JPH03275603A - Antimicrobial formed article - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial formed article containing a specific pyrrolidone compound or further other antimicrobial agent, being also excellent in safety to skin resistance to washing of antimicrobial function and consisting of a nylon fiber, etc. CONSTITUTION:The aimed antimicrobial formed article containing a compound expressed by formula I (R is chain or cyclic aliphatic hydrocarbon group; A is H, amine or cation residue derived from an alkali metal, e.g. R is 2,4,4- trimethylpentyl and A is a group expressed by formula II) at a wt. ratio to formed article of 1-30mg/g. Addition of the compound expressed by formula I to the formed article, especially fiber can be carried out by the treatment normally carried out such as kneading with or impregnation of a dope before forming. But, when solubility of the compound expressed by formula I to water is small, the compound expressed by formula I is preferably solubilized in an aqueous liquid using a surfactant or organic solvent. Other treating agent such as pyrithione zinc may be jointly used in addition to the compound expressed by formula I.

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to molded products, especially fibers, that have excellent antibacterial properties.

Regarding various antibacterial molded products including films.

<Prior art and problems to be solved by the invention> Conventionally, synthetic fibers mainly made of polyester, nylon, and acrylic;
Fibers such as natural fibers such as cotton and wool, various films, and molded products are widely used. These various molded products are often required to have specific functions in their applications. Among these, the present invention is particularly aimed at imparting antibacterial function, which has recently become important in response to diversifying social needs. A large number of treatment chemicals have been proposed in the past for the purpose of serving this field, and many of them are in the practical stage.

However, products in this field often do not solve the problem simply by having antibacterial properties.

Taking textile products as an example, issues that inevitably accompany this type of product include safety when considering contact with human skin, antibacterial function, and wash resistance. Although these issues have traditionally been emphasized,
It is no exaggeration to say that most of them have not overcome all of these.

From this point of view, the present inventor has finally arrived at the present invention as a result of various studies aimed at providing a product that has practically sufficient antibacterial properties as well as the additionally required performance.

〈Means for solving problems〉 That is, the present invention provides the following general formula [I] H3 It is an antibacterial molded product.

The antibacterial molded article of the present invention contains a pyridone compound represented by the above formula [I].

In such a pyridone compound, R represents a chain or cyclic aliphatic hydrocarbon group, and A represents a hydrogen atom or a cationic residue derived from an amine or an alkali metal.

Examples of such a chain aliphatic hydrocarbon group include a C0 to C17 alkyl group that may be branched, a C2 to C17 alkenyl group, and among these, a chain aliphatic hydrocarbon group substituted at the 6-position of the ring may be used. The 2,4,4-trimethylpentyl group is preferred. Further, examples of the cyclic aliphatic hydrocarbon group include a C3 to C8 cycloalkyl group, a cyclohexyl alkyl group, and among these, a cyclohexyl group substituted at the 6-position of the ring is preferred.

On the other hand, the cation residue derived from amine or alkali metal is not particularly limited, but monoethanolamine is preferred.

The pyridone compound of the present invention refers to the compound defined above and contains one or more of these, and among these, a specific example is 1-hydroxy-4-methyl-6-(2,4,4 -trimethylpentyl)-2(IH
) Pyridone monoethanolamine salt, 1-hydroxy-
4-Methyl-6-<cyclohexyl)-2(LH>pyridone monoethanolamine salt is preferable, and it is preferable to contain these alone or both at the same time.

Furthermore, in the present invention, "containing one or more pyridone compounds" means that the pyridone compound is present on the molded article and/or the surface of the molded article in a state where it exhibits antibacterial properties.

In order to contain such a pyridone compound in a molded product,
For example, kneading into dope before molding.

This can be carried out by a commonly used treatment such as impregnation. Moreover, this treatment can be carried out repeatedly using the same pyridone compound or repeatedly using different pyridone compounds.

The content of the pyridone compound in the molded product is 0.01 to 100 in weight ratio of the molded product and the pyridone compound.
■/g, especially 0.5 to 50 ■/g, especially 1 to 30 ■
, 7g is preferred.

When the pyridone compound of the present invention has low solubility in water, one or more types of cationic, anionic, nonionic, or even amphoteric ionic solvents are generally used, or an organic solvent within a range that poses little safety problem is used. or use
It is preferable to solubilize it in an aqueous liquid by taking measures such as adjusting the pH appropriately. A preferred example of solubilization is a method in which the product is once dissolved in propylene glycol or ethylene glycol, and then the solution is dispersed and solubilized in an aqueous solution of an appropriate surfactant, such as sodium lauryl sulfate;
Examples include a method of directly solubilizing in an aqueous surfactant solution without using a solvent; a method of solubilizing by making the pH alkaline to about 11 or higher using, for example, caustic soda. Although a method of processing in the form of an organic solvent solution dissolved in a suitable solvent such as propylene glycol or ethanol can also be mentioned, it is generally preferable to use it as an aqueous solution from the viewpoint of safety. Hereinafter, a solution in which the pyridone compound of the present invention and other surfactants are dissolved will be referred to as a treatment liquid. The concentrations of these various treatment liquids can be changed as appropriate depending on the shape of the molded product to be treated, the degree of antibacterial performance required, etc., but usually, for example, when fibers are immersed in the treatment liquid, the pyridone compound concentration is 0. 1~50g/
The fiber to treatment liquid ratio is 1=3 to 1:100, especially 1:5 to 1:100.
l: about 50 and heated to about 50 to 100℃ for 10
It is appropriate to treat for about 20 minutes to 200 minutes, repeat the treatment three times as necessary, or wash with water or treat with another treatment agent afterward as necessary. These conditions are just examples and are not limited to this range.

For example, in the case of fibers, the types of fibers include synthetic fibers such as nylon, polyester, and acrylic, chemical fibers such as acetate and rayon, and natural fibers such as cotton and wool, but especially nylon. , polyester, wool, and cotton are preferred materials because they have many uses and are easy to obtain with excellent performance.

Each of these fibers may have improved dyeability, for example. One example is polyester fibers that are dyeable with cationic dyes. The treatment method has been explained using fiber treatment as an example, but the treatment liquid containing the pyridone compound of the present invention can be similarly used for molded products such as films.

If necessary, one or more other processing agents may be added to this treatment solution for treatment, or separate treatment may be performed before and/or after the treatment of the present viridinone compound, which will defeat the purpose of the present invention. As long as it doesn't happen, it's fine, and in fact, it's preferable. Other treatment agents recommended in the present invention are chlorhexidine salts, such as 701 hexidine glyconate;
Silico-〉'-based quaternary ammonium, iodine and/or iodophor; thiahesidazole; pyrithiones,
For example, zinc pyrithione, sodium pyrithione; 2.
4.4'-)lichloro 2'-hydroxyphenyl ether; 2-bromo-2-nitro-1,3-propanediol; α-bromocinnamaldehyde + N+N-dimethyl-N'-phenyl-N'-(fluorodichloro One or more types selected from methylthio)sulfamide can be mentioned, and these can be treated simultaneously or separately as long as it does not practically impair the treatment of the pyridone compound represented by the general formula [I]. . In order to avoid undesirable side reactions with the pyridone compound represented by general formula [I], it is safe to treat it separately. for example,
It has been observed that when the pyridone compound represented by the general formula [I] and chlorhexidine salts are combined in a homogeneous liquid phase, a precipitate is formed. Therefore, in such a case, the formation of a sediment should be avoided by subjecting it to a separate process.As in the case of the pyridone compound represented by the above-mentioned general formula [I], such a treatment agent cannot be subjected to treatment as an aqueous liquid. Preferably, in this case as well, it is preferable to perform solubilization using various surfactants. Of course, it is also a preferable embodiment to use a substance that has already been considered for solubilization, such as iodophor, but it is not preferable. It goes without saying that side reactions should be avoided.

Regarding the treatment method, the present invention is not limited to the immersion method as described above. For example, conventionally known methods such as dispersion by spraying, contact with a treatment agent adhesion roller, etc. can be used without any problem.

The pyridone compound represented by the above-mentioned general formula [I] in the present invention appears to be similar to the conventionally well-known pyrithione antibacterial agent. However, compared to pyrithione antibacterial agents, the pyridone compound represented by the general formula [I] of the present invention is far superior in terms of safety. For example, 1 hydroxy-4-methyl-6-(2,4,
The LD50 value of 4-trimethylpentyl)-2(IH) pyridone monoethanolamine salt is
4300 ■/'kg for oral administration, 1-hydroxy-4-methyl-6-(cyclohexyl)-2 (IH
>2500■/k for pyridone monoethanolamine salt
However, zinc pyrithione, which is a typical example of a pyrithione-based antibacterial agent, is significantly less safe at 331*77. Therefore, when using these processing agents together, keep these safety considerations in mind.

Method 2 It is necessary to select conditions, etc.

<Effects of the Invention> According to the present invention, antibacterial molded products with excellent durability and safety can be obtained in various molded products such as textile products.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the examples, all parts represent parts by weight.

Example 1 1-Hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(IH>Pyridone monoethanolamine salt (hereinafter referred to as piroctone olamine)>0.5
part (weight) in 99.5 parts (volume) of ethanol,
This was used as a processing solution. This solution was heated to 70°C and a total denier of 90 deniers and a nylon yarn composed of 36 single yarns, a total denier of 75 deniers and a polyester yarn composed of 24 single yarns, and a total denier of 180 deniers and 2 single yarns were prepared. cotton yarn, total denier 10
Wool yarns of 0 denier were soaked and treated for 1 hour, washed with water, air dried, knitted with a stockinette knitting machine, and washed. Washing conditions are JIS L 0217 appendix <1 + washing method 1
The detergent was a commercially available product (product name, Zabu:
Kao> was used. This was used as a sample to evaluate the piroctone olamine content and antibacterial performance. Antibacterial performance was evaluated using stroke counting method (Seibunsha: Bozono Deodorant p.182-p.18
3).

The results are shown in Table 1.

Table 1 Evaluation results Table 2 Antibacterial evaluation of blended knit products (measurement of number of strokes) (Blending ratio of treatment system - 12.5%> Note 1) Content: Piroctone olamine (■/g > Bacterial count: Difference in increase/decrease value It is expressed as log 100/A-log C/A.

As shown in Table 1, piroctone olamine was contained in all types of fibers, and its antibacterial performance was such that it could withstand 50 washes.

Furthermore, each treatment system was knitted with the corresponding untreated yarn, and the antibacterial performance of the knitted product was evaluated at a mixing rate of 12.5%. The results are shown in Table 2.

Note) Values are shown as differences in increase and decrease values.

As shown in Table 2, sufficient antibacterial performance was exhibited even at a mixing ratio of 12.5%.

Example 2 A nylon yarn consisting of a total denier of 9o denier and 36 single yarn was treated in a 3 (w/v)% aqueous solution of chlorhexidine gluconate or benzalkonium chloride at 80'CX for 1 hour, washed with water and air-dried, and then treated with viroctone. It was treated in an ethanol solution containing 1.2 (w/v)% olamine at 85° C. for 2.5 hours, washed with water, and air-dried. The yarns were treated in a hot air dryer at 110° C. for 2 hours while maintaining a roughly constant length, and each yarn was knitted using a stockinette knitting machine. Table 3 shows the evaluation results.

Table 3 Evaluation by bacterial count measurement method Note) Values indicate the difference in increase/decrease value.

As shown in Table 3, the antibacterial performance of piroctone olamine was not inhibited when used in combination with other antibacterial agents.

Claims (1)

[Claims] 1. The following general formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼... [I] [In the formula, R represents a chain or cyclic aliphatic hydrocarbon group, and A represents hydrogen. Indicates an atom or a cationic residue derived from an amine or an alkali metal. ] An antibacterial molded product containing one or more pyridone compounds represented by the following. 2. The antibacterial molded article according to claim 1, wherein R is a 2,4,4-trimethylpentyl group or a cyclohexyl group substituted at the 6-position of the ring, and A is HOCH_2CH_2NH_3. 3. The antibacterial molded product according to claim 1, which contains one or more other antibacterial agents in addition to the pyridone compound. 4. The antibacterial molded article according to any one of claims 1 to 3, wherein the molded article is a fiber. 5. The antibacterial molded article according to claim 4, wherein the fiber is nylon.