JPS623805B2 - - 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. In recent years, as the number of highly airtight homes equipped with air-conditioning and heating equipment has increased, mold has begun to grow not only in relatively humid areas such as bathrooms and kitchens, but also in closets, ceiling bags, etc. Suppressing this has become a major issue from both aesthetic and aesthetic points of view. By the way, there are a wide variety of types of mold that occur in normal living environments, and unless all of them are eliminated, it is impossible to avoid the damage caused by mold. There is a need for something that can be effective against a wide range of molds and that can maintain its effectiveness over a long period of time even in humid conditions. and,
Although many household fungicides have been known to date, they all have the disadvantage that they do not have a sufficient suppressive effect on mold over a wide range of areas, and their effects do not last for a long period of time. The loss of effectiveness of this fungicide is particularly noticeable in humid conditions, and it is extremely difficult to prevent mold from growing over a long period of time in areas that are likely to get wet, such as bathrooms and kitchens. Ta. The present inventors have overcome these drawbacks of conventional fungicides, and have demonstrated complete growth-inhibiting effects on a wide variety of molds that occur in the living environment, and have long-lasting effects even in wet areas. As a result of extensive research to develop a fungicide composition that can maintain its effects over a period of time, we have found that an active ingredient that is a combination of two specific compounds is contained in a solution of a water-insoluble polymer compound. The present inventors have discovered that the composition can achieve multiple purposes, and have accomplished the present invention. That is, the present invention provides a water-insoluble polymer compound containing 2-(4-thiazolyl)-benzimidazole and a long-chain alkyldimethylbenzylammonium salt at a concentration of at least 0.05% by weight, respectively. A fungicide composition is provided. 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 and long-chain alkyldimethylbenzylammonium salt are used in combination, which cannot exhibit satisfactory effects as a household fungicide when used alone. By this,
Succeeded in obtaining a fungicide that synergistically increases anti-fungal power against individual molds, expands the anti-mold spectrum, and is highly effective against all types of mold that occur in the home environment. That's what I did. The long-chain alkyldimethylbenzyl ammonium salt used in the present invention is a compound generally known as a benzalkonium salt, and commercially available products include stearyldimethylbenzyl chloride [trade name "Cachinal OB-80E", manufactured by Toho Chemical Co., Ltd.] [manufactured by Kao Soap Co., Ltd.], lauryl dimethylbenzyl chloride [trade name ``Cachinal CB-50'', manufactured by Toho Chemical Co., Ltd.], lauryl myristyldimethylbenzyl chloride [trade name ``Sanizol C'', manufactured by Kao Soap Co., Ltd.], etc. . These may be used alone or as a mixture of two or more. The weight ratio of 2-(4-thiazolyl)-benzimidazole and long-chain alkyldimethylbenzylammonium salt is 9:1 to 1:9, preferably 4:
Used in a ratio of 1 to 1:4. Further, the amount of each of these components used should be at least 0.05% 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 0.1
% or more, preferably 0.2% or more. 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. To prepare the composition of the present invention, a predetermined polymer compound is dissolved in a suitable solvent, and a predetermined amount of 2-
Add (4-thiazolyl)-benzimidazole and long chain alkyldimethylbenzylammonium salt to form a homogeneous solution. There is no particular restriction on the order in which the polymer compound and the two active ingredients are added, and they may be added in any order or may be added at the same time. The composition of the present invention can be prepared in any usage form, such as for coating, 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. Thus, the composition of the present invention exhibits a broad antifungal spectrum at low concentrations by using 2-(4-thiazolyl)-benzimidazole and a long-chain alkyldimethylbenzylammonium salt in combination,
In addition to exhibiting a synergistic growth-inhibiting effect on a wide variety of molds, the water-insoluble polymer compound suppresses elution of the active ingredient, making it suitable as a fungicide for household use, especially in humid areas. It is. Next, the present invention will be explained in more detail with reference to Examples. Reference example 2-(4-thiazolyl)-benzimidazole (hereinafter abbreviated as TBZ) and myristyldimethylbenzylammonium chloride [Kanto Kagaku Co., Ltd. reagent "benzalkonium chloride", hereinafter abbreviated as AMB], each alone and For equal mixtures,
A mold resistance test was conducted in accordance with JIS-Z-2911, "Mold resistance test method, 7. Paint test". That is, a piece of paper (Toyo 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 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】 The results are shown in Table 1.

[Table] As is clear from this table, when TBZ and AMB are used alone, mold growth is observed on the third day even at high concentrations of 1.0% and 0.8%, but when both are used together,
Even at a concentration as low as 0.1%, mold will begin to form after the 5th day, and at 0.2%, no mold will appear at all even after 14 days. Example 1 Polyvinyl butyral (hereinafter abbreviated as PVB)
TBZ and AMB were dissolved in ethanol to a final concentration of 0.2 to 1.0% (W/V), respectively.
A fungicide composition was prepared by dissolving at a rate of 0.4%. This composition was applied to paper (Toyo Paper No. 2, diameter 30
mm) and then air-dried (A) and after air-drying, the surface was evenly washed with 20ml of water and then air-dried.
Regarding (B), a mold resistance test was conducted in the same manner as in the reference example. The results are shown in Table 2.

[Table] As is clear from this table, the anti-fungal power of TBZ and AMB did not decrease with the addition of PVB, and they exhibited sufficient anti-mold power even after getting wet with water. Example 2 Samples A' and B' were prepared in the same manner as in Example 1 except that polyvinyl acetate (hereinafter abbreviated as PVAc) was used instead of PVB, and a mold resistance test was conducted on them. The results are shown in Table 3.

[Table] As is clear from this table, the anti-fungal properties of TBZ and AMB did not decrease with the addition of PVAc, and they exhibited sufficient anti-fungal properties even after getting wet with water. Example 3 TBZ0.2% and AMB0.1% dissolved in ethanol, and TBZ0.2% and AMB0.1% dissolved in ethanol.
An aerosol-type fungicide was prepared by adding and dissolving 1.0% PVB and then 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. The results are shown in Table 4.

[Table] As described above, by spraying the composition of the present invention, it is possible to prevent the growth of mold over a long period of time in places that are easily wetted with water or in humid places in the home. Example 4 In place of AMB in Example 3, lauryldimethylbenzyl chloride (abbreviated as AMB-L) or stearyldimethylbenzyl chloride (AMB-S) was used.
An aerosol-type fungicide was prepared in the same manner as in Example 3 except that the same procedure was used as in Example 3. 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. The results are shown in Tables 5 and 6.

【table】

[Table] In this way, instead of AMB, AMB-L or AMB-
By spraying the composition prepared according to Example 3 using S, mold growth can be prevented for a long period of time in areas that are easily wetted with water or areas that are humid.

Claims (1)

[Scope of Claims] 1. In a solution of a water-insoluble polymer compound, 2-(4
- thiazolyl)-benzimidazole and a long-chain alkyldimethylbenzylammonium salt, each in a concentration of at least 0.05% by weight. 2. The composition according to claim 1, wherein the water-insoluble polymer compound is a polyvinyl alcohol derivative.