JPH05238908A - Fungicidal mildew-proofing polymer composition and its production - Google Patents

Abstract

PURPOSE:To obtain a fungicidal mildew-proofing polymer composition capable of effectively maintaining the resistance to microorganisms for a prescribed period and having excellent washing resistance by melting and mixing a polymer with a fungicidal mildew-proofing agent containing clotrimazole as a constituent component. CONSTITUTION:The objective fungicidal mildew-proofing polymer composition can be prepared by melting and mixing (A) a fungicidal mildew-proofing agent containing 1-(0-chloro-alpha, alpha-diphenylbenzyl) imidazole (clotrimazole) as at least one constituent component with (B) a polymer preferably containing a polyolefin composed of one or more 2-3C monomers, a polyamide or a polyester as at least a constituent component. The fungicidal mildew-proofing agent usable together with clotrimazole is cyabendazole, benzalkonium chloride, trichlorocarbanilide or benzimidazoylcarbamic acid methyl ester.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymer composition comprising an antibacterial and antifungal agent and a polymer.

[0002]

2. Description of the Related Art Organic polymers (hereinafter simply referred to as "polymers") are used as raw materials in all fields, and it is considered that the demand for them will increase more and more in the future. Along with its spread, deterioration of polymers due to microbial contamination and adverse effects on environmental hygiene are also spreading. Among microorganisms, fungi (molds) not only grow on the polymer but also invade the inside of the polymer to destroy its structure and deteriorate it. Furthermore, the spores float in the air and cause an allergic disease, which deteriorates the living environment. In addition, as a result of the mites feeding on the grown mold and the mites growing, the mites themselves also cause allergic diseases, and the representative example is the childhood Zensoku known as Kawasaki disease.

On the other hand, bacteria also have an environment where polymers are placed,
That is, due to water, temperature, and adhesion of nutrients, they grow on the polymer and adversely affect environmental hygiene.

Therefore, conventionally, polymers provided with resistance to microorganisms have been provided, and usually a fungicide / antifungal agent (hereinafter referred to as a drug) is kneaded into the polymer, coated on the surface of the polymer, or a surfactant or a solvent. By the method of impregnating the inside of the polymer using
Polymers are generally endowed with resistance to microorganisms.

Whichever method is used, the obtained polymer must have its resistance to microorganisms effectively maintained for a certain period of time depending on the usage conditions of the polymer. This is because even if the drug is effective immediately after being treated, if it loses its effect in a short period of time, its effectiveness is small.
Especially when the polymer is to be used as clothing, it is desirable to incorporate a drug so as to withstand repeated washing. On the other hand, since the growth of microorganisms starts from the surface of the polymer, it is desirable that sufficient drug be present on the surface to prevent the growth. Furthermore,
It is desirable not to lose the usefulness of the resulting polymer by treating the drug.

However, among the above methods,
In the method of coating on the surface of the polymer or the method of impregnating the inside of the polymer with a surfactant or the like, it is necessary to effectively secure the resistance to microorganisms for a desired certain period of time, in particular, it is poor in washing resistance, or the polymer is treated by treatment. However, there is a problem that the usefulness of is easily lost.

In addition, for example, in the method of kneading into a polymer, it is possible to uniformly disperse the polymer as a whole, and it is easy to maintain the effectiveness for a certain period of time, but when the drug is unstable to heat, it decomposes during heating and mixing. However, there is a problem in that it is difficult to obtain the intended polymer.

[0008] Therefore, resistance to microorganisms is effectively secured for a predetermined period of time, excellent washing resistance is obtained, and usefulness of the polymer is less likely to be lost by treatment with a chemical agent. Furthermore, even when a kneading method is used, heating is performed. It is desired to provide a polymer composition containing an insect repellent and mildew proofing agent capable of stably containing the drug even when mixed.

The present inventor has arrived at the present invention as a result of earnest studies in view of the problems of the prior art.

[0010]

Specifically, the present invention provides 1- (o-chloro-α, α-diphenylbenzyl).
The present invention relates to a polymer composition containing an antibacterial and antifungal agent containing at least one component of imidazole (hereinafter, referred to as a general name "clotrimazole"), and a method for producing the same.

The antibacterial and antifungal agent of the present invention contains at least one component of clotrimazole. However, the antibacterial and antifungal agent of the present invention may further contain other agents in addition to the clotrimazole. it can.

Examples of the other agents of the present invention include siabendazole, orthophenylphenol, diphenyl, esters of p-hydroxybenzoic acid, dehydroacids and salts, benzoic acid and salts, sorbic acid and salts, propionic acid. And salts, cetyltrimethylammonium bromide, benzethonium chloride, benzalkonium chloride, cetylpyridinium chloride, chlorhexidine gluconate and salts (Hibitene hydrochloride: (Sumitomo Chemical Co., Ltd.), 2,2′-
Dihydroxy-5,5'-dichlorodiphenylmethane (Preventol GD: manufactured by Bayer), benzimidazole carbamic acid methyl ester (Preventol B
CM: manufactured by Bayer), N, N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) -sulfamide (preventol A4-S: manufactured by Bayer), N-
(Fluorodichloromethylthio) phthalamide, 3-methyl-4-chlorophenol, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, bromocinnamaldehyde, trichlorocarbanilide, 2,4.
1'of 4'-trichloro-2'-hydroxydiphenyl ether, bronopol, zinc pyrithione, pyrithione Na, didecyldimethylammonium chloride, etc.
Seed or two or more.

As the other drug of the present invention, among these, one kind or two or more kinds selected from siabendazole, benzalkonium chloride, trichlorocarbanilide and benzimidazoylcarbamic acid methyl ester is preferable. It is mentioned as a thing.

As the antibacterial and antifungal agent of the present invention, clotrimazole is particularly preferable.

Examples of the polymer in the present invention include a polymer containing at least one of any one of a polyolefin, a polyamide and a polyester, which is composed of at least one kind of monomer having 2 to 3 carbon atoms. Among these,
Preferable examples include polyethylene, polypropylene, nylon 6, nylon 66, polyethylene terephthalate, and polymers comprising one or more of these. These forms include woven fabrics,
Fibers such as knits, sheets, films and chips,
Examples of the resin molding include pellets.

The method of incorporating the antibacterial and antifungal agent of the present invention into such a polymer includes the method of kneading as described above, the method of coating with a suitable binder if necessary, and the method of using a surfactant or a solvent. There are methods such as impregnation. In the present invention, in addition to the above methods, known methods conventionally used for incorporating antibacterial and antifungal agents into a polymer can be used, depending on the polymer used and the type of antibacterial and antifungal agent. Any method can be used.

Among them, the method of kneading the antibacterial and antifungal agent into the polymer is preferable because it can be applied to any product form.

The amount of the antibacterial and antifungal agent mixed in the polymer is, for example, when the antibacterial and antifungal agent is clotrimazole,
It is preferably 0.05 to 10% by weight, and the optimum amount is 0.1 to 1% by weight, based on the polymer used. 0.05% by weight
If it is less than 10%, it is difficult to obtain sufficient antibacterial property, while if it exceeds 10% by weight, the usefulness of the polymer tends to be impaired.

When the polymer composition of the present invention is produced by a kneading method, the apparatus for producing the polymer composition of the present invention can be heated and adjusted to a constant temperature of up to about 300 ° C. and has a stirring function. It is desirable that it is equipped with and can be filled, sealed, or circulated with an inert gas such as nitrogen.

Using such a device, the polymer and the antibacterial / antifungal agent are uniformly mixed and molded into a shape of a product form according to the purpose of use, or made into a chip shape.

In the polymer composition of the present invention, in addition to the antibacterial and antifungal agent, appropriate amounts of conventionally known additives used in the polymer of the present invention can be appropriately used.

Examples of such additives include stabilizers against temperature, light, etc .; pigments, dyes, etc., liquid paraffin and / or
Or the thing which strengthens antibacterial performance, such as surfactants, such as a nonionic surfactant, can be mentioned.

The production method of the polymer composition of the present invention will be described in more detail below, for example, in the case of the kneading method.

That is, about 50 g of polymer chips were weighed and put in a hard glass separable flask (300 ml) equipped with a stirring blade, and the antibacterial and fungicide of the present invention and, if necessary, other additives were added. Weigh out the required amount.

The air in the flask is replaced with pure nitrogen to keep it airtight. If necessary, flow nitrogen at an appropriate flow rate. While stirring the contents, the flask is immersed in a heating bath (oil bath, containing Shin-Etsu Silicon KF-56) and melt-kneaded. The temperature of the heating bath is controlled at a constant temperature above the melting temperature of the polymer. After kneading for a certain period of time so that the polymer and the additives are sufficiently uniformly mixed, the polymer composition is taken out to obtain a polymer composition. The form of the polymer composition may be any form such as the above-mentioned fibrous, film-like, chip-like, pellet-like resin molding and the like. As the method of melt-kneading the polymer and the additive, in addition to the above method, a known method conventionally used for adding and kneading the additive into the polymer can be used.

Regarding the resistance of the polymer composition of the present invention to microorganisms, the antibacterial performance was evaluated by storing the polymer composition of the present invention obtained by such a method in running water and at a constant temperature for a certain period of time. .. The evaluation method of the antibacterial test was based on the antibacterial test method of JIS 1902-1990 textile products. However, the fungus is Aspergillus
Niger IFO4414 (Black Aspergillus: A.nige
r), Penicillium citrinum IFO6026 (blue mold: P. citrinum) was used, and Staphylococcus aureus IAM12082 (yellow aureus: S. aureus) was used as the bacterium. The medium used for the test was a potato dextrose agar medium for fungi and a normal agar medium for bacteria.

[0027]

EFFECTS OF THE INVENTION According to the present invention, there is provided a polymer composition having excellent washing resistance, thermal stability during the period of use of the polymer, and practicality.

Hereinafter, the present invention will be described in more detail with reference to examples.

[0029]

[Example 1] A polypropylene chip (commercially available as "Ace Polypro, manufactured by Ace Polymer Co., Ltd."), which is widely used for various molded products, was used to make a trial composition as follows.

Hard glass separable flask (300
(5 ml) nitrogen gas with a stirring blade and cover attached to
The air in the flask was replaced with nitrogen by flowing at 0 ml / min. Precisely weigh 30 g of polypropylene chips and a certain amount and amount of the antibacterial and antifungal agent described in Table 1 and Table 2 in a flask and immerse in an oil bath adjusted to 230 ° C. The mixture was stirred and kneaded. The stirring speed is 10-60 rpm
Adjusted to a constant speed. A composition was prepared by kneading for about 30 minutes.

It was taken out from the flask in a molten state, and was threaded into a thread shape, or a fixed amount was pressed onto a metal flat plate to form a pellet.

Using the thus obtained sample as a sample, the antibacterial performance was evaluated by a method according to the above-mentioned JIS 1902-1990 antibacterial test method for textile products. Table 1 shows the antibacterial performance before and after being stored for 1 week in running water, and Table 2 shows the antibacterial performance before and after being stored at 70 ° C. for 1 week by evaluating the presence and the size of halo.

As shown in Table 1, clotrimazole had a .0.
With the addition amount of 05% by weight or more, antibacterial performance was maintained against any fungi and bacteria even after 1 week of washing with water.

Further, as shown in Table 2, the addition of clotrimazole in an amount of 0.05% by weight or more maintained antibacterial properties against any fungi or bacteria even after storage at 70 ° C. for 1 week and disappeared. There wasn't. That is, it has excellent washing resistance and heat resistance and is difficult to decompose.

As shown in Tables 1 and 2, when the antibacterial and antifungal agents other than clotrimazole were used alone, the antibacterial properties considered to be effective could not be exhibited. Almost no halo was found over the course of the day.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

Example 2 In the same manner as in Example 1, a polymer composition was trial-produced by using clotrimazole in combination with other antibacterial and antifungal agents in the types and addition amounts shown in Table 3.

The antibacterial performance was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 3. It is understood that clotrimazole has weaker antibacterial activity against bacteria than fungi, but it can be covered by combination with an antibacterial agent having strong efficacy against bacteria. In addition, all of these polymer compositions are 7
There was no case where the antibacterial property before storage decreased in storage at 0 ° C. for 1 week, and it was stable.

[0040]

Example 3 In the same manner as in Example 1, a polymer composition was experimentally produced by combining the antibacterial and antifungal agent with various additives in the types and the addition amounts shown in Table 4. From Table 4, it can be seen that antibacterial performance is enhanced by using clotrimazole in combination with liquid paraffin, a surfactant and the like. No decrease in antibacterial property was observed in any of these polymer compositions due to storage at 70 ° C. for 1 week.

[0041]

[Table 3]

[0042]

[Table 4]

As additives other than those shown in Table 4, polyethylene glycols, olive oil, polypropylene glycol, cetyl alcohol, etc. were not found to have the effect of enhancing antibacterial performance.

Claims (4)

[Claims] 1. A polymer composition comprising a polymer and an antibacterial and antifungal agent containing at least one component of clotrimazole. 2. The polymer composition according to claim 1, wherein the polymer comprises at least one of a polyolefin, a polyamide, and a polyester composed of one or more monomers having 2 to 3 carbon atoms. object. 3. The polymer composition according to claim 1, further comprising liquid paraffin and / or a nonionic surfactant as an additive. 4. A process for producing a polymer composition, which comprises melt-mixing a fungicide / antifungal agent containing clotrimazole as at least one constituent and a polymer.