JPH0358324B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel antifungal composition that maintains a strong antifungal effect for a long period of time even when wet with water, and has excellent storage stability. In recent years, as the number of residences that are highly airtight and equipped with air-conditioning and heating equipment has increased, they are being used not only in relatively humid areas such as bathrooms and kitchens, but also in closets, ceiling bags, etc.
Mold has started to grow, and controlling it has become a major issue from a hygienic and aesthetic standpoint. By the way, there are many different types of mold that occur in normal living environments, and unless you eliminate all of them, you will not be able to avoid the damage caused by mold. There is a need for something that is effective against the environment and that can maintain its effectiveness for a long period of time even in humid places. Although many household fungicides have been known to date, none of them have a sufficient inhibitory effect on a wide range of molds, their effectiveness does not last for a long time, and they are generally non-emulsifying types. When dissolved in the alcoholic solvent used and used in liquid form or in spray form using a propellant, there is a drawback that the stability of the liquid at low temperatures is significantly deteriorated. This loss of effectiveness of the fungicide is particularly noticeable in humid areas, and it has been extremely difficult to prevent mold from growing in areas that are likely to get wet, such as bathrooms and kitchens, over a long period of time. In addition, stability at low temperatures in alcoholic solvents was an essential requirement in order to fully exhibit the antifungal effect. The present inventors have overcome the shortcomings of conventional fungicides, have completely suppressed the growth of a wide variety of molds that occur in the living environment, and have long-lasting effects even in wet areas. We developed a fungicide composition containing a water-insoluble polymer compound to maintain its effectiveness over a period of time, but it was found that these had poor storage stability at low temperatures when used in alcohol-based solvents. . Therefore, the present inventors aimed to obtain a composition that exhibits a complete growth-inhibiting effect against mold, maintains its effect for a long period of time even in locations that are easily wetted with water, and has excellent liquid stability. As a result of extensive research, the present invention has been completed. That is, the present invention provides 2-(4-thiazolyl)-benzimidazole, a long-chain alkyldimethylbenzylammonium salt, and a lower alkyl ester of a N-long-chain acyl basic amino acid in a solvent containing a water-insoluble polymer compound. The present invention provides a fungicide composition containing salts each at a concentration of at least 0.01% by weight. The 2-(4-thiazolyl)-benzimidazole used as one active ingredient of the composition of the present invention has the structural formula The compound represented by is known to exhibit a growth-inhibiting effect on many molds, but alone it does not exhibit sufficient anti-fungal activity to completely suppress molds that grow in the home environment. The long chain alkyldimethylbenzylammonium salt used as the other active ingredient has the general formula (In the formula, R is an alkyl group having 8 to 22 carbon atoms, and X is a halogen atom.) It is a compound represented by It does not show sufficient fungicidal effects against all the various types of mold that occur. In the present invention, 2-(4-thiazolyl)-benzimidazole, a long-chain alkyldimethylbenzylammonium salt, and a long-chain N-long-chain By using it in combination with a lower alkyl ester salt of an acyl basic amino acid, it synergistically increases the anti-fungal power against individual molds and expands the anti-fungal spectrum. They succeeded in obtaining a fungicide that exhibits excellent effects against all of them and also has excellent liquid stability. Particularly suitable as the long-chain alkyldimethylbenzylammonium salt used in the present invention is benzalkonium chloride. These long-chain alkyldimethylbenzylammonium salts may be used alone or in combination of two or more. The blending ratio of the 2-(4-thiazolyl)-benzimidazole and the long-chain alkyldimethylbenzylammonium salt is preferably 9:1 to 1:9 by weight, particularly preferably 4:1 to 1:4. used. Further, the amount of each of these components used should be at least 0.01% by weight, based on the total composition. If the amount is less than this, a sufficient antifungal effect cannot be obtained. Next, water-insoluble polymer compounds include, for example, polyvinyl acetate, partially saponified polyvinyl acetate, formalized polyvinyl alcohol, formalized partially saponified polyvinyl acetate, butyralized polyvinyl alcohol, butyralized partially saponified polyvinyl acetate, ethylene- Saponified products of vinyl acetate copolymer, vinyl acetate-acrylamide copolymer, vinyl acetate-methyl vinyl ether copolymer, saponified product of vinyl chloride-vinyl acetate copolymer, etc. can be used, but vinyl acetate is preferred. homopolymers, copolymers, their saponified products, and their acetalized products. In addition, from the viewpoint of the solvent used to make the target composition into a homogeneous solution, alcohol-soluble ones are advantageous. In the present invention, this polymer compound has a concentration of 0.01
It is used as a solution with a concentration of at least 0.1% by weight, preferably at least 0.1% by weight. The solvent for preparing the solution of the polymer compound may be an organic solvent or a mixture of an organic solvent and water. Suitable organic solvents include lower alcohols such as methanol, ethanol, propanol, and isopropanol, lower diols such as ethylene glycol and propylene glycol, and lower ketones such as acetone and methyl ethyl ketone. Ethanol, propanol or isopropanol are particularly suitable in terms of safety and drying properties, and these are used in combination with water if necessary. The lower alkyl ester salt of N-long chain acyl basic amino acid in the composition of the present invention is a component for stably retaining the active ingredient in solution, and the long chain acyl group is a fatty acid having 8 to 16 carbon atoms. The residues used are, for example, lauroyl, cocoyl or myristoyl, preferably cocoyl, and the basic amino acid is arginine or lysine, preferably arginine. Particularly suitable is the general formula (RCO- in the formula is a fatty acid residue having 8 to 16 carbon atoms). The composition of the present invention contains this compound in a proportion of 0.01% by weight or more, preferably 0.02% by weight or more. To prepare the composition of the present invention, a given polymer compound is dissolved in a suitable solvent, and a given amount of 2
Add -(4-thiazolyl)-benzimidazole and long chain alkyldimethylbenzylammonium salt to form a homogeneous solution. In this case, the polymer compound and two active ingredients and
There is no particular restriction on the order of addition of the lower alkyl ester of N-long chain acyl basic amino acid, and they may be added in any order or may be added at the same time. Since the composition of the present invention has good liquid stability, it can be prepared into any form of use such as application, spraying, and spreading. When the composition of the present invention is applied to a desired location, after drying, the two active ingredients become immobilized by the polymer compound. Since this polymer compound is water-insoluble, the active ingredient will not be removed even if it gets wet with water, and it can maintain a strong antifungal effect for a long period of time. As described above, the composition of the present invention uses 2-(4-thiazolyl)-benzimidazole in combination with a long-chain alkyldimethylbenzylammonium salt and a lower alkyl ester salt of an N-long-chain acyl basic amino acid, It has excellent liquid stability during use, exhibits a wide antifungal spectrum at low concentrations, and has a synergistic growth-inhibiting effect on a wide variety of molds, and the water-insoluble polymer compound prevents the elution of active ingredients. Therefore, it is suitable as a fungicide for household use, especially in humid places. Next, the present invention will be explained in more detail with reference to Examples. Reference example 2-(4-thiazolyl)-benzimidazole (hereinafter abbreviated as TBZ), benzalkonium chloride (hereinafter abbreviated as AMB) and lower alkyl ester salt of N-long chain acyl basic amino acid, each alone and Dissolve the combined mixture in ethanol,
A mold resistance test was carried out in accordance with JIS-Z-2911 "Mold resistance test method, 7. Testing of paints". That is, filter paper (Toyo Filter Paper, No. 2, diameter 30 mm) was soaked in the ethanol solution of each sample, pulled out, left indoors for 2 hours, and then placed in the center of the culture surface of a specified culture medium in a Petri colander. 1 c.c. of the test mold spore suspension was evenly spread thereon, and then the Petri dish was covered with a lid and cultured at a temperature of 28° C. for 14 days. The culture medium at this time is 1000ml of water,
The composition used was 40 g of glucose, 10 g of peptone, and 25 g of agar. In addition, the molds shown below were used as test molds.

【table】

[Table] Liquid stability was evaluated visually after a predetermined period of time after storing the product in a 100 ml glass bottle at -5°C. Evaluation criteria: ○...No abnormality observed Δ...Very slight insoluble matter present ×...Clearly cloudy or insoluble matter observed The results are shown in Table 1. Each symbol in the table has the following meaning. −: No mold growth is observed +: Some mold growth is observed ++: Significant mold growth is observed

【table】

[Table] Example TBZ0.2%, AM0.1% and N〓− in ethanol
Cocoyl-L-arginine ethyl ester D.L
Pyrrolidone carboxylate 0.2% dissolved,
and TBZ0.2%, AMB0.1%, N〓−cocoyl−
Add and dissolve 1.0% of PVB (butyralized polyvinyl alcohol) to 0.2% of L-arginine ethyl ester D.L pyrrolidone carboxylate,
Furthermore, an aerosol type fungicide was prepared by adding the propellant Freon 12 at a rate of 25 g/100 ml. This fungicide was sprayed on areas in the home where mold is likely to grow, and the mold growth status was investigated over a period of 6 months. Also, at the same time, regarding the liquid stability of the content liquid.
It was placed in a 100 ml glass bottle, stored at -5°C, and visually evaluated, but no abnormality was observed even after 30 days. The results are shown in Table 2.

[Table] -: No mold occurs
＋；Mold occurs

Claims (1)

[Claims] 1. In a solvent containing a water-insoluble polymer compound,
A fungicide composition comprising 2-(4-thiazolyl)-benzimidazole and a long-chain alkyldimethylbenzylammonium salt and a lower alkyl ester salt of an N-long-chain acyl basic amino acid at a concentration of at least 0.01% by weight, respectively. thing. 2. The composition according to claim 1, wherein the water-insoluble polymer compound is a polyvinyl alcohol derivative. Claim 1, wherein the long chain acyl moiety of the lower alkyl ester salt of a 3 N-long chain acyl basic amino acid is a lauroyl group, a cocoyl group, or a myristoyl group, and the basic amino acid moiety is arginine or lysine. Compositions as described.