JPH08284066A - Water-absorbing antibacterial synthetic fiber and its production - Google Patents

Abstract

PURPOSE: To obtain a synthetic fiber having antibacterial property and deodorizing activity as well as water-absorptivity and safe to human body by applying a chitosan salt to a polyester or polyamide synthetic fiber graft-polymerized with an alkali metal acrylate and/or methacrylate. CONSTITUTION: A polyester or polyamide synthetic fiber cloth is graft- polymerized with acrylic acid and/or methacrylic acid at a polymerization ratio of 1-20%, preferably 2-10%. The graft-polymerized cloth is treated in an aqueous solution of anhydrous sodium carbonate to substitute the terminal acidic group of the acrylic acid and/or methacrylic acid with an alkali metal. The cloth is padded in an aqueous solution of a chitosan salt, squeezed and dried to obtain the objective water-absorbing antibacterial fiber holding 0.1-2.0wt.% of the chitosan salt in terms of chitosan based on the fiber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic fiber which is safe for humans, has antibacterial properties, deodorant properties, water absorption properties, and excellent wash resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Clothes, bedding, etc. that come into contact with the human body are prone to unpleasant phenomena such as perspiration and stains in the air that cause microorganisms to propagate and decomposed substances to give off a bad odor.
Antibacterial and deodorant fibers are desired. One of the methods for producing such fibers is a method of kneading an antibacterial agent into a spinning dope, which is disclosed in, for example, JP-A-1-250413 and JP-A-3-250413.
No. 227403, and many others.
Another method is a manufacturing method in which antibacterial and deodorant properties are imparted after forming fibers as in the case of natural fibers or synthetic fibers, and for example, JP-A-62-69883 and JP-A-62-17728.
No. 4, for example. However, quaternary ammonium salts, chlorine-based organic compounds and the like are used in these methods, and the obtained fiber is not satisfactory in terms of the durability of the antibacterial and deodorant effect and the safety of the human body. I could not say.

Therefore, in recent years, a method for producing a fiber using chitosan, which is a deacetylated product of chitin obtained from crab and shrimp as a raw material and which has been recognized as a food additive, has been disclosed in Japanese Patent Laid-Open No. 2-41473, Japanese Patent Laid-Open No. 5-33210, Japanese Patent Laid-Open No. 5-1487
No. 58 is disclosed. However, these methods also have poor wash resistance simply by coating and drying chitosan on the fiber, or the use of a cross-linking agent for imparting wash resistance makes the texture remarkably rough. In any case, it was a level that could withstand up to 10 washes.

For imparting washing resistance and antibacterial properties to fibers using chitosan, polyester fibers having chitosan and collagen fixed by the application of graft polymerization of a hydrophilic monomer are known. Is still insufficient. For imparting water absorption, there is a physical method utilizing the capillary phenomenon due to the atypical cross-section of fibers. However, this method has a problem in that an effective capillary phenomenon does not appear depending on the contact condition between the fibers of different cross-sections and the water absorption effect is insufficient.

A large number of various water absorbing agents for fibers are commercially available, but polyester-based synthetic fibers or polyamide-based synthetic fibers which are essentially non-water-absorbing are coated with these water-absorbing agents on the fiber surface. However, the water-absorbing agent is gradually removed by washing, and it is difficult to form a permanent water-absorbing synthetic fiber. Therefore, for example, as disclosed in Japanese Patent Laid-Open No. 6-108362,
A water-absorbent synthetic fiber is obtained by graft-polymerizing a water-soluble vinyl monomer. However, the water absorbency of such a water-absorbent synthetic fiber is still insufficient, and the water absorbency measured by the dropping method is several tens of seconds or more.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a synthetic fiber which is safe for humans, has antibacterial properties, deodorant properties, water absorption properties, and is excellent in washing resistance, and a method for producing the same. To do.

[0007]

Means for Solving the Problems The present inventors have sought a substance which is extremely safe for the human body and has excellent antibacterial properties in order to achieve the above-mentioned objects, and a polyester-based synthetic fiber which is a non-water-absorbing substance. Or, as a result of research on how strongly the polyamide-based synthetic fiber can be strongly bonded and can be made water-absorbent, and whether it can be made water-absorbent and antibacterial excellent in washing resistance, It was the invention. That is, the first aspect of the present invention is that acrylic acid and / or methacrylic acid in which the terminal acidic group is substituted with an alkali metal has a polymerization rate of 1 to 20.
% Of the polyester-based synthetic fiber or the polyamide-based synthetic fiber graft-polymerized with 0.1% by weight of the chitosan salt in terms of chitosan. In the second aspect of the present invention, a polyester synthetic fiber or a polyamide synthetic fiber is graft-polymerized with acrylic acid or methacrylic acid, then treated with an alkaline aqueous solution of an alkali metal, and then treated with a chitosan salt aqueous solution. A method for producing a water-absorbing antibacterial synthetic fiber, comprising:

The water-absorbing antibacterial synthetic fiber of the present invention comprises, firstly, acrylic acid in which the terminal acidic group is substituted with an alkali metal and / or
Alternatively, it is necessary that methacrylic acid is graft-polymerized at a polymerization rate of 1 to 20%. Graft polymerization requires that the terminal acidic group be substituted with an alkali metal. Examples of the alkali metal include lithium, potassium and sodium. Also, the graft polymerization has a polymerization rate of 1
It is necessary to be 20%. Graft polymerization rate is 1
When it is lower than 20%, the washing resistance and water absorption of the chitosan salt applied in the subsequent treatment step are poor, and when it is higher than 20%, the texture becomes coarse and hard, which is not preferable. A more preferable graft polymerization rate is 2 to 10%.

In the present invention, a water-soluble vinyl monomer other than acrylic acid and / or methacrylic acid in which the terminal acidic group is substituted with an alkali metal, such as itaconic acid and 2-hydroxyethyl methacrylate, is used. It is also possible to mix and perform graft polymerization. Examples of the polyester-based synthetic fiber in the present invention include ethylene glycol, a fiber composed of a glycol component such as tetraethylene glycol and a dicarboxylic acid such as terephthalic acid and isophthalic acid, and as the polyamide-based synthetic fiber,
Examples of such fibers include nylon 6 and nylon 66. The synthetic fiber used in the present invention is a mixed fiber product, a cotton-like product, a tow, a top, a yarn, a non-woven fabric, a knitted fabric, a bag shape, a tubular shape, etc., containing at least 30% by weight of one or more of the above fibers. Various types of products and sewn products (hereinafter, all of them are collectively referred to as fibers).

The fiber used in the present invention may be a fiber from which unnecessary impurities are removed by scouring or scouring and bleaching.
Alternatively, a knitted fabric or a woven fabric containing polyester-based synthetic fibers may be fibers subjected to alkali weight reduction treatment. In that case, the present invention can be carried out without drying. The preferable adsorption amount or adhesion amount of the chitosan salt to the fiber (hereinafter referred to as the imparted amount, which is expressed in weight% by converting the chitosan salt into chitosan) is 0.1% to 2.0%. 0.1
% Or less, SEK (Synthetic Processing Council for Textile Products)
May not reach the antibacterial performance specified by. In the present invention, the applied amount of chitosan may be 2.0% or more, but when it is 2.0% or more, it is uneconomical because it imparts more antibacterial properties than necessary, and the texture may be hard. There is. A more preferable amount of chitosan applied is 0.2 to 1.
It is 0%.

Next, a method for producing the water-absorbent antibacterial synthetic fiber of the present invention will be described. Graft polymerization of acrylic acid and / or methacrylic acid (hereinafter referred to as water-soluble vinyl monomer) onto the fiber in the present invention may be carried out by a known method. For example, a method of irradiating a fiber with an active energy ray such as an electron beam or γ-ray and then impregnating the aqueous solution of a water-soluble vinyl monomer, a method of irradiating a fiber with an aqueous solution of a water-soluble vinyl monomer and then irradiating with an active energy ray, Azo-based vinyl monomers such as isobutyronitrile, azobisvaleronitrile, or other azo-based compounds, or benzoyl peroxide- or other organic-based compounds or potassium persulfate or ammonium persulfate-based inorganic peroxide radical initiators Any method such as a graft polymerization method may be used.

After the graft polymerization reaction, it is important to remove unreacted water-soluble vinyl monomer on the fiber and homopolymers thereof. The removal method is 90 to 120 fibers.
A method of washing with water at ℃ can be recommended. In the present invention, the graft polymerization rate can be determined as follows. That is, after the graft polymerization reaction, it was thoroughly washed with water having a bath ratio of 1:20 at 100 ° C. for 30 minutes (hereinafter, the graft polymerization includes the homopolymer removal step), and the graft polymerization rate (%) = 100. It can be calculated and calculated by x (weight of absolutely dry fiber after graft polymerization-weight of absolutely dry fiber before graft polymerization) / weight of absolutely dry fiber before graft polymerization.

In the present invention, after the graft polymerization, it is immersed in an aqueous solution containing an alkali metal alkaline substance, washed with water,
Treatments such as hot water washing, pickling, and water washing are performed (a series of treatments such as water washing, hot water washing, pickling, water washing, etc., performed with an aqueous solution containing an alkaline metal alkaline substance is referred to as alkali treatment).
These alkaline substances include hydroxides, carbonates, bicarbonates and the like, for example, lithium hydroxide, potassium carbonate, sodium bicarbonate and the like. The amount of these alkaline substances used may be appropriately selected depending on the mixing ratio of fibers, the type of alkaline substance, the graft polymerization rate, and the bath ratio. For example, when the bath ratio is 1:50, 0.1% to 2. 0%
The use of aqueous solutions is preferred. A temperature of 50 ° C. to 100 ° C. and a time of 10 minutes to 30 minutes are suitable. After the graft polymerization reaction, it is possible to simultaneously perform the treatment for removing the homopolymer and the alkali treatment.

To obtain dyed fibers, after graft polymerization,
Before performing alkali treatment, disperse dye, acid dye, etc.
Dye or print with a dye suitable for the fiber. Then, it is preferable to carry out an alkali treatment. It is also possible to carry out washing and alkali treatment at the same time to improve dyeing fastness. Treatments such as washing with water, washing with hot water, and pickling after the immersion treatment in an aqueous solution containing an alkaline substance of an alkali metal are treatments for removing unreacted excess alkaline substance. It may be appropriately selected, but 10 to 50
C. is preferable, and it is preferable to wash thoroughly with water at the end. After alkaline treatment, dehydration and drying, or without dehydration and drying,
An aqueous chitosan salt solution is applied to the fiber.

The chitosan used in the present invention is obtained by deacetylation of chitin isolated from cuticles of crab and shrimp. It is not necessary to specify the degree of deacetylation, but 85
% Or more is preferable because it is easily dissolved. Chitosan is poorly soluble in water, and is used by dissolving it in inorganic acids such as hydrochloric acid and sulfuric acid, and in organic acids such as formic acid, acetic acid, lactic acid, tartaric acid, malic acid, citric acid and gluconic acid. Preferred are lower fatty acids such as formic acid and acetic acid, and more preferred are lactic acid, tartaric acid and the like from the viewpoint of odor, price, and safety in terms of food additives.

The amount of acid used may be a concentration at which chitosan can be dissolved in water.
Use 3 times as much. If the amount of acid used is small, the chitosan will not dissolve, or it will take a long time to dissolve, and if the amount of acid used is large, when chitosan is added to the fiber by method A described below, the chitosan salt from the aqueous chitosan salt solution will be used. Since there is a phenomenon that the adsorption rate to the alkali-treated fiber becomes low, it is better to avoid using an unnecessarily large amount of acid.

The method of applying the chitosan salt to the fiber can be classified into two methods. One of the methods is a method in which after the alkali treatment, the fibers are immersed and stirred in an aqueous solution of chitosan salt to adsorb the chitosan salt to the fibers (hereinafter referred to as method A), and another method.
The method includes applying an aqueous chitosan salt solution to the fiber after the alkali treatment using a coating machine, or spraying the fiber using a sprayer having a spray nozzle, or passing the fiber through the liquid, and then using an excessive amount of mangle. This is a method that does not depend on the adsorption method (hereinafter referred to as method B), such as a pad for squeezing the solution.

Any method can be applied to the method of applying the chitosan salt in the present invention. However, in the case of Method A, the adsorption of the chitosan salt greatly depends on the pH of the aqueous solution of the chitosan salt, so Method B is preferably recommended. It The present invention, at the same time as the application of the chitosan salt, or after the application of the chitosan salt, for the purpose of further improving the objects other than the present invention or the objects of the present invention, a penetrating agent, a softening agent, an antistatic agent, other Does not interfere with the application of the drug. The chitosan salt treated fiber is then dried. The drying temperature and time are the moisture content of the fiber treated with chitosan salt, the basis weight, the drying model,
Take into consideration the air volume, etc. 60 ° C to 180 ° C is preferable.
If the temperature is low, the time is long, and if the temperature is high, the time is short. Excessive drying undesirably causes thermal yellowing of the fiber itself or chitosan.

The washing resistance and antibacterial property of the water-absorbent antibacterial synthetic fiber of the present invention is such that the fibers not graft-polymerized are hardly dyed with a cationic dye, but the fibers subjected to alkali treatment after the graft polymerization are dark-colored with a cationic dye. As in the case of dyeing in the same manner, chitosan is a polycation, and fibers that have not undergone graft polymerization do not adsorb chitosan salt from the chitosan salt aqueous solution, but fibers that have undergone alkali treatment after graft polymerization do not absorb chitosan salt from the chitosan salt aqueous solution. It is presumed that it was obtained due to the strong ionic bond since it adsorbs well.

The antibacterial effect of chitosan is presumed to be that the anionic constituents in the cell wall of the bacterium are adsorbed by the quaternized amino group of chitosan, the cell wall biosynthesis is inhibited, and the antibacterial effect is expressed. Has been done. It is presumed that the extremely excellent washing resistance and water absorbency of the fiber of the present invention was obtained by substituting hydrogen for the terminal group of the graft-polymerized water-soluble vinyl monomer with an alkali metal. Further, the water-absorbent antibacterial synthetic fiber of the present invention exhibits a surprisingly water-absorbing property even after washing up to 50 times, although the chitosan salt is added to the fiber surface.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Textile washing conditions are JIS L0217-103
The procedure was performed 0 to 50 times using a neutral detergent. Antibacterial property is Staphylococcus aureusAT
Using CC6538P, it was measured by the bacterial count method (SEK certified antibacterial effect test method). According to this measuring method, the antibacterial property is expressed as a difference in increase / decrease value, and the difference in increase / decrease value is 1.6
Based on the above, it is determined to have antibacterial properties. Water absorption is JI
SL1096.6.26. Water absorption. 1. Water absorption rate (1) Measured by method A (dropping method). In the table, 60 ↑ indicates that the time is 60 seconds or more.

[0022]

[Example 1] Leofeel (Nylon 66 manufactured by Asahi Kasei Kogyo KK) 30d / 10f basis weight, 160g / m
The half tricot of No. ² was scoured with a nonionic surfactant and dried at 100 ° C. for 2 minutes (the fiber that has undergone the above steps is referred to as Sample 1). Sample 1 was irradiated with an electron beam with an accelerating voltage of 200 KV and an irradiation dose of 3 Mrad in a nitrogen stream, immersed in acrylic acid, and washed with boiling water to obtain a fiber having a graft polymerization rate of 2.6%. Then, a bath ratio of 1: 2.0 g anhydrous sodium carbonate / liter.
It was dipped in an aqueous solution of 50 at 80 ° C. for 30 minutes, washed thoroughly with water, dehydrated and dried. (The fiber that has undergone the above steps is referred to as Sample 2.) Then, the fiber is treated with a pad method in a mixed solution of 0.5% chitosan K and 0.5% lactic acid manufactured by Katakura Chikkarin Co., Ltd. It was dried at 0 ° C for 2 minutes. The applied amount of chitosan K was 0.5%. The water absorbency before and after washing and the difference in increase / decrease value are as shown in Table 1.

[0023]

Comparative Examples 1 to 4 Sample 1 is referred to as Comparative Example 1. A fiber obtained by treating Sample 1 with a 0.5% chitosan K aqueous solution and a 0.5% aqueous lactic acid solution by a pad method and drying at 100 ° C. for 2 minutes is designated as Comparative Example 2. The applied amount of chitosan K was 0.5%.
Sample 2 is referred to as Comparative Example 3. Sample 2 is treated in the same manner as Comparative Example 2, and a fiber having the same amount of chitosan K applied is set as Comparative Example 4. The water absorbency before and after each washing and the difference in increase / decrease value are as shown in Table 1.

[0024]

[Example 2] Sample 1 with a bath ratio of 1:20, benzoyl peroxide 0.1%, monochlorobenzene 0.7%, methacrylic acid 0.9%, Emulgen 906 (manufactured by Kao Corporation, surface activity) Agent) Immersion and stirring in a mixed aqueous solution of 0.1% and soda ash 0.05%, heating from 40 ° C to 100 ° C in 40 minutes, treating at 100 ° C for 30 minutes, washing with water, and then boiling water For 30 minutes (the fiber that has undergone the above steps is referred to as Sample 3). The graft polymerization rate was 9.6%.
Sample 3 was treated in an aqueous solution containing 2.0 g / liter of anhydrous sodium carbonate at a bath ratio of 1:50 at 80 ° C. for 30 minutes, thoroughly washed with water, dehydrated and dried. Next, the fiber was treated with a pad method in a mixed aqueous solution of 0.5% chitosan S and 1.5% lactic acid manufactured by Taiyo Kagaku Kogyo Co., Ltd., and dried at 100 ° C. for 2 minutes. The applied amount of chitosan S was 0.5%.
The water absorbency before and after washing and the difference in increase / decrease value are as shown in Table 1.

[0025]

[Comparative Example 5] Sample 3 was dehydrated and dried to obtain chitosan S.
The fiber was treated with a pad method in a mixed aqueous solution of 5% and lactic acid at 1.5% and dried at 100 ° C. for 2 minutes, which is referred to as Comparative Example 5. The applied amount of chitosan S was 0.5%. The water absorbency before and after washing and the difference in increase / decrease value are as shown in Table 1.

[0026]

[Example 3] A unit weight of 30d / 12f of polyester synthetic fiber brand BZD manufactured by Asahi Kasei Co., Ltd., 16
A 0 g / m ² half tricot was refined with a nonionic surfactant (the fiber that has undergone the above steps is referred to as Sample 4). Then, with a bath ratio of 1:20, benzoyl peroxide 0.2%, monochlorobenzene 1.6%, methacrylic acid 1.0%, Plysurf A-217E (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., a surfactant) ) Immersion and stirring in a mixed aqueous solution of 0.2% and anhydrous sodium carbonate 0.05%, and 40 ° C to 40 ° C.
The temperature is raised to 100 ° C for 30 minutes, and the treatment is performed at 100 ° C for 30 minutes.
It was washed with water and then treated in boiling water for 30 minutes. The graft polymerization rate was 5.8%. Then Uvitex E
BF250 (Ciba Geigy Co., Ltd., fluorescent dye) 1.0
% (Vs. fiber weight), Nikkasan Salt 7000 (manufactured by Nichika Kagaku Co., Ltd., surfactant) 1.0 g / liter, acetic acid 1.0 cc / liter mixed at a bath ratio of 1:20, 70 ° C.
Immerse in the dyeing bath of No. 1 and stir, raise the temperature to 130 ° C in 40 minutes, and
It was dyed at 30 ° C. for 30 minutes and washed with water.

Then, the mixture was treated at 80 ° C. for 30 minutes in an aqueous solution containing 2.0 g of sodium carbonate at a bath ratio of 1:50, washed with water, and an aqueous solution containing 0.1 cc of acetic acid at a bath ratio of 1:20. Pickle at 5 ℃ for 5 minutes in
It was washed with water, dehydrated and dried. (The fiber that has undergone the above steps is referred to as sample 5.) Next, the fiber is treated with a pad method in a mixed aqueous solution of 0.5% chitosan S and 0.3% lactic acid, and 12
It was dried at 0 ° C. for 2 minutes. Chitosan S application amount is 0.5%
Met. The water absorbency before and after washing and the difference in increase / decrease value are as shown in Table 1.

[0028]

Comparative Examples 6 to 9 Samples 4 and 5 were dehydrated, and 120
The fibers dried at 2 ° C. for 2 minutes are referred to as Comparative Example 6 and Comparative Example 8, respectively. Dehydrating and drying sample 4 and sample 5,
Next, fibers treated with a pad method in a mixed aqueous solution of 0.5% chitosan S and 0.3% lactic acid and dried at 80 ° C. for 5 minutes are designated as Comparative Example 7 and Comparative Example 9, respectively. The applied amount of chitosan S was 0.5%. The water absorbency before and after each washing and the difference in increase / decrease value are as shown in Table 1.

[0029]

Example 4 Sample 4 in a bath ratio of 1:20 in a mixed aqueous solution of benzoyl peroxide 0.2%, methyl benzoate 1.0%, methacrylic acid 0.8% and Plysurf A-217E 0.15%. Immersion and agitation, 100 at 40 ° C for 40 minutes
The temperature is raised to ℃, treated for 30 minutes at 100 ℃, washed with water, hot water,
It was washed with water, then treated in boiling water for 30 minutes and thoroughly washed with water. The graft polymerization rate was 2.8%. Then ka
yalonPolyesterNavyBlueTK-
SF200 (manufactured by Nippon Kayaku Co., Ltd., disperse dye) 4.0%
(Vs. fiber weight), Nikka sun salt 7000, 1.0g
/ L and 1.0 cc / L of acetic acid mixed at a bath ratio of 1:20 and immersed in a dyeing bath at 70 ° C for 30 minutes in 40 minutes
The temperature was raised to 0 ° C., dyeing was carried out at 130 ° C. for 60 minutes, and washing with water was carried out.
(The fiber that has undergone the above steps is referred to as Sample 6.) Next, 2.0 g / liter of sodium hydroxide, 2.0 g / liter of hydrosulfite, and Sunmor RC700 (manufactured by Nichika Chemical Co., Ltd., a surfactant). A 2.0 g / liter mixed aqueous solution was treated at a bath ratio of 1:20 at 80 ° C. for 30 minutes, washed with water, and at a bath ratio of 1:20 containing 0.1 cc / liter of acetic acid at 25 ° C. for 5 minutes. It was pickled, washed with water, and dehydrated and dried. Next, 0.3% of chitosan S and 0.1% of lactic acid.
The fibers are treated with a pad method in a 3% mixed aqueous solution, and the temperature is 120 ° C.
And dried for 2 minutes. The applied amount of chitosan S was 0.3%. The water absorbency before and after washing and the difference in increase / decrease value are as shown in Table 1.

[0030]

[Comparative Example 10] Sample 6 was dehydrated and dried to obtain chitosan S.
The fiber was treated with a pad method in a mixed aqueous solution of 3% and 0.3% lactic acid, and dried at 80 ° C. for 5 minutes. The applied amount of chitosan S was 0.3%. The water absorbency before and after washing and the difference in increase / decrease value are as shown in Table 1.

[0031]

[Table 1]

[0032]

INDUSTRIAL APPLICABILITY The present invention uses chitosan, which is a highly safe substance derived from a natural product, and has excellent washing resistance, antibacterial property, deodorant property, and water absorption property. Therefore, it is suitable for applications such as clothes and bedding utilizing these properties, and can be widely used.

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Claims (3)

[Claims] 1. Acrylic acid and / or methacrylic acid having a terminal acidic group substituted with an alkali metal has a polymerization rate of 1 to 2.
A water-absorbent antibacterial synthetic fiber obtained by adding chitosan salt to a polyester synthetic fiber or a polyamide synthetic fiber graft-polymerized at 0%. 2. The water-absorbent antibacterial synthetic fiber according to claim 1, wherein the chitosan salt is provided in an amount of 0.1 to 2.0% by weight based on the fiber in terms of chitosan. 3. A synthetic polyester fiber or a synthetic polyamide fiber is graft-polymerized with acrylic acid or methacrylic acid, treated with an alkaline aqueous solution of an alkali metal, and then treated with a chitosan salt aqueous solution. Method for producing water-absorbing antibacterial synthetic fiber.