JPS633965B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an antibacterial fiber with good texture and a method for producing the same. Conventional technology Acrylic synthetic fibers are widely used for clothing and bedding, but in recent years they have been used in the sanitary field such as mats and carpets, as well as sports clothing, socks, underwear, sheets, etc. that come in contact with sweat secreted by the human body. BACKGROUND ART Blankets and the like have come to be required to have antibacterial and deodorizing properties. Conventionally, methods have been known in which natural or synthetic fibers are coated or sprayed with antibacterial compounds, or the fibers are impregnated with a compound solution, but these methods do not maintain their effectiveness long-term and do not last long after washing, etc. This has the disadvantage that the antibacterial agent that has been attached easily falls off. Furthermore, if the fibers are processed with a resin containing an antibacterial agent in order to impart washing resistance to the fibers, the texture of the fibers will be impaired. On the other hand, thiabendazole exhibits a strong antibacterial effect against many microorganisms even in minute amounts, and has almost no toxicity, so it is even approved as a food additive in the United States. However, this thiabendazole is expensive;
Acrylic polymers are easily soluble in many organic solvents,
When wet-spinning a conventional organic solvent solution with an acrylic polymer, a large amount of thiabendazole is eluted into the spinning bath during spinning, resulting in poor yield of thiabendazole contained in the fiber and increased costs. ing. The inventors of the present invention have conducted extensive research in order to improve these drawbacks. By mixing thiabendazole dispersed in a plasticizer with an acrylonitrile polymer, we have developed a method that provides washing resistance without deteriorating the texture or physical properties. We obtained the knowledge that it has good antibacterial properties. Problems to be Solved by the Invention The purpose of the present invention is to have excellent antibacterial and deodorizing properties,
To provide an antibacterial acrylic synthetic fiber with low toxicity, less irritation to the skin and mucous membranes, wash resistance, and no deterioration in texture or physical properties. Another object is to provide a method for manufacturing such acrylic synthetic fibers industrially easily and at low cost. Means for Solving the Problems The gist of the present invention is as follows. (1) General formula for 100 parts by weight of acrylonitrile polymer, 0.05 to 20 parts by weight of a plasticizer insoluble in an inorganic solvent in which 0.05 to 3 parts by weight of thiabendazole represented by is dispersed in the acrylonitrile polymer. Antibacterial fiber with good combination (2) General formula for 100 parts by weight of acrylonitrile polymer: 0.05 to 3 parts by weight of thiabendazole represented by is dispersed in a plasticizer insoluble in an inorganic solvent, and then 0.05 parts by weight of the plasticizer insoluble in the inorganic solvent is dispersed.
Production of antibacterial fiber with good texture by adding ~20 parts by weight to an acrylonitrile polymer previously dissolved in an inorganic solvent solution and dispersing it to prepare a spinning stock solution, which is then spun using a conventional method. Method. The acrylic polymer used in the present invention contains at least 60% by weight of acrylonitrile, and refers to acrylonitrile copolymers with other polymerizable vinyl monomers and mixed polymers with other polymers. do. Other polymerizable vinyl monomers include vinyl acetate, vinyl chloride, vinylidene chloride, acrylic acid,
Copolymerized with acrylonitrile, such as acrylic esters, methacrylic acid, methacrylic esters, acrylamide, methacrylamide, monoalkyl substituted products thereof, vinyl compounds such as vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, and their salts. Refers to all monomers that can be used. The plasticizer used in the present invention is at least one selected from the group consisting of chlorinated paraffin, phosphate ester, phthalate ester, aliphatic-basic acid ester, aliphatic dibasic acid ester, dihydric alcohol ester, etc. It is. The spinning method adopted in the present invention is a wet spinning method using a concentrated inorganic acid such as concentrated nitric acid or concentrated sulfuric acid, and a concentrated aqueous solution of an inorganic salt such as Rodan salt or zinc chloride as a solvent.
Conventionally known methods such as spinning, washing with water, stretching, drying, etc. can be applied, and there is no need to specifically limit the method. By employing wet spinning using an inorganic solvent, elution of thiabendazole into the spinning bath can be completely prevented. The chemical name of thiabendazole in the present invention is 2
-(4-thiazolyl)-benzimidazole, and preferably 0.05 to 3 parts by weight is dispersed per 100 parts by weight of the acrylonitrile polymer. If the content of thiabendazole is less than 0.05 part by weight, the antibacterial effect will be poor. It also has an antibacterial effect.
No more than part by weight is required. In addition, it may be used in combination with other known antibacterial or antifungal substances. The concentration of the inorganic solvent solution of the polymer used for spinning is usually 10 to 20% by weight. Thiabendazole may be dispersed in a plasticizer in advance, added after dissolving the acrylonitrile polymer in the inorganic solvent, and sufficiently stirred to disperse into fine particles.
The plasticizer must be dispersed finely enough to form fibers. Example 1 A copolymer consisting of 93.1% by weight of acrylonitrile, 6.3% by weight of methyl acrylate, and 0.6% by weight of sodium methallylsulfonate was dissolved in 69.0% by weight of concentrated nitric acid to have a copolymer concentration of 15.3% by weight. A solution was prepared, and a solution in which chlorinated paraffin and thiabendazole with a chloride degree of 40% were mixed and dispersed in the composition shown in Table 1 was added to the solution based on 100 parts of the coweight, and the mixture was stirred and desorbed for 30 minutes. The foamed material was used as a spinning dope.
This was formed into fibers by a conventionally known method through steps such as spinning, water washing, stretching, drying, and relaxation heat treatment. Create a knitted fabric with the obtained fibers and divide it into 5cm x 5
The pieces were cut into cm-sized pieces and placed on an agar medium, sprinkled with a mixed mold spore suspension, and cultured at 28°C for 14 days. A sample in which no bacterial growth was observed around the knitted fabric was graded as (-), and a sample in which growth was observed was graded as (+). The results are shown in Table-1.

[Table] The concentration of thiabendazole in the fiber is determined by
It was dissolved in DNF and analyzed by gas chromatography. It can be seen that there is almost no loss with respect to the amount added. Example 2 Among the fibers produced in Example 1, No. 1 shown in Table 1 was used.
A knitted fabric was prepared for No. 4, and the antibacterial properties of this knitted fabric after washing 0, 5, 10, 15, and 20 times were examined in the same manner as in Example 1. The results are shown in Table-2.

[Table] Example 3 Among the fibers produced in Example 1, the No. 1 fibers shown in Table 1.
A knitted fabric was created for item 4, and this knitted fabric was designated as A. In addition, a knitted fabric made from the No. 1 additive-free fiber shown in Table 1 was treated with a resin treatment by soaking it in a 2.0% washing solution of a resin containing an antibacterial agent, squeezing it 10.0%, and then drying and curing it. Let it be B. A knitted fabric made from additive-free fibers and without resin processing is designated as C.
When 20 people compared the textures of A and B, the results shown in Table 3 were obtained.

[Table] Example 4 A copolymer consisting of 89.8% by weight of acrylonitrile, 3.5% by weight of methyl acrylate, 6.3% by weight of acrylamide, and 0.4% by weight of sodium methallylsulfonate was prepared, and in the same manner as in Example 1, phosphoric acid was added. Fibers were prepared by adding and spinning tricresyl and thiabendazole at 2.5% and 0.5%, respectively, based on the weight of the copolymer. When a knitted fabric was made from this fiber and its antibacterial properties were examined in the same manner as in Example 1, no mold growth was observed. Example 5 Among the fibers produced in Example 1, No. 1 shown in Table 1 was used.
No. 1 without additives was added to A, No. 4 was added to B, and only thiabendazole was added to the same copolymer concentrated nitric acid solution as in Example 1 so that the amount was 0.5% by weight based on the copolymer weight. - The dispersed and spun fibers are referred to as C. The physical properties of each fiber were compared. The results are shown in Table 4.

[Table] It can be seen that the method of the present invention has almost no effect on the fiber properties compared to the method in which thiabendazole is directly added. As shown in the examples, the method of the present invention makes it possible to produce antibacterial acrylic fibers with excellent wash resistance without impairing the texture or physical properties of the fibers at low cost without loss of chemicals. Effects of the Invention The antibacterial acrylic synthetic fiber of the present invention exhibits a strong antibacterial effect against various microorganisms, and is extremely safe with low toxicity. In addition, because a small amount of plasticizer containing an antibacterial agent is dispersed in the fiber, it maintains the same fiber performance and texture as normal acrylic fiber, and the antibacterial agent on the surface of the fiber can be washed away by washing. However, plasticizer containing antibacterial agents constantly bleeds out from inside.
Since it is regenerated on the fiber surface, it will not lose its effectiveness even after repeated washing. The antibacterial acrylic synthetic fiber of the present invention can be used as it is or in combination with other fibers such as silk or polyester to have antibacterial and antifungal properties for a wide range of applications such as socks, sheets, sports clothing, and underwear. It is extremely meaningful industrially because it can be used for many purposes. In the production method of the present invention, thiabendazole is pre-dispersed in a plasticizer that is insoluble in an inorganic solvent of an acrylonitrile-based polymer, and wet spinning is performed as a spinning stock solution. This method solves the problem of poor yield of thiabendazole, which was a major drawback of organic solvent wet spinning because it does not elute.

Claims (1)

[Claims] 1. General formula for 100 parts by weight of acrylonitrile polymer, A plasticizer insoluble in an inorganic solvent in which 0.05 to 3 parts by weight of thiabendazole is dispersed.
An antibacterial fiber with good texture, characterized in that 0.05 to 20 parts by weight of the acrylonitrile polymer is dispersed in the acrylonitrile polymer. 2 General formula for 100 parts by weight of acrylonitrile polymer, 0.05 to 3 parts by weight of thiabendazole represented by is dispersed in a plasticizer insoluble in an inorganic solvent, and then 0.05 to 20 parts by weight of the plasticizer insoluble in the inorganic solvent is dissolved in advance in the inorganic solvent solution. A method for producing antibacterial fibers with good texture, which comprises adding and dispersing acrylonitrile-based polymers to prepare a spinning stock solution, and spinning the fibers by a conventional method.