JP2004300650A - Fibrous material having anti-trichophyton property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fibrous material having an excellent anti-trichophyton property, especially exhibiting effectiveness for preventing the infection and aggravation of athlete's foot, further satisfying both a high washing durability and touch feeling for various fibrous materials and aiming at the uses of them as a mat, a carpet, slippers, sockes, panty stockings, tights, underwares, insoles for shoes, a towel, a cloth for an interior, etc. <P>SOLUTION: This fibrous material having the anti-trichophyton property contains a metal pyrithion-based compound expressed by general formula [1] [wherein, (n) is 1-4 integer; and M is a metal] as an antifungal component. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fibrous material which has an unprecedented superior anti-tineamyces property, and is particularly effective in preventing infection and deterioration of athlete's foot. Furthermore, it has high washing durability and texture for various fiber materials, and is used for mats, carpets, slippers, socks, pantyhose, tights, underwear, insoles, towels, interior cloths, etc. It relates to an optimal anti-tineamycium fiber material.

  Athlete's foot is an infectious disease caused by Trichophyton, a kind of fungus (mold). Trichophyton uses keratin, a keratin component of the skin, as a nutrient source and, like other molds, prefers a hot and humid environment. Causes symptoms. In the past, athlete's foot was common among middle-aged and elderly men who often wear tight-sealed shoes all day, even during the rainy season, when it is damp and humid, even in the summer, but in recent years it has become fashionable It is said that the incidence of athlete's foot in young women wearing airtight boots throughout the year since the epidemic has increased. In addition, if a family member has an infected person in a house, it may be transmitted to other members of the house through a bathroom mat or slippers that are likely to be hot and humid. It has been reported that one person suffers from foot athlete's foot (Journal of the Japanese Dermatological Association, Vol. 111, No. 14).

  Oral and topical medicines are used to treat athlete's foot, but oral medicines that require a doctor's prescription have a high healing effect but are not very popular among modern people who are busy and have no time to spare. It takes a long time to completely cure, and if you stop using it before the bacteria are completely killed, there is a disadvantage that athlete's foot will recur, and there are also problems such as complicated application to the affected area and adhesion contamination to clothing . There is also the subconscious that buying a remedy for athlete's foot is embarrassing, especially for young female infections. An even more fatal problem is that these measures cannot prevent transmission to cohabitants unless they are completely cured. In other words, people living with people with athlete's foot or sharing a bathroom are always at risk of athlete's foot infection.

The use of textile products with antibacterial and antifungal properties as personal items in response to such problems and drawbacks is not an option for infected persons to treat textile products in their daily lives without conscious treatment. The effect of preventing deterioration of athlete's foot is obtained just by using it, and it is also an effective means for non-infected persons from the viewpoint that infection from a carrier through daily necessities can be prevented. Regardless of the background and reasons, many fiber materials with antibacterial and antifungal properties have been proposed so far. Properties are insufficient (Japanese Patent No. 3281640 and the like), and the texture of a product is impaired because components are fixed via a binder resin (Japanese Patent Application Laid-Open No. 7-310284 and Japanese Patent No. ). In addition, antibacterial fibers imparted with good washing durability without using a binder resin and a method for producing the same are disclosed in Japanese Patent Nos. 1805853, 8-2226078, 9-194304, and 2000-8275. JP-A-2001-123375, JP-A-2001-159073, and the like, but all of these are limited to synthetic fibers such as polyester, polyamide, and acrylic, and are versatile. There was a problem that lacked.
Japanese Patent No. 3281640 JP-A-7-310284 Japanese Patent No. 3169992 Japanese Patent No. 1805853 JP-A-8-226078 JP-A-9-194304 JP 2000-8275 A JP 2001-123375 A JP 2001-159073 A

  The present invention has been made in view of the above background, and has as its object to provide a fiber material having an unprecedented excellent anti-tineamycosis property, and particularly effective in preventing infection and deterioration of athlete's foot. Furthermore, it has high washing durability and texture for various fiber materials, and is used for mats, carpets, slippers, socks, pantyhose, tights, underwear, insoles, towels, interior cloths, etc. The purpose of the present invention is to provide an optimal anti-tineamycium fiber material.

  The present invention employs the following means in order to solve the above problems. That is, the anti-tineamyces fiber material of the present invention is characterized by comprising a metal pyrithione-based compound represented by the following general formula [I] as an antibacterial component.

(Where n is an integer of 1 to 4 and M represents a metal)

  ADVANTAGE OF THE INVENTION According to this invention, it has excellent anti-tineamyces property which has not existed conventionally, and can provide the fiber material which is especially effective in preventing infection and deterioration of athlete's foot. Furthermore, it has high washing durability and texture for various fiber materials, and is used for mats, carpets, slippers, socks, pantyhose, tights, underwear, insoles, towels, interior cloths, etc. It is possible to provide an optimal anti-tineamyces fiber material.

  Hereinafter, the present invention will be described in detail.

  The fiber material of the present invention may contain a metal pyrithione-based compound as an antibacterial component in order to exhibit excellent anti-tineamycosis properties and to achieve high washing durability and texture for various fiber materials. This is an essential condition, and the metal pyrithione compound must be represented by the following general formula [I].

(Where n is an integer of 1 to 4 and M represents a metal)
Since the metal pyrithione compound represented by the general formula [I] can act at multiple points by mechanisms such as inhibition of the function of the microbial cell membrane and structural destruction, the microorganism can be killed, and almost no resistant bacteria are generated. In the invention, it exerts a very excellent anti-trichophyton effect. Usually, when infected with foot athlete's foot caused by Trichophyton, the skin of the affected area is swollen and the skin is turned over.Easily infected with staphylococci etc. and swells red, but such a metal pyrithione compound is also excellent against these bacteria Since it shows an antibacterial effect, it has the effect of suppressing the deterioration of the affected area and accelerating healing. Furthermore, it can also suppress the unpleasant foot odor caused by the growth of bacteria.

  Among such metal pyrithione compounds, in terms of ease of handling and industrial productivity, M in the general formula [I] is at least one metal selected from Na, Zn, Fe, Cu, and Ag. And more specifically, sodium (2-pyridylthio-1-oxide) sodium in which M is Na (n = 1) or bis (2-pyridylthio-1-oxide) zinc in which M is Zn (n = 2) And the like. Among them, bis (2-pyridylthio-1-oxide) zinc is particularly preferably used in the fiber material of the present invention, which has extremely high safety for humans and has many opportunities for contact with the human body.

  Further, the metal pyrithione compound represented by the above general formula [I] has a higher adsorptivity to various fibers than other antibacterial agents and fungicides, and can be fixed to a fiber material without using a binder resin. . Accordingly, it is preferable that the anti-tineaplastic fiber material of the present invention has the antibacterial component adhered to the fiber surface and / or diffused into the fiber without the intervention of the binder resin. It is also possible to use a binder resin in combination, but in this case, the washing durability of the anti-tineaphylococcus effect tends to be worse.

  In the present invention, the metal pyrithione compound which is an antibacterial component is preferably contained in the fiber at a ratio of 0.05 to 5% by weight based on the total weight of the fiber material. When the content is less than 0.05% by weight, the obtained effect becomes unstable. On the other hand, when the content exceeds 5% by weight, further effects are hardly obtained, and the robustness of the obtained fiber material is deteriorated. May have adverse effects.

  As a method for applying such an antibacterial component to the fiber material, various methods generally used as a fiber processing method can be applied. Among them, a padding method, a spray method, a coating method, and an absorption / exhaustion method in a bath. Is preferably used. In addition, in consideration of a normal production process, the padding method is preferable when the fiber material is a fabric such as a woven fabric or a knitted fabric, and the fiber material is in the form of a yarn (including hull, cheese, and beam), pantyhose, tights, and the like. In this case, the adsorption / exhaustion method in a bath is preferably used. When the antibacterial component is applied by a padding method, a spraying method, or a coating method, it is preferable to perform a dry heat treatment at 130 ° C. or higher after pre-drying. It is preferable to perform simultaneous / same bath treatment or two-stage / separate bath treatment. By performing the treatment under such conditions, the antibacterial component adheres to the fiber surface and / or diffuses inside the fiber without the intervention of the binder resin, and the washing durability of the obtained anti-tineaphylactic effect is dramatically improved. In addition, when imparting such an antibacterial component to the fiber material, it is also preferable to previously disperse the particles in water together with an anionic and / or nonionic surfactant as fine particles having an average particle diameter of 2 μm or less, from the viewpoint of improving processability. Done. Prior to the application of the antibacterial component, pretreatment of the fiber material such as desizing, scouring, and bleaching is also preferably performed for uniform processing. In particular, natural fibers such as cotton originally contain a large amount of fats and oils and tend to inhibit the exhaustion of antibacterial components. By performing these pretreatments, it is possible to further improve the durability of the anti-ringworm effect. I can do it.

  Next, the fibers constituting the fiber material in the present invention will be described. The type of the fiber is not particularly limited, and it can be used without any particular limitation, such as synthetic fiber, regenerated fiber, and natural fiber. Specifically, polyester, polyamide, polyurethane, acrylic, vinylon, chloride, and the like can be used. Synthetic fibers such as vinyl and polypropylene, semi-synthetic fibers such as diacetate and triacetate, recycled fibers such as rayon, cupra, and tencel, and natural fibers such as cotton, hemp, kenaf, pulp, wool, and silk can be used. . There is no problem even if two or more of them are used in an arbitrary ratio by kneading, blending, blending or knitting. When the fiber material is used for applications such as mats, carpets, slippers, socks, pantyhose, tights, underwear, insoles, towels, interior cloths, etc., polyester, polyamide, acrylic, rayon, It is preferable that at least one fiber selected from cotton is contained in an amount of 30% by weight or more. Further, when these fibers are used, the metal pyrithione compound is particularly excellent in adsorptivity and washing durability. Further, the form of the fiber may be any form such as a woven fabric, a knitted fabric, a nonwoven fabric, etc. More preferably, it is any one form selected from textiles and textiles.

  As is evident from the above, the fiber material of the present invention has an excellent anti-tineamycosis property which has never been seen before, and has both high washing durability and good texture for various fiber materials. Therefore, it is used for daily necessities such as foot mats, carpets, slippers, towels, and interior cloths that can transmit the Trichophyton bacillus possessed by people with athlete's foot and that can infect non-infected individuals. It has a great effect on prevention and can keep such textiles clean. In addition, the use of the fiber material in applications such as slippers, socks, pantyhose, tights, underwear, insoles, and the like is very effective in preventing athlete's foot from aggravating the athlete's foot. In this case, the growth of staphylococci and the like can be suppressed, so that the occurrence of swelling and itching of the feet due to infection with such bacteria can be suppressed, and the generation of offensive odor due to the growth of the bacteria can also be suppressed.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The quality and performance evaluations in the examples were performed according to the following methods.

<Anti ringworm bacteria> Cells of Trichophyton mentagrophytes are applied to a PDA medium (dish: 9 cm × 9 cm), and a test piece cut into 30 mm × 30 mm is attached thereto and cultured at 28 ° C. for 7 days. Then, the growth status of the mycelium was determined by the halo diameter and the mold resistance test evaluation method of JIS Z 2911 described below (a determination of "0" was accepted).
0: Almost no hyphal growth was observed in the inoculated portion of the test piece.
1: The area of the hyphal growth area observed in the inoculated portion of the test piece was
Does not exceed 1/3 of the total area.
2: The area of the hyphal growth area observed in the inoculated portion of the test piece was
Exceeds 1/3 of total area.

  <Antibacterial and deodorant properties> Staphylococcus aureus was used as a test bacterial species and evaluated according to JIS L1920 b) Quantitative test method (a bacteriostatic activity value of 2.2 or more was accepted).

  <Washing Durability> Home washing was performed according to the JIS L0217 103 method, and the anti-tineamyces property and antibacterial deodorant property after 50 washes were evaluated.

  <Feel> The feeling when the test piece was lightly rubbed by hand was evaluated in three grades: "soft", "slightly hard", and "very hard".

Example 1
Bis (2-pyridylthio-1-oxide) zinc, which is an antibacterial component, was wet-pulverized with glass beads together with a nonionic surfactant in advance to form a colloid solution having an active ingredient concentration of 20% by weight. Subsequently, a pantyhose consisting of nylon 6 and polyurethane elastic yarn obtained by a conventional method and a 20% by weight colloid solution of bis (2-pyridylthio-1-oxide) zinc obtained in a conventional manner were added to a drum dyeing machine in a ratio of 20: 1. The mixture was charged so as to have a weight ratio, then prepared with water so that the bath ratio in the drum dyeing machine was 1:20, and then the temperature was raised from room temperature to 80 ° C. and maintained for 30 minutes. Thereafter, the pantyhose was taken out and dried at 130 ° C. for 1 minute to obtain a desired fiber material. The antibacterial component content in the obtained fiber material was 1% by weight, and as a result of analysis by a scanning electron microscope (SEM) and an X-ray microanalyzer, about half of the antibacterial component was in a ring shape on the surface layer of nylon 6 fiber. And the other half was fixed in a film on the fiber surface. As shown in the evaluation results shown in Table 1, favorable results were obtained for all items.

Example 2
Spinning, stretching, washing with water, and cutting were performed by a wet spinning method, and an acrylic fiber having a single fiber fineness of 3.3 dtex and a single fiber length of 76 mm was used to obtain a spun yarn having a hair count of 1/60. When this is wound into a cheese and then dyed with a cationic dye by a conventional method using a package dyeing machine, the bis (2-pyridylthio-1-oxide) zinc 20% by weight colloidal solution obtained in Example 1 is placed in a bath. Was added at a rate of 3% owf. After the dyeing, a spun yarn obtained by dehydration and drying was knitted into a knitted fabric with a basis weight of 135 g / m ² and used to sew underwear for women. The antibacterial component content in the obtained fiber material was 0.5% by weight, and as a result of analysis by a scanning electron microscope (SEM) and an X-ray microanalyzer, most of the antibacterial component was in the form of a ring on the surface layer of the acrylic fiber. Was distributed. As shown in the evaluation results shown in Table 1, favorable results were obtained for all items.

Example 3
A 20% by weight colloid solution of bis (2-pyridylthio-1-oxide) zinc obtained in Example 1 was applied to a commercially available 100% cotton toweling mat made of towel cloth by a spray method, and after predrying at 100 ° C. At 170 ° C. for 1 minute to obtain a fiber material having an antibacterial component content of 1.5% by weight. As a result of analysis by a scanning electron microscope (SEM) and an X-ray microanalyzer, most of the antibacterial components were fixed in the form of a film on the surface of the cotton fiber. As shown in the evaluation results shown in Table 1, favorable results were obtained for all items.

Example 4
A short fiber woven fabric composed of 30% polyester and 30% polyester 65% rayon having a woven count of 30 s and a woven density of 130 × 74 yarns / inch was desizing, scouring, heat setting, dyeing and drying by a conventional method. This short fiber fabric was immersed in a 10% by weight solution of a 20% by weight colloidal solution of bis (2-pyridylthio-1-oxide) zinc obtained in Example 1, squeezed with a mangle, and preliminarily dried at 120 ° C. Heat treatment was further performed at 180 ° C. for 30 seconds to obtain a fiber material having an antibacterial component content of 0.5% by weight. Slippers were prepared using this as a side ground, and analyzed by a scanning electron microscope (SEM) and an X-ray microanalyzer. As a result, the antibacterial component was distributed in a ring shape on the surface layer of the polyester fiber and rayon fiber. As shown in the evaluation results shown in Table 1, favorable results were obtained for all items.

Example 5
The same treatment and evaluation as in Example 1 were performed, except that sodium (2-pyridylthio-1-oxide) was used instead of bis (2-pyridylthio-1-oxide) zinc as the antibacterial component in Example 1. The content of the antibacterial component in the obtained fiber material was 1% by weight, and as a result of analysis by a scanning electron microscope (SEM) and an X-ray microanalyzer, about half of the antibacterial component was nylon 6 fiber as in Example 1. Was distributed in the form of a ring on the surface layer portion, and the other half was fixed in the form of a film on the fiber surface. As shown in the evaluation results shown in Table 1, favorable results were obtained for all items.

Example 6
Spinning, drawing, washing, and cutting of a single yarn fineness of 1.45 dtex and a single fiber length of 38 mm, 50% of acrylic fiber obtained by spinning, drawing, washing and cutting by a wet spinning method, with 50% of U.S.-made cotton cotton. Got. This was made into a cheese, and then charged into a high-pressure package dyeing machine. First, hydrogen peroxide bleaching and washing with hot water were performed at 60 ° C. to remove impurities contained in cotton. Next, a cationic dye was added, the temperature was raised to 100 ° C., and the acrylic fiber was dyed. After draining, the 20% by weight bis (2-pyridylthio-1-oxide) zinc zinc colloid solution obtained in Example 1 was used. A processing liquid containing 5% owf was added to the bath, and the temperature was raised again to 100 ° C., and all the antibacterial components were exhausted and adsorbed to the fiber. Thereafter, the cotton fiber was further dyed with a reactive dye at 60 ° C., and a desired spun yarn was obtained through a dehydration and drying process. Using the spun yarn, sports socks for men were prepared and used for evaluation, and analyzed by a scanning electron microscope (SEM) and an X-ray microanalyzer. As a result of the analysis, most of the antibacterial components were distributed in a ring shape on the surface layer of the acrylic fiber and the cotton fiber. In addition, as shown in the evaluation results shown in Table 1, all items were favorable.

Comparative Examples 1-4
In Examples 1 to 4, those not subjected to treatment with a 20% by weight colloidal solution of bis (2-pyridylthio-1-oxide) zinc were subjected to evaluation. As is evident from the evaluation results shown in Table 1, when the treatment with the antibacterial component was not performed, neither anti-tineaplastic property nor antibacterial deodorant property was obtained.

Comparative Example 5
The same treatments and evaluations as in Example 1 were performed, except that a silver zeolite-based antibacterial / antifungal agent was used instead of bis (2-pyridylthio-1-oxide) zinc. As a result of analysis with a scanning electron microscope (SEM) and an X-ray microanalyzer, the antibacterial component was only slightly fixed on the fiber surface. Table 1 also shows the evaluation results. Anti-tineamyces properties were not obtained, and antibacterial and deodorant properties were not durable.

Comparative Example 6
The same treatment as in Example 2 except that a 20% by weight solution of a polyoxyalkylene ammonium type antibacterial and antifungal agent was used in place of the 20% by weight colloidal solution of bis (2-pyridylthio-1-oxide) zinc in Example 2. Was evaluated. As a result of analysis by a scanning electron microscope (SEM), the antibacterial component was fixed in a lump on the surface of the acrylic fiber. Table 1 also shows the evaluation results. Neither anti-tineaplastic property nor antibacterial and deodorant properties resulted in durability.

Comparative Example 7
The same treatment and evaluation as in Example 3 except that a 20% by weight aqueous solution of chitosan was used as an antibacterial and antifungal agent in place of the 20% by weight colloid solution of bis (2-pyridylthio-1-oxide) zinc in Example 3. Was done. As a result of analysis by a scanning electron microscope (SEM), the antibacterial component was fixed in a lump on the surface of the cotton fiber. Table 1 also shows the evaluation results. Neither anti-tineaplastic property nor antibacterial and deodorant properties resulted in durability. Further, the texture became very coarse and hard.

Comparative Example 8
In Example 4, instead of a 10% by weight solution of a 20% by weight colloidal solution of bis (2-pyridylthio-1-oxide) zinc, 10% by weight of polyhexamethyleneguanidine hydrochloride and 5% by weight of a melamine resin binder were used as antibacterial and antifungal agents. The same processing and evaluation as in Example 4 were performed except that the mixed solution was used. As a result of analysis by a scanning electron microscope (SEM), the antibacterial component was fixed in a lump on the fiber surface. Table 1 also shows the evaluation results. Although the anti-tineamyces property and the antibacterial deodorant property were the result of the first and the washing durability of the effect, the texture was coarse and hard and the commercial value was significantly reduced.

Claims (7)

An anti- Trichophyton fiber material comprising a metal pyrithione compound represented by the following general formula [I] as an antibacterial component.

(Where n is an integer of 1 to 4 and M represents a metal) 2. The anti-tineaplastic bacillus fiber material according to claim 1, wherein in the general formula [I], M is at least one metal selected from Na, Zn, Fe, Cu and Ag. The anti-tineamyces fiber material according to claim 1 or 2, wherein the antibacterial component is fixed to the fiber surface and / or diffused into the fiber without the intervention of a binder resin. The tinea bacillus fiber according to any one of claims 1 to 3, wherein the antibacterial component is contained in the fiber at a ratio of 0.05 to 5% by weight based on the total weight of the fiber material. material. 5. The anti-tineamyces fiber material according to claim 1, wherein said fiber material contains at least 30% by weight of at least one fiber selected from polyester, polyamide, acrylic, rayon and cotton. The anti-tineamyces fiber material according to any one of claims 1 to 5, wherein the fiber material is in one form selected from cotton, tow, thread, nonwoven fabric, knitted fabric and woven fabric. Mats, carpets, slippers, socks, pantyhose, tights, underwear, shoe insoles, towels and cloths for interiors, wherein the anti-tineaphytic fiber material according to any one of claims 1 to 6 is used for at least a part thereof. Daily necessities to be chosen.