JPH10158978A - Antifungal acrylic fiber and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain antimicrobial fiber that is rich in durability causing no deterioration of its antifungal activity due to processing or washing by allowing wet-spun acrylic fiber to contain chitosan and a specific quaternary ammonium salt, then drying and densifying the treated fiber. SOLUTION: An acrylonitrile polymer containing >=50wt.% of acrylonitrile units and unsaturated monomer units copolymerizable with acrylonitrile, for example, acrylic acid is dissolved in a solvent, for example, dimethylacetamide. Then, the dope is wet-spun, then the fiber is dipped in a solution of chitosan and a quaternary ammonium of the formula (R1 and R2 is a 8-18C alkyl; X<-> is at least one of organic acid anion or oxo acid ion selected from the group of halides, carboxylate, sulfonate, sulfate, phosphate), for example, didecyldimethylammonium chloride, dried and densified to give the objective antimicrobial acrylic fiber containing 0.05-2wt.% of chitosan and the quaternary ammonium salt in an amount of more than the content of chitosan and lower than 3wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial acrylic fiber which can be used for clothing, interior and material applications, and a method for producing the same.

[0002]

2. Description of the Related Art Antibacterial fibers have been widely used in recent years for the purpose of suppressing the growth of various bacteria and preventing the generation of unpleasant off-flavors. In response to consumer needs for greater comfort, it is widely distributed throughout the city as a product for general consumers.

[0003] Various antibacterial agents are used in such antibacterial fibers, and there are various methods of compounding antibacterial agents into textile products. For example, as an antibacterial agent, a technique using an inorganic metal material represented by silver-zeolite (JP-A-5-272008, etc.), a copper compound or a metal fine powder such as copper or zinc is added to the fiber. Method (Japanese Unexamined Patent Publication No.
No. 115440, etc.) A method using a derivative of a quaternary ammonium salt (JP-A-59-130371), a method using a halodiallyl urea compound such as trichlorocarbanilide (JP-A-2-259169), and others. As a compound, a thiabendazole compound (JP-A-61
616), phenolic compounds (JP-A-60-1985)
No. 252713) and a method using a fatty acid ester-based compound (JP-A-63-6173).

However, there is a problem that a fiber obtained by compounding a silver and a copper compound undergoes a bleaching treatment, whereby the silver and the copper compound are denatured and the antibacterial property is lost.

[0005] Against this background, attention has recently been paid to a function-imparting agent for a natural antibacterial agent. For example, hinokitiol extracted from Aomori Hiba or Taiwan Hinoki has antibacterial, antifungal, insect repellent and other functions, and chitosan, which is a deacetylated product of natural polysaccharide chitin obtained from crustaceans, etc., has antibacterial deodorization, MRSA, etc. It is said to have a growth inhibitory effect, high moisture retention, prevention and improvement of atopic dermatitis, and many other functions, and there is a known case in which a comfortable feel can be obtained when applied to textiles for use in clothing.

As a method for applying chitosan to acrylic fibers, a method using an adhesive, a method of kneading fine chitosan powder into a spinning solution, a method of treating with an acidic solution of chitosan, and the like are known. However, when chitosan is applied to fibers using an adhesive, the adhesive is coagulated and hardened due to the cohesive action of chitosan, and the amount of adhesive is limited when trying to express the original function of chitosan. Inferior in washing durability. Further, even if chitosan is pulverized into fine powder, uniformly dispersed in an acrylonitrile-based polymer solution, and spinning is performed by a known method, it is difficult to spin with good productivity due to clogging in a spinning hole of a spinneret.

The antibacterial performance of the chitosan-added acrylic fiber obtained by immersing the acrylic fiber in a chitosan acidic solution and subsequently neutralizing it with an alkaline bath to precipitate on the fiber surface is determined by post-processing such as dyeing and softening. Or easily lost by washing.

[0008]

Accordingly, the present invention is effective against many bacteria required for antibacterial fiber products, and is useful for post-processing such as dyeing, bleaching and softening of fibers, washing, ironing and the like. It is an object of the present invention to provide an antibacterial acrylic fiber which avoids a decrease in antibacterial and deodorant properties due to various treatments applied to a textile product in a use environment and does not generate harmful substances in all processes from production to disposal, and a method for producing the same. .

[0009]

The present invention is characterized in that the chitosan content is in the range of 0.05 to 2% by weight, the quaternary ammonium salt content is higher than the chitosan content and is not more than 3% by weight. The antibacterial acrylic fiber described above is the first gist.

[0010] Further, the yarn before the polymer solution obtained by dissolving the acrylonitrile-based polymer in a solvent is wet-spun and dried and densified, is immersed in a mixed solution of chitosan and a quaternary ammonium salt, or A second aspect of the present invention is a method for producing an antibacterial acrylic fiber, which is sequentially immersed in a quaternary ammonium salt solution and then dried and densified.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, an acrylonitrile polymer is a vinyl polymer containing at least 50% by weight of an acrylonitrile unit and an unsaturated monomer unit copolymerizable therewith. When the amount of the acrylonitrile unit in the acrylonitrile-based polymer is less than 50% by weight, the sharpness of coloring and the coloring property, which are the characteristics of the acrylic fiber, are deteriorated, and other physical properties such as thermal properties are also reduced.

The unsaturated monomers copolymerizable with acrylonitrile include acrylic acid, methacrylic acid or alkyl esters thereof, vinyl acetate, acrylamide,
Vinyl chloride, vinylidene chloride, and, depending on the purpose, ionic unsaturated monomers such as sodium vinylbenzenesulfonate, sodium methallylsulfonate, sodium allylsulfonate, sodium acrylamidomethylpropanesulfonate, and sodium parasulfophenyl methallyl ether. Can be used.

The chitosan used in the present invention is, for example, crab,
It is a basic polysaccharide obtained by removing calcium carbonate and protein from chitin that forms the exoskeleton of shellfish such as shrimp, and deacetylating chitin obtained by heating with concentrated alkali.

The antibacterial acrylic fiber of the present invention has a chitosan content of 0.1 as measured by the measuring method described later.
It is necessary that the content be in the range of from 0.5 to 2% by weight from the viewpoint of achieving both antibacterial and deodorant properties, dyeing properties and flexibility. When the chitosan content is less than 0.05% by weight, sufficient flexibility and antibacterial properties are not exhibited.
Alternatively, the operability is deteriorated due to the loss of chitosan in the spinning process. In particular, in order to maintain the color clarity, which is an advantage of acrylic fiber, the chitosan content must be 0.05% by weight.
Particularly preferred is a range of １1% by weight.

In the present invention, the chitosan content is measured by the method described in Examples.

The antibacterial acrylic fiber of the present invention must contain a quaternary ammonium salt together with chitosan. Surprisingly, this arrangement makes the flexibility afforded by containing chitosan permanent. It is necessary that the content of the quaternary ammonium salt exceeds the chitosan content and is not more than 3% by weight. When the content of the quaternary ammonium salt is less than the chitosan content, the flexibility becomes low, and the dispersion stabilization of the chitosan during drying and densification during the production process of dipping in a mixed solution of chitosan and the quaternary ammonium salt is performed. The effect of suppressing the sticking of the fibers is reduced. On the other hand, if the content exceeds 3% by weight, the dyeability may be reduced, or the operability may be deteriorated due to the dropout of the quaternary ammonium salt in the spinning process.

The combined use of chitosan and a quaternary ammonium salt is effective in maintaining the stable dispersion of chitosan in the production step of dipping in a mixed solution of chitosan and the quaternary ammonium salt, and further, in the step of drying and densification, the fibers are stuck together. It also has the advantage that prevention is possible.

In particular, in order to maintain the antibacterial performance of chitosan during post-processing such as dyeing and bleaching, or even during washing, and to facilitate stable dispersion of chitosan in the manufacturing process, the general formula:

[0019] _{[R 1 R 2 (CH 3} ) 2 N] + X - ( where, R _1, R ₂ are the same or different alkyl group of 8-18 carbon atoms, X ^- is a halogen ion, organic acid anion or oxo The use of quaternary ammonium salts is preferred. Here, the organic acid anion is at least one selected from the group consisting of carboxylate, sulfonate, sulfate, phosphate and phosphonate, and carboxylate and sulfate are particularly preferred. The use of an organic acid anion is advantageous in that the problem of rusting in a later step such as a spinning step caused by a halogen ion or an oxo acid ion attached to the fiber when another anion is used can be suppressed.

Examples of such quaternary ammonium salts include didecyldimethylammonium chloride, dihydroxyethyldecylethylammonium chloride, N-hydroxyethyl N, N-dimethylN-stearylamidoethylammonium ethylsulfonate, and didecyldimethylammonium adipate. And didecyldimethylammonium gluconate are preferably used.

[0021] The antibacterial acrylic fiber of the present invention comprises 3
Even when the process oil is removed by the 0-minute treatment, a low coefficient of static friction between fibers is maintained. This means that a low coefficient of static friction between fibers-fibers, that is, flexibility is maintained even after washing after the dyeing process and the textile product,
When the fiber of the present invention is used in the final fiber product in an amount of 70% by weight or more, it is possible to reduce the amount of the softener usually used in the final finishing step of the acrylic fiber product.

When the antibacterial acrylic fiber of the present invention is used as a fiber composite such as a spun yarn, a cloth, or a nonwoven fabric, the antibacterial acrylic fiber of the present invention is mixed in an amount of 70% by weight or more in order to obtain antibacterial performance and flexibility. However, to obtain only antibacterial properties, 2
It is preferable that 0% by weight or more is mixed. The fiber to be mixed with the antibacterial acrylic fiber of the present invention is not particularly limited as long as it is selected according to the purpose of use. Examples thereof include known fibers such as ordinary acrylic fiber, cotton, rayon, wool, hemp, silk, and polyester. Can be

Next, a method for producing the antibacterial acrylic fiber of the present invention will be described. The solvent for dissolving and spinning the acrylonitrile-based polymer is not particularly limited as long as the polymer can be dissolved in a concentration at which the polymer can be spun, and organic solvents such as dimethylacetamide, dimethylformamide, and dimethylsulfoxide; nitric acid; A concentrated aqueous solution of an inorganic substance such as salt soda and zinc chloride can be used. Organic solvents such as dimethylacetamide, dimethylformamide, and dimethylsulfoxide are preferably used from the viewpoint of forming microvoids in the acrylic fiber yarn before drying and densification described below.

In the present invention, chitosan forms a salt in the presence of an acid and dissolves in an acrylic fiber in a stage called a coagulated yarn, a washing yarn, or a drawn yarn before being dried and densified. The provision of a quaternary ammonium salt is necessary in order to suppress the loss of chitosan and the deactivation of the antibacterial and deodorant performance of chitosan in use environments such as post-processing and washing. Chitosan provided to the acrylic fiber of the present invention,
Many quaternary ammonium salts are incorporated into microvoids present in acrylic fiber yarns before drying and densification and relatively loose parts in the fiber structure, and are deposited and precipitated. Is estimated to last.

The method of immersing the acrylic fiber yarn before drying and densification in a mixed solution of chitosan and a quaternary ammonium salt simplifies the process and is advantageous in terms of stability of the chitosan solution. The method of sequentially immersing the fibers in a quaternary ammonium salt solution is advantageous in that the process can be easily controlled and the degree of impregnation of the fibers with chitosan can be controlled independently.

The tank for the quaternary ammonium salt solution can be provided independently of the process oil treatment tank for acrylic fiber, or can also serve as the process oil treatment tank. It is preferable to add a process oil to the quaternary ammonium salt solution and to treat the acrylic fiber yarn before drying and densification because permanent flexibility becomes more remarkable.

The concentration of chitosan dissolved in the acidic aqueous solution is preferably 5% by weight or less, because it can be easily dissolved. The type of the acid is not particularly limited, but hydrochloric acid, acetic acid, lactic acid, formic acid and the like can be suitably used. Further, the concentration of the acid is preferably as low as possible within the range in which chitosan is dissolved from the problem of corrosion in the spinning process.

In the present invention, a cationic or nonionic surfactant may be used in addition to the quaternary ammonium salt.

[0029]

The present invention will be described more specifically with reference to the following examples. In Examples, “% by weight” is simply expressed as “%”. (Method of measuring chitosan content) 1) 10 ml of a 70% zinc chloride solution was added to 0.2 g of weighed acrylic fiber to dissolve the fiber. 2) 2 ml of dimethylacetamide was added and left for 1 hour.

3) 1 ml of Erich reagent (1% ethanol solution of p-dimethylaminobenzaldehyde) was added. 4) After 2 hours, the absorbance of the solution of 3) was measured at a wavelength of 435 nm. 5) The chitosan concentration was determined from the calibration curve, and converted to the acrylic fiber content.

(Method of measuring quaternary ammonium salt content)
Was dissolved to 4% acrylic fibers in DMSO-d _6, ¹ 1 H-NMR was measured, contained in the fibers from the peak area ratio of the peak derived from acrylonitrile polymer and quaternary ammonium salt The amount was determined.

(Reduced Viscosity of Polymer) The reduced viscosity ηred of an acrylonitrile polymer is determined by measuring the viscosity of a polymer solution obtained by dissolving an acrylonitrile polymer in dimethylformamide to 0.5% at 25 ° C. with a Cannon fence. It was measured using a viscometer.

(Measurement of antibacterial performance) The difference in the increase or decrease in the number of bacteria due to Staphylococcus aureus was determined by the method of measuring the number of bacteria determined by the Textile Sanitary Processing Council. A difference of 1.6 or more of the increase and decrease values of the number of bacteria was used as a standard for antibacterial activity. In addition, the washing method followed the method determined by the council.

(Fiber-to-fiber static friction coefficient) The fiber-to-fiber static friction coefficient was measured using a radar method fiber friction coefficient measuring device (produced by Koa Shokai).

Example 1 An acrylonitrile-based polymer (acrylonitrile / vinyl acetate = 93/7 by weight) having a reduced viscosity of 1.96 was obtained by an aqueous suspension polymerization method. This was dissolved in dimethylacetamide so as to have a copolymer concentration of 25% to prepare a spinning stock solution.

This spinning dope is wet-spun in a spinning bath filled with a 30% aqueous solution of dimethylacetamide at 40 ° C., stretched 5 times while washing the solvent in boiling water, and subsequently chitosan (Kyowa Technos Co., Ltd.) Flownac C)
0.1%, acetic acid 0.05%, polyoxyethylene (degree of polymerization 200) 0.3% as a surfactant, didecyldimethylammonium chloride 0.3 as a quaternary ammonium salt
5% of the dispersed process oil was introduced into an oil bath for application, and dehydrated so that the amount of water adhering to the fiber weight was 100%. Thereafter, drying and densification were performed with a hot roller at 150 ° C.

Further, relaxation treatment was performed in steam of 2.5 kg / cm ² to obtain chitosan-treated acrylic fibers having a single fiber fineness of 3 denier. The amount of attached chitosan and the amount of quaternary ammonium salt in the fiber were 0.08% and 0.33% when measured by the above-mentioned methods. No separation of chitosan in the oil bath and no sticking of fibers in the drying and densification process were observed.

The fiber was treated in boiling water having a bath ratio of 1:50 for 30 minutes, washed with water and air-dried, and the coefficient of static friction between the fibers was measured to be 0.285.

This fiber was cut to a length of 51 mm to produce a spun yarn. 50 g of this spun yarn, 0.25 g of dye (Hodogaya Chemical Co., Ltd., Katilon blue KGLH),
1 g of acetic acid, 0.25 g of sodium acetate and 1000 g of pure water
The mixture was heated to 100 ° C., kept at that temperature for 30 minutes, washed with water, dehydrated and dried. At the same time as evaluating the color vividness of the spun yarn after dyeing by naked eye judgment, before washing,
The antibacterial properties after 10 washes were evaluated. The results were as shown in Table 1.

(Examples 2 to 4, Comparative Examples 1 to 3) Example 1
, The chitosan concentration in the oil bath, acetic acid concentration, surfactant concentration, the moisture content after immersion in chitosan acidic aqueous solution is changed step by step to obtain acrylic fibers with different chitosan content and didecyldimethylammonium chloride content Was. In all cases, no separation of chitosan in the oil bath and no sticking of fibers in the drying and densification process were observed. The operation was performed in the same manner as in Example 1, and the static friction coefficient between fibers and the antibacterial property were evaluated. The results are as shown in Table 1. Chitosan content 2.4%,
2.88% raw cotton with didecyldimethylammonium chloride content (Comparative Example 2) and 0.4% chitosan content, and 3.25% raw material with didecyldimethylammonium chloride (Comparative Example 3) spinning and drying roller and spinning Adhesion of chitosan (Comparative Example 2) or didecyldimethylammonium chloride (Comparative Example 3) to the process was large, and a spun yarn could not be obtained.

(Comparative Example 4) The same as in Example 1 except that the surfactant was made of only a polyoxyethylene concentration of 0.2% and a dimethyldidecylammonium chloride concentration of 0.2% and was treated in an oil bath containing no chitosan. To obtain an acrylic fiber having a single fiber fineness of 3 denier. The coefficient of static friction between the fibers measured in the same manner as in Example 1 was 0.455.

This fiber was dyed into a spun yarn by performing the same operation as in the example, and the antibacterial property was evaluated before and after washing 10 times after the dyeing. As a result, as shown in Table 1, the antibacterial property was developed. Did not.

Example 5 A spun yarn was produced by mixing 30% of the acrylic fiber obtained in Example 1 and 70% of cotton. After cationic dyeing under the same conditions as in Example 1, the antibacterial properties before and after washing 10 times were evaluated, and were 2.8 and 1.9, respectively.

Example 6 A quaternary ammonium salt and a surfactant in an oil bath were prepared with a concentration of dihydroxyethyldecylethylammonium chloride of 0.3% and a concentration of polyoxyethylene (degree of polymerization of 200) of 0.3%. An acrylic fiber was obtained in the same manner as in Example 1 except that the procedure was repeated. Chitosan content is 0.0
The content of 9% and dihydroxyethyldecylethylammonium chloride was 0.29%. The coefficient of static friction between the fibers was 0.320, the antibacterial property was 2.8 before washing, and 2.2 after 10 washings.

Example 7 A quaternary ammonium salt and a surfactant in an oil bath were N-hydroxyethyl N, N-dimethyl N-stearylamidoethylammonium ethyl sulfonate at a concentration of 0.4%, ethylene oxide and propylene oxide. Block polyether (ethylene oxide / propylene oxide = 40/60, molecular weight 500
An acrylic fiber was obtained in the same manner as in Example 1 except that the concentration of 0) was changed to 0.2%. Chitosan content in raw cotton is 0.0
The content of 9%, N-hydroxyethyl N, N-dimethyl N-stearylamidoethylammonium ethyl sulfonate was 0.38%. The coefficient of static friction between fibers was 0.290, the antibacterial property was 2.6 before washing, and the
After the test, it was 2.0.

Example 8 The concentration of chitosan (Kyowa Technos Co., Ltd., Flownac C) in an oil bath was set to 0.1%, the concentration of acetic acid was set to 0.05%, and the concentration of didecyldimethylammonium chloride was set to 0.35%. Ethylene oxide propylene oxide block polyether (ethylene oxide / propylene oxide = 40 /
Acrylic fiber was obtained in the same manner as in Example 1 except that the concentration of the compound (60, molecular weight 5000) was 0.2%. The chitosan content was 0.09%, and the attached amount of didecyldimethylammonium chloride was 0.32%. The coefficient of static friction between fibers was 0.295, the antibacterial property was 5.0 before washing, and the
It was 4.8 after 0 times.

(Comparative Example 5) Acrylic acid was prepared in the same manner as in Example 1 except that the concentration of the surfactant in the oil bath was 0.5% of polyoxyethylene (degree of polymerization: 200) and no quaternary ammonium salt was added. Fiber was obtained. Chitosan content is 0.09%
Met. However, the coefficient of static friction between fibers was 0.41.
It was 0, and the spun yarn could not be obtained because the amount of sticking of the raw cotton was large.

EXAMPLE 11 0.1% of chitosan (Kyowa Technos Co., Ltd., Flownac C), 0.05% of acetic acid, 0.3% of polyoxyethylene (degree of polymerization: 200) as a surfactant Instead of introducing into the oil bath a process oil agent dispersing 0.35% of didecyldimethylammonium chloride as a quaternary ammonium salt is added, "chitosan (Kyowa Technos Co., Ltd. Flownac C) 0.1%,
A process oil in which 0.3% of polyoxyethylene (degree of polymerization: 200) is dispersed as a surfactant and 0.35% of didecyldimethylammonium chloride is dispersed as a quaternary ammonium salt after being introduced into an immersion tank of acetic acid 0.05%. To give an acrylic fiber. In the same manner as in Example 1,
The results of evaluating the coefficient of static friction between fibers and the antibacterial properties were as shown in Table 1.

(Examples 12 to 14, Comparative Examples 6 and 7) In Example 11, the concentration of chitosan in the chitosan solution tank and the concentration of didecyldimethylammonium chloride in the oil bath were changed stepwise, and chitosan and didecyldimethyl chloride were changed. An acrylic fiber containing ammonium was obtained. Table 1 shows the results of evaluating the coefficient of static friction between fibers and the antibacterial properties in the same manner as in Example 1. 2.48 chitosan content
%, Didecyldimethylammonium chloride content 2.96
% Of the raw cotton (Comparative Example 6) had a large amount of chitosan attached to the spinning drying roller and the spinning process, and a spun yarn could not be obtained.

(Comparative Example 8) The procedure of Example 1 was repeated except that the treatment was carried out in an oil bath containing 0.2% of polyoxyethylene and 0.2% of didecyldimethylammonium chloride as surfactants without passing through a chitosan solution tank. By operating in the same manner as in No. 11, an acrylic fiber having a single fiber fineness of 3 denier was obtained. In the same manner as in Example 1, the measured coefficient of static friction between fibers was set at 0.1.
446.

This fiber was treated in the same manner as in Example 1 to obtain a dyed spun yarn. The antibacterial properties before and after washing 10 times were evaluated. As a result, no antibacterial property was exhibited as shown in Table 1. .

Example 15 A spun yarn was produced by mixing 30% of the acrylic fiber obtained in Example 11 and 70% of cotton. After cationic dyeing under the same conditions as in Example 1, the antibacterial properties before and after washing 10 times were evaluated, and were 3.1 and 2.4, respectively.

Example 16 In Example 11, the quaternary ammonium salt and the surfactant in the oil bath were changed to a dihydroxyethyldecylethylammonium chloride concentration of 0.3% and a polyoxyethylene (degree of polymerization 200) concentration of 0.1%. An acrylic fiber was obtained in the same manner as in Example 11 except that the content was 3%. The content of chitosan in the raw cotton was 0.1%, and the content of dihydroxyethyldecylethylammonium chloride was 0.29%. The coefficient of static friction between the fibers was 0.334, the antibacterial property was 4.26 before washing, and 3.5 after 10 washings.

Example 17 In Example 11, the quaternary ammonium salt and the surfactant in the oil bath were replaced with N-hydroxyethyl N, N-dimethyl N-stearylamidoethyl ammonium ethyl sulfonate at a concentration of 0.4%. , Ethylene oxide propylene oxide block polyether (ethylene oxide / propylene oxide = 4
Acrylic fiber was obtained in the same manner as in Example 11 except that the concentration was 0.2% (0/60, molecular weight 5000). The content of chitosan in the raw cotton was 0.1%, and the content of N-hydroxyethyl N, N-dimethyl N-stearylamidoethylammonium ethylsulfonate was 0.40%. The coefficient of static friction between the fibers was 0.298, the antibacterial property was 3.2 before washing, and 2.3 after 10 washings.

(Example 18) In Example 11, chitosan in an oil bath (Kyowa Technos Co., Ltd., Flownac C)
The concentration was set to 0.1%, the concentration of acetic acid was set to 0.05%, the concentration of didecyldimethylammonium chloride was set to 0.35%, and the ethylene oxide / propylene oxide block polyether (ethylene oxide / propylene) in the process oil treatment tank was set. Oxide = 40/60, molecular weight 50
Acrylic fiber was obtained in the same manner as in Example 11 except that the concentration of (00) was 0.2%. The chitosan content is 0.1
%, Dihydroxyethyldecylethylammonium chloride content was 0.32%. The coefficient of static friction between fibers was 0.295, the antibacterial property was 5.0 before washing, and the
After the test, it was 4.8.

Comparative Example 9 The procedure of Example 11 was repeated except that the concentration of the surfactant in the oil bath was 0.5% of polyoxyethylene (degree of polymerization: 200) and no quaternary ammonium salt was added. An acrylic fiber was obtained in the same manner as described above. The chitosan content was 0.09%. However, the coefficient of static friction between the fibers was 0.410, and raw cotton was so stuck that a spun yarn could not be obtained.

Example 19 An acrylic fiber was obtained in the same manner as in Example 11, except that the quaternary ammonium salt in the oil bath was changed to a didecyldimethylammonium adipate concentration of 0.4%. The chitosan content is 0.
The content of 1% didecyldimethylammonium adipate was 0.39%. The coefficient of static friction between the fibers was 0.287, and the antibacterial property was 4.8 before washing and 4.4 after washing 10 times.

Example 20 Example 11 was repeated except that the quaternary ammonium salt in the oil bath was changed to a didecyldimethylammonium gluconate concentration of 0.5%.
An acrylic fiber was obtained in the same manner as described above. The chitosan content was 0.1% and the didecyldimethylammonium gluconate content was 0.47%. The coefficient of static friction between fibers was 0.269, the antibacterial property was 5.2 before washing, and the
After 4.5 times, it was 4.5.

[0059]

[Table 1]

[0060]

According to the present invention, there can be obtained an acrylic fiber whose antibacterial performance is not deteriorated by post-processing such as dyeing and bleaching of fiber, washing and ironing in the environment where the fiber product is used. In addition, when the fiber of the present invention is used in a final fiber product in an amount of 70% or more because of its flexibility, the amount of the softening agent used in the final finishing step can be significantly reduced. Further, according to the production method of the present invention, the fibers can be produced efficiently.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshihiro Nishihara 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Otake Works (72) Inventor Masako Iwamoto 201-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd.

Claims (6)

[Claims] (1) a chitosan content of 0.05 to 2% by weight;
An antibacterial acrylic fiber having a quaternary ammonium salt content exceeding the chitosan content and not more than 3% by weight. 2. A quaternary ammonium salt represented by the general formula: [R ₁ R ₂ (CH ₃ ) ₂ N] ⁺ X ⁻ (where R ₁ and R ₂ are the same or different alkyl groups having 8 to 18 carbon atoms, X ^- is a halogen ion, an organic acid anion or an oxo acid ion.). 3. The antibacterial acrylic fiber according to claim 2, wherein X ⁻ is one or more organic acid anions selected from the group consisting of carboxylate, sulfonate, sulfate, phosphate and phosphonate. 4. A yarn obtained by dissolving a polymer solution obtained by dissolving an acrylonitrile-based polymer in a solvent before wet-spinning and drying and densifying the polymer solution is immersed in a mixed solution of chitosan and a quaternary ammonium salt, or A method for producing an antibacterial acrylic fiber, characterized by sequentially immersing in a quaternary ammonium salt solution, followed by drying and densification. 5. A quaternary ammonium salt represented by the general formula: [R ₁ R ₂ (CH ₃ ) ₂ N] ⁺ X ⁻ (where R ₁ and R ₂ are the same or different alkyl groups having 8 to 18 carbon atoms, X ^- is a halogen ion, a manufacturing method of antimicrobial acrylic fiber according to claim 4, wherein a represents an organic acid anion or an oxoacid ion).. 6. The method for producing an antibacterial acrylic fiber according to claim 4, wherein a process oil is contained in a mixed solution of chitosan and a quaternary ammonium salt or in a quaternary ammonium salt solution.