention has the structural formula [], and CIF has the structural formula []

【formula】

TBZ or CIF alone is a compound that is widely used as an industrial fungicide, but a synergistic effect is observed when TBZ and CIF are used together, and the present invention The composition became an anti-mildew composition with even better efficacy. The ratio of TBZ and CIF used varies depending on the conditions of use, but it is best to use about 0.2 to 5 parts of CIF, more preferably 0.5 to 2 parts, to 1 part of TBZ.
Mix according to this combination. When compounding, it can generally be applied directly to various industrial products and their raw materials as base materials, or mixed with a suitable carrier, and if necessary, emulsifiers, dispersants, penetrants, stabilizers, and organic blowing agents can be added. etc. are added,
It can be used in any dosage form such as liquid, emulsion, wettable powder, transpiration agent, aerosol, etc. Examples of solvents that can be used in the composition of the present invention include water, fats, and alicyclic hydrocarbons such as kerosene and
For aromatic hydrocarbons such as α-pinene, benzene and
Chlorinated hydrocarbons such as toluene and xylene, dichloromethane and chlorocene, ketones such as acetone and cyclohexanone, esters such as amyl acetate and benzyl acetate, and alcohols such as ethyl alcohol, isopropyl alcohol, and n-butyl alcohol. , these can be used alone or in combination. Examples of carriers that can be used in wettable powders include vegetable powders such as soybean flour, wood flour, and diatomaceous earth, and mineral powders such as mica powder, talc, kaolinite, calcite, and dolomite. They can be used in combination, and the preferred proportion is usually 1 to 100 parts by weight per 1 part by weight of the composition of the present invention. Examples of surfactants that can be used as emulsifiers and dispersants include anionic surfactants such as α-olefin sulfonic acid, alkyl ether sulfate salts, and polyoxyethylene alkyl ether sulfate salts, and nonionic surfactants such as polyoxyethylene alkyl ether sulfate salts. Oxyethylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amines and fatty acid amides, polyethylene glycol fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, and tetraalkylammonium as cationic surfactants. amphoteric surfactants such as salts, trialkylbenzylammonium salts, alkylcarboxybetaine type,
These surfactants are of the alkylaminocarboxylic acid type, and it is usually preferable to use 0.01 to 5 parts by weight per 1 part by weight of the composition of the present invention. Dispersion stabilizers that can be used in the composition of the present invention include, for example, casein and gelatin for proteins, gum tracanth and gum acacia for rubbers, and alginic acid, carboxymethylcellulose, nitrocellulose, acetyl cellulose, and acetyl glycol for carbohydrate derivatives. Chylcellulose, methylcellulose, ethylcellulose, acetylpropionylcellulose, benzylcellulose, hydroxypropylcellulose, etc.; among polymer compounds, vinyl resins such as vinyl acetate resin, vinyl acetate-vinyl chloride copolymer resin, polyvinyl butyral, acrylic resin, etc.; alkyd resins For example, oils or fatty acid modified resins of condensates of polyhydric alcohols such as glycerin or pentaerythritol and polybasic acids such as phthalic acid; aminoalkyd resins such as melamine or mixtures of urea resins and alkyd resins; acid-curing urea System resins such as urea or urea-melamine cocondensation resins with a low degree of etherification; Epoxy resins such as blends of epoxy resin solutions and organic amine curing agents such as diethylenetriamine and ethylenediamine, epoxy resin amine adducts, etc.; Polyester resins such as A mixture of a chain alkyd having a large number of unsaturated double bonds in the molecule and a curing catalyst and accelerator based on methyl ethyl ketone peroxide-cobalt naphthenate or benzoyl peroxide-dimethylaniline; urethane resin such as hexamethylene diisocyanate, etc. Examples include addition reaction resins of isocyanates and polyols such as ethylene glycol and glycerin; natural resins such as those containing lacquer and cashew as main components. Examples of organic blowing agents that can be used as transpiration agents include azo compounds such as azodicarbonamide,
Examples of the sulfonyl hydrazide compound include benzenesulfonyl hydrazide and toluenesulfonyl hydrazide, and the preferred proportion is usually 1 to 20 parts by weight per 1 part by weight of the composition of the present invention. The composition of the present invention can be applied to a base material by impregnation, coating, or mixing with the base material, depending on the characteristics and usage conditions of houses, fittings, furniture, household goods, industrial products, and various raw materials. It can be used for mold-proofing walls and ceilings, tatami mats, floors, furniture, etc. in general homes, or for general industrial products such as paints, resins, pastes, adhesives, wood, bamboo, leather, cleaning agents, etc. Ideal as a fungicide for many industrial raw materials and products. Furthermore, the composition of the present invention has little risk of residual toxicity, pollution, etc., and can be used safely. The present invention will be explained in more detail below with reference to Test Examples and Examples, but the scope of the present invention is not limited thereby. Next, specific anti-mildew properties depending on the mixing ratio of the anti-mildew composition used in the present invention will be explained in the following test examples. <Antibacterial spectrum test> Potato decoction agar medium containing a predetermined concentration of the antifungal composition of the present invention with a constant total amount was placed in a Petri dish for 10 minutes.
After solidification, one platinum loop of mycelia or spores of the test bacteria cultured on a test tube slant medium was inoculated onto the streak line, and left in a constant temperature room at 25℃ for 7 days. was determined. The following seven types of bacteria were tested, and the results are shown in Table 1. Bacterium A AsPergillus niger ATCC 6275 Bacterium B Aspergillus oryzae IFO 4075 Bacterium C Penicillium citrinum ATCC 9849 Bacterium D Rhizopus Japanicus SN 32 Bacterium E Chaetomium globosum ATCC 6205 Bacterium F Coriolellus Palustric
Forestry Research Institute 0527 Bacterium G Coriolus versicolor
Forestry Research Institute 1030

[Table] As is clear from the above results, the composition of the present invention had a synergistic effect, and its antifungal efficacy was high and showed a broad antibacterial spectrum. Example 1 1 part of TBZ, 2 parts of CIF, and 120 parts of ethyl alcohol are uniformly mixed and dissolved to obtain the antifungal composition of the present invention as a liquid. When used, the liquid preparation of the above composition is used as it is or after being diluted as appropriate depending on the purpose. Example 2 5 parts of TBZ, 5 parts of CIF, 100 parts of dimethyl sulfoxide
part, glyceryl monostearate 1 part, polyoxyethylene castor oil derivative (POE addition mole number 60
2 parts (mol) were mixed uniformly to obtain the antifungal composition of the present invention as an emulsion. When used, the emulsion having the above composition may be used as is or diluted with water to a predetermined concentration. Example 3 1 part of TBZ, 2 parts of CIF, and 20 parts of azodicarbonamide are uniformly mixed to obtain an antifungal composition of the present invention as a transpiration agent. When using, use the specified amount of the above transpiration agent.
Heating at 250°C to 300°C evaporates the active ingredients. Example 4 An antifungal composition of the present invention for coating having the composition shown in Table 2 below was obtained.

【table】

[Table] <Wood preservative test> The liquid agent shown in Example 1 and each single agent with the same active ingredient content for comparison were impregnated at high pressure into beech wood (4 cm x 5 cm x 0.5 cm) at 5 kg/cm ³ for 1 hour. After the treatment, it was placed on a potato decoction agar plate in a Petri dish, and FG among the bacteria tested in Test Example 1 was
After inoculation, the two species were cultured at 25°C ± 2°C for 14 days, and the growth status of the bacteria was observed. The test was conducted in triplicate, and the results are shown in Table 3. In addition, the results were displayed according to the following criteria. 4...No growth of mycelium is observed on the treated wood pieces. 3...The area of mycelial growth observed on treated wood pieces does not exceed 1/3 of the total area. 2...The area of mycelial growth observed on the treated wood piece is 1/3 or more and 2/3 or less of the total area. 1...The area of mycelial growth observed on treated wood pieces exceeds 2/3 of the total area.

[Table] <Paint test> The emulsion in Example 2 and each single agent with the same active ingredient content for comparison were added to an acrylic emulsion paint at 100, 200, 500, and 1000 ppm.
Add the following amount and mix until homogeneous, then add 3
It was applied twice on both sides of a plywood board measuring cm x 6 cm, dried at room temperature, and then placed on a plate of a potato decoction agar medium. A mixture of spores of five types of bacteria A to E among the bacteria tested in Test Example 1. The suspension was inoculated by spraying, and after culturing at 25°C±2°C for 7 days, the growth state of the bacteria was observed. The test was conducted in triplicate, and the results are shown in Table 4. In addition, the results were displayed using the same criteria as the wood preservative test.

[Table] <Transpiration agent efficacy test> The transpiration agent in Example 3 and each single agent with the same active ingredient content for comparison were tested in advance in Test Example 1 using five types of bacteria A to E. A fixed amount of the spore mixture suspension was placed on a potato decoction agar plate, and after drying, it was placed on the top, side, and floor of a room (34.5 m ³ ) at 0.5, ¹ ,
Heat and foam an amount of 2.4 g at 250 to 300°C, leave it in a closed state for a day and night, then take out the sample shear.
After culturing at 25°C ± 2°C for 5 days, the minimum amount of the transpiration agent to inhibit bacterial growth was determined based on the presence or absence of bacterial growth. The results are shown in Table 5.

【table】

Claims (1)

[Claims] 1. An anti-mildew composition comprising a mixture of 2-(4-thiazolyl)benzimidazole and 4-chlorophenyl-3'-iodopropargyl formal as an active ingredient.