JPH0782663A - Production of antifungal fibers - Google Patents

Abstract

PURPOSE:To obtain an antifungal fiber having high washing durability by treating fibers with an aqueous solution containing a specific antifungal com pound and fixing the compound to the fiber. CONSTITUTION:The fibers such as natural fibers or synthetic fibers are treated with an antifungal agent of poly(hexamethylene-biguanide) and a phenolic compound such as tannic acid by the soaking method or padding method, dried and heat-treated to fix the compound to the fiber whereby the objective antifungal fibers of high washing durability are readily obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an antibacterial fiber, and more particularly to an antibacterial processing method for a fiber product using a polyhexamethylene biguanide compound.

[0002]

2. Description of the Related Art Antibacterial treatment of fibers to prevent discoloration of fibers, embrittlement of fibers, generation of odor, etc. due to propagation of mold and bacteria in microorganisms such as underwear, socks, sheets and pillow covers. Fibers that have been applied have been announced. In recent years, so-called nosocomial infections caused by contact infection with bacteria resistant to antibiotics (MRSA; methicillin-resistant Staphylococcus aureus) in hospitals and treatment centers have become a social problem, and sheets, lab coats, pajamas, etc. Antibacterial processing is required.

As antibacterial agents used for these antibacterial treatments, benzalkonium chloride, polyoxyethylene trimethyl ammonium chloride, benzethonium chloride, cetylpyridinium chloride, alkyl trimethyl ammonium salt, p
-Isooctylphenoxyethoxyethyl dimethylbenzylammonium chloride, phenododecium bromide,
Quaternary ammonium salt antibacterial agents such as cetyl dimethyl ammonium chloride and 3- (trimethoxysilyl) propyl octadecyl dimethyl ammonium chloride are generally used. However, the adhesion of these antibacterial agents to the fibers is weak, and most of them are removed by washing with a general synthetic detergent several times, the washing durability (antibacterial property after washing) is low, and the antibacterial effect disappears. There was a problem that it would end up.

On the other hand, the polyhexamethylene biguanide compound is represented by the chemical formula 1 and is a high molecular weight water-soluble antibacterial agent having a large number of alternating biguanide groups and hexamethylene groups. It is usually sold in the form of hydrochloride and is a highly safe industrial fungicide. Using this, JP-A-61-6
In No. 3772, there is an example of processing a non-woven fabric material, but this is an application limited to a disposable material, and it was not sufficient in terms of washing durability when used multiple times while washing.

[0005]

[Chemical 1] [However, n represents an integer of 4 to 7] In order to improve washing durability, Japanese Patent Publication No. 61-4544.
As described in JP-A-1 and JP-B-62-60509, there has been proposed a method of fixing a polyhexamethylene biguanide compound after treating a fiber with a polyacrylate or an anion group-containing polymer. However, since this method requires pretreatment, the cost of the manufacturing process is high, and further improvement has been required. Further, as described in JP-A-3-39310, there is also a method of preparing a processing emulsion by previously copolymerizing a polyhexamethylene biguanide compound, a sulfone group-containing monomer and an acrylate ester. The method also requires a polymerization step, which is a pre-reaction when preparing the processing agent, so that preparation of the processing agent is time-consuming and costly.

Further, Japanese Patent Publication No. 4-29780 discloses an example in which a specific antibacterial agent is combined with a phenol compound, which treats the phenol compound at the same time as or after the antibacterial agent is fixed to the fiber. The present inventor uses a phenol-based antibacterial agent, 1,6-di- (4-chlorophenyldiguanidide) hexane or a quaternary ammonium salt-based antibacterial agent, which is mentioned as an example of a specific antibacterial agent. When they were actually treated in combination with a phenolic compound, the antibacterial properties after washing were almost lost, and it is considered that the antibacterial components were removed from the fibers after washing, and there was a problem with washing durability. It was

[0007]

DISCLOSURE OF THE INVENTION The present invention aims to solve the problems of these conventional techniques and to provide a method for producing an antibacterial fiber having improved washing durability. The purpose is to enable economical processing in a simple process that does not require treatment or synthetic reaction.

[0008]

[Means for Solving the Problems] In order to realize economical processing consisting of a simple process having excellent washing durability by using a polyhexamethylene biguanide compound having excellent antibacterial property, As a result of intensive studies, when a phenolic compound is combined with a polyhexamethylene biguanide compound, the sticking property on the fiber is remarkably improved,
It was found that excellent washing durability that can withstand washing with a synthetic detergent is obtained, and the present invention has been completed.

That is, the present invention is a method for producing an antibacterial fiber having a step of bringing an aqueous solution containing a polyhexamethylene biguanide compound and a phenol compound into contact with the fiber to fix the compound to the fiber. The present invention also includes a step of bringing an aqueous solution containing a phenolic compound into contact with the fiber to fix the phenolic compound to the fiber, and bringing an aqueous solution containing a polyhexamethylene biguanide compound into contact with the fiber to fix the phenolic compound to the fiber. You may provide a process separately.

In the present invention, the phenolic compound means one of tannic acid represented by the chemical formula 2, tannin, dimethylolphenol resin or polymethylolphenol resin represented by the chemical formula 3, catechin, gallocatechin and the like.
A compound having a plurality of phenol skeletons having one or more hydroxyl groups and having a molecular weight of about 300 to 10,000 is preferable, and one having a molecular weight of about 300 to 2,000 is preferable. If the molecular weight is too large, solubility will be a problem, and if it is too small, the washing durability will be reduced.

[0011]

[Chemical 2]

[Chemical 3] In the present invention, when the treatment of the polyhexamethylene biguanide compound and the treatment of the phenolic compound are carried out as separate steps, the phenolic compound can be arbitrarily selected and used. When fixed to the fiber with an aqueous solution in which a polyhexamethylene biguanide compound and a phenol compound coexist in a single process,
Tannic acid or tannin is preferable because it has excellent stability in an aqueous solution.

[0012] In the field of textile processing, tannins generally form a ligand with tartarite to obtain stickiness.
In the case of the present invention, it is considered that the polyhexamethylene biguanide compound itself forms a complex with tannin to improve the stability, and not only tartar is unnecessary but tartar and polyhexan When a methylene biguanide compound is mixed, a sparingly soluble precipitate is formed and the stability of the mixed solution is impaired, which is not preferable.

Further, in the present invention, the phenolic compounds may be used alone or in combination of two or more kinds.

In the present invention, it is not clear why the combination of the polyhexamethylene biguanide compound and the phenolic compound remarkably improves the washing durability, but the polyhexamethylene biguanide compound is cationic in the molecule. It is considered that a complex with a phenolic compound is generated at various places in the molecule due to the large number of biguanide groups, and this is considered to prevent the antibacterial agent from falling off by washing.

On the other hand, many other antibacterial agents usually have one ionic group, and even in the case of 1,6-di- (4-chlorophenyldiguanidide) hexane, there are two ionic groups. It is presumed that it is likely to fall off due to the influence of detergent etc.

In the present invention, when the polyhexamethylene biguanide compound and the phenol compound are mixed and used as a processing liquid, the amount of the phenol compound added is 10 with respect to the solid content of the polyhexamethylene biguanide compound. ˜500 wt%, preferably 50-200 wt%. If the added amount is less than 10% by weight, the washing durability is insufficient, and if it exceeds 500% by weight, the antibacterial performance is deteriorated or the texture of the fiber is impaired.
Further, it may turn yellow, which is not preferable.

In the present invention, it is useful to use a cross-linking agent together in order to further improve the durability to washing. Melamine resin, glycoluril resin, urea resin, epoxy resin, aldehyde compound, aziridine compound, blocked isocyanate. Aqueous crosslinking agents such as compounds can be used.

In the present invention, the amount of the antibacterial agent polyhexamethylene biguanide compound fixed to the fiber may be appropriately adjusted according to the intended use and the desired antibacterial activity level.
Generally, it is in the range of 0.001 to 5% by weight with respect to the fiber. Below this range, the antibacterial performance decreases, and above this range, the manufacturing cost becomes high, and the texture of the fiber is impaired or the fiber falls off. It is also not preferable in terms of safety against skin.

In the present invention, the method of fixing to the fiber by using the processing liquid containing the polyhexamethylene biguanide compound depends on the form of the target fiber, but the dipping method,
After treatment by a known method such as a padding method or a spray method, excess processing solution is removed by mangle, centrifugal dehydration method or other methods, if necessary, and then heat drying and crosslinking reaction are performed. In addition, the processing of the present invention is not limited to the method of fixing the aqueous solution containing the phenolic compound and the polyhexamethylene biguanide compound to the fiber, but the phenolic compound after fixing the polyhexamethylene biguanide compound to the fiber or before fixing. It is also possible to fix the fiber to an aqueous solution containing. In this case, the number of steps is increased, but when a phenolic compound having a problem such as gelation or precipitation when mixed is used, the processing can be performed without problems in the steps.

Since the crosslinking reaction is accelerated by heat, it is preferable to provide a heating and drying step at 100 to 160 ° C. after the processing because the quality is stabilized.

The fibers in the present invention include cotton, hemp, wool,
Natural fibers such as silk, chemical fibers such as rayon and suf,
This refers to so-called textile products such as woven fabrics, non-woven fabrics, threads, and aggregates mainly composed of synthetic fibers such as nylon, polyester, vinylon, and acrylic. The method of the present invention can be applied to these fibers.

The processing of the present invention can be carried out at any time after dyeing, softening, resin processing, sewing, other fiber processing or before fiber processing. Simultaneous processing with these steps is also possible.

Further, in the processing liquid used in the present invention, a function imparting agent such as a resin processing agent, a dye, a softening agent, an antistatic agent, a deodorant, an insect repellent, a water repellent and an ultraviolet absorber is added. You may add and use it as needed. When the stability of the function-imparting agent and the polyhexamethylene biguanide compound in the processing solution becomes a problem, a surfactant, a stabilizer and the like may be further added.

The evaluation method of the present invention will be described below.

(Evaluation Method of the Present Invention) A. Evaluation of antibacterial performance The antibacterial performance was evaluated by the bacterial count method specified by the Textile Sanitary Processing Council.
After 0.2 g of the test cloth was put in a vial and sterilized in an autoclave, about 1 million Staphylococcus aureus of the test bacterium Staphylococcus aureus was added to a normal broth medium.
Inoculate 0.2 ml of the bacterial solution adjusted to 1 to 36
The cells were cultivated at 18 ° C for 18 hours in an incubator. Then, 20 ml of physiological saline was added, and the mixture was shaken vigorously by hand to disperse the viable bacteria in the test solution, and 1 ml diluted with 10 culture dilution series was mixed with 15 ml of ordinary agar medium. After culturing at ° C for 24 hours, the viable cell count C was determined by the following formula.

Viable cell count C = Counted colony count × 20 × Dilution ratio Viable cell count when the untreated cloth was cultured under the same conditions as B
Further, after inoculating the untreated cloth with the bacterial solution, the viable bacteria were dispersed in saline without culturing for 18 hours, and the similarly obtained viable cell count A before culturing was used to obtain an increase / decrease deviation according to the following equation: It was used as an antibacterial index. It is to be noted that the Council for Textile Hygiene Processing states that an increase / decrease difference of 1.6 or more has an antibacterial effect.

Increase / decrease deviation = log (B / A) −log (C / A) Washing test method The test cloth is used in a household washing machine to JIS-0201-1.
According to method No. 03, washing was carried out for 5 minutes with a washing liquid of 0.2% by weight of a detergent (manufactured by Kao Corporation, Liquid Zab), and two cycles of rinsing for 2 minutes were repeated for 10 cycles. , Dried indoors. In the washing test, liquid zab, which is said to have almost no antibacterial effect, was used because the antibacterial effect of the detergent generally appears in commercially available powder type synthetic detergents.

Examples of the present invention will be shown below, but the present invention is not limited thereto. All parts and% are based on weight.

[0029]

【Example】

[0030]

Example 1 A 20% aqueous solution of polyhexamethylene biguanide hydrochloride (Proxel IB manufactured by Zeneca Corp.) per 100 parts of a 0.4 wt% aqueous solution of tannic acid (molecular weight 493) (manufactured by Kanto Chemical Co., Inc.) 1 The parts were mixed to prepare a processing liquid. A cotton cloth (gold cloth obtained from Shikiso Co., Ltd., about 100 g / m2) was dipped in this, and 1 at 1000 RPM.
Centrifugal dehydration was carried out for 10 minutes to obtain a squeezing ratio of about 100%, which was dried at 60 ° C for 10 minutes and then heat-cured at 140 ° C for 10 minutes. When the antibacterial property of the obtained processed cloth was evaluated by the above-mentioned A, the increase / decrease deviation was 7.6 as shown in Table 1, showing a high antibacterial property. Further, the increase / decrease deviation of B of the processed cloth after the washing test was not changed to 7.6, which had sufficient antibacterial performance and showed excellent washing durability.

[0031]

[Comparative Example 1] The same cotton cloth as in Example 1 which was not subjected to antibacterial treatment was evaluated. Using this, the same antibacterial properties as in Example 1 were evaluated. The test results are shown in Table 1, and the increase / decrease deviation was almost zero before and after the washing test.

[0032]

Comparative Example 2 A processing liquid was prepared by mixing 1 part of Proxel IB used in Example 1 and 100 parts of water. Using this, a processed cloth was obtained in the same manner as in Example 1, and the same antibacterial evaluation as in Example 1 was performed. The test results are shown in Table 1.

The work cloth thus obtained had an increase / decrease deviation of 7.6, but the increase / decrease deviation after the washing test was 3.2, which was significantly inferior to that of Example 1.

[0034]

[Comparative Example 3] A 0.4 wt% aqueous solution of tannic acid (molecular weight: 493, manufactured by Kanto Chemical Co., Inc.) was used as a processing liquid, and using this, a processed cloth was obtained in the same manner as in Example 1 and Similar antibacterial properties were evaluated. The test results are shown in Table 1.

The work cloth thus obtained had an increase / decrease deviation of 7.6, but the increase / decrease deviation after the washing test was 1.0, which was significantly inferior to that of Example 1.

[0036]

Comparative Example 4 A processing liquid was prepared by mixing 0.2 part of an antibacterial agent, benzalkonium chloride, with 100 parts of a 0.4 wt% aqueous solution of tannic acid (molecular weight: 493) (manufactured by Kanto Chemical Co., Inc.). . Using this, a work cloth is obtained in the same manner as in Example 1,
The same antibacterial evaluation as in Example 1 was performed. The test results are shown in Table 1.

The work cloth thus obtained had an increase / decrease deviation of 7.6, but the increase / decrease deviation after the washing test was 1.4, indicating that the washing durability was much inferior to that of Example 1.

[0038]

Comparative Example 5 Tannin acid (molecular weight 493) (manufactured by Kanto Chemical Co., Inc.) 0.4 parts by weight aqueous solution 100 parts, antibacterial agent chlorhexidine gluconate (manufactured by ICC Pharma Co., Ltd.) 3 parts Were mixed to prepare a processing liquid.
Using this, a processed cloth was obtained in the same manner as in Example 1, and the same antibacterial evaluation as in Example 1 was performed. The test results are shown in Table 1.

The work cloth thus obtained had an increase / decrease deviation of 7.6, but the increase / decrease deviation after the washing test was 2.2, and the washing durability was much inferior to that of Example 1.

[0040]

Example 2 1 part of tannic acid (molecular weight 493) (manufactured by Kanto Chemical Co., Inc.), 2 parts by weight of Proxel IB and water 10
0 parts were mixed to prepare a processing liquid.

Using this, a processed cloth was obtained in the same manner as in Example 1 and evaluated for antibacterial properties in the same manner as in Example 1. The test results are shown in Table 1.

The obtained work cloth had an increase / decrease deviation of 7.6, and the increase / decrease deviation after the washing test was not changed to 7.6, which had sufficient antibacterial performance and showed excellent washing durability.

[0043]

Example 3 A cotton cloth (gold cloth obtained from Shikiso Co., Ltd., about 100 g / m 2) was immersed in a 1% by weight aqueous solution of a phenol-based polymer Nylon Fix SZ-2 (manufactured by Senka Co., Ltd.), and 1000 rpm was applied. Centrifugal dehydration for about 1 minute
It was set to 00%, dried at 60 ° C for 10 minutes, and then 1
It was cured by heating at 40 ° C for 10 minutes. Then, the obtained cotton cloth is dipped in a 1% by weight aqueous solution of Proxel IB,
Centrifuge dehydration for 1 minute at 0 RPM to make the squeezing rate about 100%,
This is dried at 60 ° C for 10 minutes and then at 140 ° C for 1 minute.
After heating for 0 minutes and performing antibacterial processing, a processed cloth was obtained, and Example 1
The same antibacterial property was evaluated. The test results are shown in Table 1.

The obtained work cloth had an increase / decrease deviation of 7.6, and the increase / decrease deviation after the washing test did not change to 7.6, which showed sufficient antibacterial performance and showed excellent washing durability.

[0045]

[Example 4] A polyester taffeta cloth (obtained from Shikiso Co., Ltd.) was dipped in the processing solution used in Example 1 to a centrifugal dehydration squeezing ratio of about 30% and dried at 60 ° C for 10 minutes. After that, it was heated at 140 ° C. for 10 minutes to obtain a work cloth, and the same antibacterial property was evaluated as in Example 1. The test results are shown in Table 1.

The obtained work cloth had an increase / decrease deviation of 7.6, and the increase / decrease deviation after the washing test was slightly decreased to 6.6.
It had sufficient antibacterial performance and showed washing durability.

[0047]

Example 5 A processed cloth was obtained in the same manner as in Example 4 except that nylon taffeta cloth (obtained from Shikiso Co., Ltd.) was used and the squeezing ratio for centrifugal dehydration was changed to about 25%. The same antibacterial property was evaluated. The test results are shown in Table 1.

The obtained work cloth had an increase / decrease deviation of 7.6, and the increase / decrease deviation after the washing test was reduced to 4.3, but it had sufficient antibacterial performance and showed washing durability.

[0049]

[Example 6] Nylon taffeta cloth (obtained from Shikiso Co., Ltd.) was immersed in a 1% by weight aqueous solution of Hifix SL (Dainippon Pharmaceutical Co., Ltd.), which is a mixture of phenolic polymer and tartarite, and centrifugally dehydrated. The drawing rate is about 25%, 60 ° C10
After being dried for 1 minute, it is immersed in a 1% by weight aqueous solution of Proxel IB to a centrifugal dehydration squeezing ratio of about 25%, which is then heated to 60 ° C.
After being dried for 10 minutes and subjected to antibacterial processing, a processed cloth was obtained, and the same antibacterial evaluation as in Example 1 was performed. The test results are shown in Table 1.

The obtained work cloth had an increase / decrease deviation of 7.6, and the increase / decrease deviation after the washing test was reduced to 4.3, but it had sufficient antibacterial performance and showed washing durability.

[0051]

[Table 1]

[0052]

According to the method for producing an antibacterial fiber of the present invention, the processed cloth thus obtained exhibits excellent antibacterial performance and has sufficient washing durability. Therefore, the present invention is a clothing material,
It can be applied to a wide range of applications such as sheets, pillowcases, futon cotton, etc. and is extremely useful.

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Claims (3)

[Claims] 1. A method for producing an antibacterial fiber, comprising a step of bringing an aqueous solution containing a polyhexamethylene biguanide compound and a phenol compound into contact with the fiber to fix the polyhexamethylene biguanide compound to the fiber. 2. A step of bringing an aqueous solution containing a phenolic compound into contact with the fiber to fix the phenolic compound to the fiber, and bringing an aqueous solution containing the polyhexamethylene biguanide compound into contact with the fiber, and the polyhexamethylene biguanide compound into the fiber. A method for producing an antibacterial fiber, which comprises the step of fixing the antibacterial fiber to the. 3. The method for producing an antibacterial fiber according to claim 1, wherein the phenolic compound is a tannin.