JP2006249609A - Method for imparting fiber structural product with antibacterial and antifungal performance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for imparting fiber structural products with antibacterial and antifungal performance without deteriorating properties including touch feeling, hygroscopicity and water-absorbing tendency required for the individual fiber structural products. <P>SOLUTION: The method is characterized by comprising incorporating a silver-based compound-containing acrylonitrile-based fibers with 5-15 wt%, in terms of the constituent fibers of the structural product, of silver-carrying acrylonitrile-based fibers heat-treated within the range of pH 1-6. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a method for imparting antibacterial and antifungal performance to a fiber structure and a fiber product containing the fiber structure obtained by applying the method.

In recent years, with the maturity and aging of society, and the tendency to demand a rich and comfortable living environment, the demand for maintenance and promotion of health has increased, and cleaner and more comfortable clothing, bedding, interior products or living materials, etc. The appearance of is desired. As a means for realizing such cleanliness and comfort, antibacterial and antifungal performance is often imparted.

For example, Patent Document 1 discloses a method for producing antibacterial fibers in which fibers are impregnated with a solution of didecyldimethylammonium polyfunctional organic acid salt. Quaternary ammonium salts, such as polyfunctional organic acid salts of didecyldimethylammonium, are organic antibacterial agents, and have been widely used in the past because of their excellent processability. There is a problem that the antibacterial and antifungal performance is lost.

Patent Document 2 discloses an antibacterial processing agent obtained by dispersing an inorganic antibacterial agent in which an antibacterial metal such as silver is supported on an inorganic carrier such as zeolite or apatite in water with an inorganic dispersant, a cationic surfactant, and the like. Disclosed is an antibacterial processing method in which a textile is immersed in the presence of. The fiber product processed by the processing method is said to have an improved texture as compared with the case of using a binder, but it is inevitable that the texture decreases compared to the fiber product before processing. In addition, there is a problem that the inorganic antibacterial agent falls off due to friction or the like and the effect is likely to be lowered.

Further, Patent Document 3 discloses a method for producing an antibacterial fiber product in which an antibacterial fiber obtained by kneading an inorganic antibacterial agent in which silver ions are supported on activated carbon or zeolite into a synthetic fiber such as polyester is blended or woven with cotton fiber. Is disclosed. However, in order to obtain a sufficient antibacterial effect, the mixing ratio of antibacterial fibers is required to be at least 20% or more, and a considerable amount of antibacterial fibers must be mixed. For this reason, there exists a problem that characteristics, such as the texture derived from a cotton fiber, dyeing | staining property, and a hygroscopic property, will not be impaired.
JP 10-331069 A JP 2002-370911 A JP-A-7-109672

As described above, it has been eager to give antibacterial and antifungal performance to fiber structures so far, and issues such as deterioration of antibacterial and antifungal performance due to washing and deterioration of texture should be taken into consideration. However, it has become impossible to provide a sufficiently satisfactory performance due to the demand for advanced performance. The present invention has been made on the basis of the present situation, and imparts antibacterial and antifungal performance to the fiber structure without deteriorating the properties required for the individual fiber structure such as texture, hygroscopicity, and water absorption. It aims to provide a method.

As a result of diligent studies to achieve the above-mentioned object, the present inventor has reached the present invention shown below.

That is, the present invention is achieved by the following means.
(1) A silver-supported acrylonitrile fiber formed by heat-treating an acrylonitrile fiber containing a silver compound within a pH range of 1 to 6 is contained as a constituent fiber of a fiber structure in an amount of 5 to 15% by weight. A method for imparting antibacterial and antifungal performance to fiber structures
(2) The method for imparting antibacterial and antifungal performance to a fiber structure according to (1), wherein the acrylonitrile fiber containing a silver compound has an anionic functional group.
(3) The method for imparting antibacterial and antifungal performance to a fiber structure according to (1) or (2), wherein the heat treatment is wet heat or dry heat treatment at 100 to 160 ° C.
(4) The method for imparting antibacterial and antifungal performance to a fiber structure according to any one of (1) to (3), wherein the silver content of the silver-supporting acrylonitrile fiber is 1 to 100 mmol / kg.
(5) The method for imparting antibacterial and antifungal performance to a fiber structure according to any one of (1) to (4), wherein the fiber structure contains cotton fibers.
(6) A fiber product having at least a part of a fiber structure imparted with antibacterial and antifungal performance by the application method according to any one of (1) to (5) above.
(7) Textile products are from underwear, stomach wraps, supporters, masks, gloves, socks, stockings, insoles, shoe lining materials, pajamas, bathrobes, towels, bath mats, carpets, blankets, bedding, curtains, chair upholstery. The textile product according to (6), which is selected.

According to the present invention, various fiber structures such as underwear, stomach wraps, supporters, masks, gloves, socks, stockings, pajamas, bathrobes, towels, bath mats, carpets, blankets, bedding, curtains, chair upholstery fabrics, fiber structures It is possible to impart antibacterial and antifungal performance with excellent durability without impairing the inherent characteristics of the product. That is, the silver-supported acrylonitrile fiber employed in the present invention has excellent antibacterial and antifungal performance, and in addition, has a so-called photocatalytic activity that can enhance the antibacterial and antifungal performance by light irradiation, so a small amount. A sufficient effect can be obtained by using. Further, since the silver content in the silver-supporting acrylonitrile fiber is small, coloring hardly occurs. Furthermore, since the fibers have higher durability than organic antibacterial agents such as quaternary ammonium, the fiber structure obtained by the present invention does not deteriorate the antibacterial and antifungal performance even after repeated washing.

Hereinafter, the present invention will be described in detail. In the present invention, silver-supported acrylonitrile fiber formed by heat-treating acrylonitrile fiber containing a silver compound within a pH range of 1 to 6 is employed as an active ingredient that exhibits antibacterial and anti-weather performance. The fiber is imparted with photocatalytic activity by heat treatment, and exhibits higher antibacterial and antifungal performance than acrylonitrile fiber containing a silver compound before heat treatment. Therefore, a sufficient effect can be obtained even if it is not contained in a large amount in the fiber structure, and it is possible to develop antibacterial and antifungal performance with addition of a small amount, which was difficult to obtain with a conventional antibacterial fiber. is there. In a normal case, 5 to 15% by weight, preferably 7 to 10% by weight, may be contained as a constituent fiber of the fiber structure, and the effect can be obtained even with a content of less than 10% by weight. Thus, since the content of the silver-supported acrylonitrile fiber may be small, there is almost no influence on the properties such as the texture and dyeability of the fiber structure due to the inclusion of the fiber, and the fiber structure originally has It is possible to impart antibacterial and antifungal properties while maintaining the properties that have been achieved.

The fiber structure in the present invention is a composite of yarn, yarn, filament, woven fabric, knitted fabric, non-woven fabric, paper-like material, sheet-like material, laminate, cotton-like material, and combinations thereof produced by a usual method. It is a generic term for pointing.

The acrylonitrile fiber containing the silver compound used as the raw material for the silver-supported acrylonitrile fiber is a fiber formed from an acrylonitrile polymer, and is not particularly limited as long as it contains a silver compound. As such acrylonitrile-based polymer, a copolymer of acrylonitrile and a known monomer of preferably 60% by weight or more, more preferably 80% by weight or more can be used.

The monomer used for the copolymerization is not particularly limited as long as it can be copolymerized with acrylonitrile such as a polymerizable unsaturated vinyl compound. For example, vinyl esters such as vinyl acetate; vinyl chloride, vinyl bromide, vinylidene chloride, etc. Vinyl halides or vinylidenes of (meth) acrylic acid alkyl esters such as methyl acrylate and methyl methacrylate (hereinafter, (meth) acrylic description represents both acrylic and methacrylic); Acrylamides such as (meth) acrylamide; sulfonic acid group-containing monomers such as styrene, methallyl sulfonic acid soda, 2-acrylamido-2-methylpropane sulfonic acid, p-styrene sulfonic acid soda, vinyl sulfonic acid soda; Carboxylic acid group-containing monomers such as (meth) acrylic acid and maleic acid However, in order to efficiently contain a silver compound, it contains 0.1 to 20% by weight of an anionic functional group-containing monomer such as a sulfonic acid group or carboxylic acid group-containing monomer. It is desirable.

The amount of the silver compound to be contained in the fiber is not particularly limited, but the silver content in the finally obtained silver-supported acrylonitrile fiber is preferably 1 to 100 mmol / kg, more preferably 1 to 50 mmol / kg. It is good to be. Since sufficient antibacterial and antifungal performance can be obtained with such a small amount of silver, there is almost no problem that the fibers are colored by heating or aging, and the cost is kept low, which is industrially advantageous.

The method for incorporating such a silver compound into acrylonitrile fiber is not particularly limited. For example, in the method disclosed in JP-A-3-199418, that is, when an acrylonitrile fiber is produced, a drying and heat relaxation step is performed. A method in which the previous gel structure fiber is continuously treated with a silver-based aqueous solution and a silver-based compound is contained in the fiber, or a method disclosed in JP-A-52-92000 or JP-A-7-243169, An example is a method in which an acrylonitrile fiber is produced by a normal method and then a silver compound is contained by post-processing.

The silver-supporting acrylonitrile fiber employed in the present invention is obtained by subjecting the acrylonitrile fiber containing the silver compound obtained as described above to a heat treatment within the range of pH 1-6, preferably pH 2-4. Can do. Although it does not specifically limit as the method of this heat processing, The method of processing by 100-160 degreeC wet heat or dry heat is preferable, for example, the acrylonitrile fiber containing a silver type compound is made into acidic aqueous solution of pH 1-6. Examples thereof include a method of wet-heat treating the dipped and drained fibers with steam in an autoclave, or a method of directly drying and heat-treating the drained fibers with a hot air dryer. The processing time is set in consideration of the processing temperature.

Here, when the pH during the heat treatment is less than 1, the fiber physical properties are remarkably inhibited, and when the pH exceeds 6, the photocatalytic activity is not imparted. Further, when the heat treatment temperature is less than 100 ° C., the treatment time becomes longer and it is not an industrially advantageous method. When the heat treatment temperature exceeds 160 ° C., physical properties such as the hue and strength of the silver-supported acrylonitrile fiber are hindered. Therefore, it is not preferable.

The method for incorporating the silver-supported acrylonitrile fiber obtained as described above into the fiber structure is not particularly limited, and may be incorporated by blending, blending, blending, or the like with other fibers. Other fibers are not particularly limited, and are usually used fibers such as natural fibers such as cotton, hemp, silk and wool, recycled fibers such as rayon and cupra, and synthetic fibers such as acrylic, nylon, polyester and vinylon. It doesn't matter.

In particular, when the other fibers are cotton, that is, when it is desired to impart antibacterial and antifungal performance to a fiber structure mainly composed of cotton fibers, the antibacterial and antifungal performance imparting method of the present invention is suitable. Since cotton fibers are soft on the skin and rich in water absorption, they are used after being processed into various fiber structures, but on the other hand, they have the disadvantage of being easily moldy. According to the method of the present invention, since the content of the silver-supported acrylonitrile-based fiber may be small, it becomes possible to impart antibacterial and anti-wrinkle performance while taking advantage of the soft and water-absorbing properties of the cotton fiber skin. . Thus, when it is desired to utilize the characteristics of the cotton fiber, the content of the cotton fiber in the fiber structure is 50 to 95% by weight, preferably 85 to 95% by weight.

The fiber structure obtained by the method of the present invention described above includes yarns, yarns, filaments, woven fabrics, knitted fabrics, nonwoven fabrics, paper-like materials, sheet-like materials, laminates, cotton-like materials, and composites thereof. Examples include the body. These fiber structures should be used as they are or after further processing to make products that come in direct contact with skin, such as towels, clothing, rugs, footwear, etc. Can do. Specific products include underwear, stomach wraps, supporters, masks, gloves, socks, stockings, insoles, shoe lining materials, pajamas, bathrobes, towels, bath mats, carpets, blankets, bedding, curtains, chair upholstery, etc. be able to.

Examples are shown below for facilitating the understanding of the present invention. However, these are merely examples, and the gist of the present invention is not limited thereto. In the examples, parts and percentages are based on weight unless otherwise specified. Further, the silver content and antibacterial and antifungal performance described in the following production methods are measured by the following methods.

(1) Atomic absorbance of a solution obtained by wet decomposition of 0.1 g of silver content sample fiber with 95% concentrated sulfuric acid and 62% concentrated nitric acid solution using an atomic absorption spectrometer AA855 manufactured by Nippon Jarrell Ash Co., Ltd. Was measured.

(2) Antibacterial activity Based on the JIS L1902 quantitative test (bacterial liquid absorption method), the bactericidal activity value and the bacteriostatic activity value were determined by the following mathematical formula. The number of viable bacteria was measured by the pour plate culture method, and a standard cotton cloth was used as the unprocessed cloth.
Bactericidal activity value = log A−log C
Bacteriostatic activity value = logB−logC
Here, A = the number of bacteria recovered immediately after inoculation of the unprocessed cloth, B = the number of bacteria recovered after 18 hours of culturing the unprocessed cloth, and C = the number of bacteria recovered after 18 hours of culturing of the processed cloth. According to the fiber product certification standard of the Japan Fiber Evaluation Technology Council, antibacterial and deodorizing processing has a bacteriostatic activity value> 2.2, and bactericidal processing (general use) has a bactericidal activity value ≧ 0.
(3) The bacterial solution prepared in the anti-fertile 1/20 Sabouraud liquid medium was inoculated into the sample, and the number of viable bacteria on the sample after 18 hours of culture in an incubator at 27 ± 1 ° C. was measured.
(4) Washing method It was carried out by the test method of JIS L0217 103. The detergent used was a JAFET standard detergent.

[Production Example 1 of Silver Compound-Containing Acrylonitrile Fiber]
An acrylonitrile polymer composed of 91.1% acrylonitrile, 8.6% acrylic acid methyl ester, and 0.3% sodium methallyl sulfonate obtained by polymerization according to a conventional method is dissolved in an aqueous solution of rhodium soda having a concentration of 45%. A spinning stock solution having a polymer concentration of 12% was prepared. The stock solution was extruded into a 10%, -3 ° C aqueous rhodium soda solution using a known die, washed with water, stretched, and heat-treated to prepare acrylonitrile fiber (fiber A). Next, in order to introduce silver into the fiber, 100 g of fiber A was introduced into a solution adjusted to pH 3 with a 1% nitric acid aqueous solution of 1000 ml of an aqueous silver nitrate solution adjusted to 20 mmol / l and treated at 98 ° C. for 10 minutes. After washing with water and drying, the solution was added to 1000 ml of an aqueous sodium oxalate solution adjusted to 10 mmol / l, treated at 98 ° C. for 10 minutes, washed with water, dried, and silver compound-containing acrylonitrile fiber (fiber B). Created.

[Production Example 2 of Silver Compound-Containing Acrylonitrile Fiber]
A silver compound-containing acrylonitrile was prepared in the same manner as in Production Example 1 of a silver compound-containing acrylonitrile fiber, except that an acrylonitrile polymer comprising 95% AN and 5% vinyl acetate was used and the treatment time in the aqueous silver nitrate solution was 30 minutes. A system fiber (fiber C) was prepared.

The silver-based compound-containing acrylonitrile fiber (fibers B and C) obtained as described above is immersed in an aqueous solution adjusted in pH with nitric acid, drained, and then autoclaved (when the heat treatment temperature exceeds 100 ° C.) Alternatively, it is put into a hot air dryer (when the heat treatment temperature is 100 ° C. or lower) and heat treated at the pH and temperature shown in Table 1, and fiber No. Six types of fibers 1 to 6 were prepared. Fiber No. 7 is the silver compound-containing acrylonitrile fiber (fiber B) itself in Production Example 1 of silver compound-containing acrylonitrile fiber.

[Examples 1-5, Comparative Examples 1-2]
Fiber No. As for Nos. 1 to 7, 10% of each fiber and 90% cotton were mixed at the time of spinning, and a spun yarn having a cotton count of 20/1 was obtained by a cotton spinning method according to a conventional method. After the spun yarn was exposed in the form of cheese and processed, a towel was created using a towel loom. About the obtained towel, using Staphylococcus aureus ATCC 6538P, log A = 4.3, log B = 7.0 and Escherichia coli NBRC 3301, log A = 4.4, log B = 7.5 The results of evaluating antibacterial properties are shown in Table 2.

In each of Examples 1 to 5, the bactericidal activity value greatly exceeded 0, and the effect of reducing the number of bacteria exceeding the effect of inhibiting the growth of bacteria, that is, the antibacterial effect was obtained. On the other hand, the fiber No. used in Comparative Example 1 was used. Although No. 6 was heat-treated, since the treatment temperature was low and the pH was 7, it seems that the antibacterial property was lowered due to insufficient photocatalytic activity. In addition, the fiber No. used in Comparative Example 2 was used. Since No. 7 was not heat-treated, photocatalytic activity was not imparted, and the antibacterial processing level was not reached.

[Examples 6-7, Comparative Examples 3-4]
Fiber No. A towel was prepared in the same manner as in Example 1 except that 2 and cotton were mixed at the ratio shown in Table 3 during spinning. About the obtained towel, the result of having evaluated antibacterial property using Staphylococcus aureus ATCC 6538P, logA = 4.3, logB = 7.0 is shown in Table 3.

In Comparative Example 3, it is considered that the antibacterial property was lowered because the content of the silver-supported acrylonitrile fiber was small. On the other hand, in Comparative Example 4, since the content of the silver-supporting acrylonitrile fiber is large, the antibacterial property is high. However, compared with Example 7, the antibacterial property is different from the difference in the content of the silver-supporting acrylonitrile fiber. The difference in the above is slight, and it is not efficient to contain the silver-supported acrylonitrile fiber in excess of 15% by weight.

[Examples 8 to 10]
In Production Example 1 of the silver compound-containing acrylonitrile fiber described above, the pH of the silver compound-containing acrylonitrile fiber obtained in the same manner except that the concentration of the silver nitrate aqueous solution was changed as shown in Table 4 was adjusted with nitric acid. After soaking in an aqueous solution, drained and placed in an autoclave, heat treated at pH 3 and a temperature of 120 ° C. Three types of fibers of 8 to 10 were prepared and the silver content was measured. For these fibers, towels were prepared in the same manner as in Example 1, and antibacterial properties were evaluated using Staphylococcus aureus ATCC 6538P, log A = 4.3, log B = 7.0. The results are shown in Table 4.

As can be seen from Table 4, antibacterial properties improved with increasing silver content, but practical antibacterial performance was also obtained in Example 8 where the silver content was low. In Example 10, high antibacterial performance was obtained. 10 was slightly colored. This is thought to be due to the fact that coloring during the heat treatment becomes obvious due to the high silver content.

[Example 10]
Fiber No. 12%, 88% of acrylic fiber K8G0-1.7T38 manufactured by Nippon Exlan Industries Co., Ltd. was blended and spun according to a conventional method to produce a spun yarn having a cotton count of 30/1. This was dyed black by a conventional method for dyeing cotton blends (acrylic fiber: cationic dye, cotton: reactive dye). The obtained yarn was knitted according to a conventional method to create a sock. The antibacterial performance of the socks obtained before and after washing 10 times was confirmed by Staphylococcus aureus ATCC 6538P, log A = 4.2, log B = 7.0, and Klebsiella pneumoniae ATCC 4352, log A = 4. 4, log B = 7.4). The socks obtained as shown in Table 5 had excellent antibacterial properties.

[Example 11]
Fiber No. 10%, Nippon Exlan Industries Co., Ltd. acrylic fiber K85-1.3T51 40%, the company's water-absorbing acrylic fiber K626-1.7T51 50% blended, spun in accordance with conventional methods, After obtaining the spun yarn, a casserole having a weight of 250 g was prepared with a casket frame circumference of 200 cm. The prepared casserole was dyed with a cationic dye according to a conventional method, and water-absorbing treatment was performed with a water-absorbing softener. A bath mat having a pile length of 12 mm and a weight per unit area of 800 g / m ² was prepared from a case subjected to water absorption treatment using a 5/32 gauge sewing machine. About the obtained bath mat, using Staphylococcus aureus ATCC 6538P, log A = 4.3, log B = 7.1 and Escherichia coli NBRC 3301, log A = 4.4, log B = 7.5 Antibacterial properties were evaluated. The bath mat obtained as shown in Table 6 had excellent antibacterial properties.

In addition, the antibacterial properties of the bath mat prepared above were evaluated using two types of ringworm. The bath mats obtained as shown in Table 7 were effective against fungi.

Claims (7)

A fiber structure comprising 5 to 15% by weight of silver-supported acrylonitrile fiber formed by heat-treating acrylonitrile fiber containing a silver compound within a pH range of 1 to 6 as a constituent fiber of the fiber structure. For imparting antibacterial and antifungal performance. The method for imparting antibacterial and antifungal performance to a fiber structure according to claim 1, wherein the acrylonitrile fiber containing the silver compound has an anionic functional group. The method for imparting antibacterial and antifungal performance to a fiber structure according to claim 1 or 2, wherein the heat treatment is wet heat or dry heat treatment at 100 to 160 ° C. The method for imparting antibacterial and antifungal performance to a fiber structure according to any one of claims 1 to 3, wherein the silver content of the silver-supporting acrylonitrile fiber is 1 to 100 mmol / kg. The method for imparting antibacterial and antifungal performance to a fiber structure according to any one of claims 1 to 4, wherein the fiber structure contains cotton fibers. A fiber product having at least a part of a fiber structure imparted with antibacterial and antifungal performance by the application method according to claim 1. Textile products are selected from underwear, stomach wraps, supporters, masks, gloves, socks, stockings, insoles, shoe lining materials, pajamas, bathrobes, towels, bath mats, carpets, blankets, bedding, curtains, chair upholstery The textile product according to claim 6.