JP2000314035A - Antimicrobial textile product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial textile product capable of avoiding deterioration of antimicrobial and deodorizing properties due to various treatments received by the textile product under use environments, excellent in degree of whiteness and color developing clarity and useful for clothes, etc., by including acrylic fibers containing a prescribed amount of a nonelutable antimicrobial agent in a specific mixing ratio. SOLUTION: This antimicrobial textile product comprises acrylic fibers containing 0.05-2.0 wt.% of a nonelutable antimocrobial agent such as a natural antimicrobial agent, e.g. chitosan which is basic polysaccharides prepared by removing calcium carbonate and proteins from a chitinous material forming the outer skeleton of crustaceans such as a crab or a lobster or a shrimp, heating the resultant chitin with a concentrated alkali and deacetylating the chitin in 20-60 wt.% mixing ratio. Furthermore, the bacteriostatic activity value of the antimicrobial textile product is >=2.2. A method for including an acidic aqueous solution of chitosan in a washed yarn prepared by washing a solvent contained in a coagulated yarn in a wet production process for the acrylic fibers, then neutralizing the resultant yarn and washing the chitosan is preferred as the method for including the nonelutable antimicrobial agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial fiber product which can be used for clothing, jewelry, interior decoration, material and the like without adversely affecting the human body and the environment.

[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 germs 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. Various antibacterial agents are used in such antibacterial fibers,
There are various methods of complex treatment of an antibacterial agent to textiles. For example, as an antibacterial agent, a technique using an inorganic metal material represented by silver-zeolite (JP-A-5-272008), a method of adding a copper compound or a metal fine powder such as copper or zinc to fibers. (JP-A-55-115440) A method using a derivative of a quaternary ammonium salt (JP-A-59-130371) and a method using a halodiallyl urea compound such as trichlorocarbanilide (Japanese Patent Laid-Open No.
JP-A-259169), and thiabendazole compounds (JP-A-61-616) as other compounds.
A method using a phenolic compound (JP-A-60-252713) and a fatty acid ester-based compound (JP-A-6-252713).
No. 3-6173).

[0003] 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. In addition, even for fibers that have been compounded with some organic compounds, the antimicrobial agent loses its antibacterial properties due to elution and falling off of the antibacterial agent due to post-processing such as dyeing and softening, and washing. There is a problem that the possibility of producing harmful substances cannot be completely ruled out under the above conditions. Therefore, when the ratio of these antibacterial fibers is high in the final fiber product, the problems of deactivation of antibacterial properties due to the above-mentioned exposure, dissolution and dropout due to post-processing and washing, and environmental load are more obvious. Will be transformed.

[0004] Against this background, attention has been paid to a function-imparting agent that is a natural antibacterial agent. For example, hinokitiol extracted from Aomori Hiba or Taiwan Hinoki has antibacterial, antifungal and insect repellent functions, and chitosan, which is a deacetylated product of natural polysaccharide chitin obtained from crustaceans, is antibacterial and deodorant, and proliferates against MRSA. It is said to have an inhibitory effect, high moisturizing property, 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 and used for clothing. For this reason, highly safe acrylic fiber composited with chitosan has been proposed as an antibacterial fiber (Japanese Patent Application Laid-Open No. 9-273081, 10).
-140418).

However, the fiber obtained by compounding chitosan has a hue inherent to chitosan, so that the resulting fiber has a yellowish tinge, which tends to reduce whiteness and poor color clarity. Therefore, when the mixture ratio in the final product is high, the commercial value is reduced due to the yellowness. Furthermore, in the final fiber product, if the antibacterial fiber content is high,
At present, the production cost is increased and the mixing ratio of the fiber of the mixing partner is reduced, so that the range of options for imparting the function in fiber composite is reduced.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems and is effective against many bacteria required for antibacterial fibers. Avoids deterioration of antibacterial and deodorant properties of textile products such as washing and ironing due to various treatments received in the use environment, generates harmful substances in all processes from production to disposal without impairing whiteness and color vividness It is an object to provide a non-bacterial fiber product.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the following invention. That is, the gist of the present invention is that the non-elutable antibacterial agent is contained in 0.1.
20 to 60% by weight of acrylic fiber containing 20 to 60%
The antimicrobial fiber products contained in the mixture by weight%.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The antibacterial fiber product of the present invention is excellent in dye clarity and color development, and acrylic fibers are preferable from the viewpoint of fiber properties such as thermal characteristics. In particular, an acrylic fiber made of an acrylonitrile-based polymer containing acrylonitrile at 60% by weight or more is preferable.

In the antibacterial fiber product of the present invention, an acrylic fiber containing 0.05 to 2.0% by weight of a non-eluting antibacterial agent is used. The non-elutable antibacterial agent is not limited to inorganic and organic compounds as long as it is hardly soluble in water, but a natural antibacterial agent that does not generate harmful substances in all processes from production to disposal is preferable. . As natural antibacterial agents, Aomori Hiba oil,
Examples include hinokitiol, mugwort extract aloe, dokudami, licorice and the like, and chitosan is particularly preferred for the following reasons.

[0010] Chitosan is a basic polysaccharide obtained by removing calcium carbonate and protein from chitin forming the exoskeleton of crustaceans such as crabs and shrimps, and deacetylating chitin obtained by heating with a concentrated alkali. . Since chitosan is hardly soluble in water, the antibacterial agent is less eluted in post-processing such as dyeing and softening and washing, and has excellent antibacterial retention. Also,
In post-processing and washing, chitosan is less likely to fall off, which is also preferable as an antibacterial agent. The reason why the shedding is small is presumed that chitosan has a high molecular weight and therefore has excellent fixation to fibers.

The content of the non-eluting antibacterial agent for obtaining the expected antibacterial effect is 0.05 to 2.0% by weight based on the fiber. If the amount is less than 0.05% by weight, the effect is insufficient. If the amount is more than 2.0% by weight, no further increase in the effect can be expected. Is not preferred because it becomes defective.

The non-elutable antibacterial agent may be contained only in the surface layer of the fiber. However, in order to reduce the mechanical shedding during the post-processing step or washing, the non-elutable antibacterial agent is dispersed inside the fiber. In particular, when chitosan is used, it is preferable that chitosan be dispersed and contained in the form of particles even inside the fiber.

It is necessary that the mixing ratio of the acrylic fiber containing the non-elutable antibacterial agent in the fiber product of the present invention is 20 to 60% by weight. If the mixing ratio is less than 20% by weight, the antibacterial properties are rapidly insufficient, and if it exceeds 60% by weight, the antibacterial properties reach saturation and the effect cannot be expected to increase. When the acrylic fiber containing chitosan is used, if it exceeds 60% by weight, the antibacterial property tends to be slightly reduced, and the hue inherent in chitosan becomes large, resulting in poor whiteness.

The mechanism by which the antibacterial property rapidly deteriorates when the mixing ratio is less than 20% by weight is unclear at present, but the present inventors have determined that the mixing ratio of the antibacterial fiber in the fiber product is determined by D.S. STAU
It is speculated that this is related to the effect of the permeation theory described by FFER et al. (Basic of permeation theory p23 Stouffer published by Yoshikawa Shoten). In other words, for the expression of antibacterial properties, contact between the antibacterial agent and the cells can be mentioned. However, since the antibacterial agent of the present invention is a non-eluting type, the cells and antibacterial fibers are directly Contact is required. If the mixing ratio of the antibacterial fiber is small, the area occupied by the antibacterial fiber becomes discontinuous, and the region where the growth of bacterial cells can be suppressed is cut off. As a result, it is estimated that the antibacterial activity sharply decreases at a certain fiber mixing ratio. Is done.

In the case of using an acrylic fiber containing chitosan, if the mixing ratio exceeds 60% by weight, the mechanism of slightly reducing the antibacterial property is not inferred, but chitosan as an antibacterial agent is a polysaccharide. Therefore, there is a possibility that the cells may take chitosan as a nutrient source. For this reason, it is presumed that the antibacterial action and the proliferative action are antagonized with an increase in the fiber mixture ratio in which the chitosan is compounded, and as a result, the antibacterial property is slightly reduced.

As for the antibacterial performance, a bacteriostatic activity value of 2.2 or more in a measuring method described later is preferably used as an antibacterial fiber product.

The acrylonitrile-based polymer comprises acrylonitrile and an unsaturated monomer polymerizable therewith. As such unsaturated monomers, acrylic acid, methacrylic acid, or their alkyl esters, vinyl acetate, acrylamide, vinyl chloride, vinylidene chloride, and, depending on the purpose, sodium vinylbenzene sulfonate,
Sodium methallylsulfonate, sodium allylsulfonate,
Ionic unsaturated monomers such as sodium acrylamidomethylpropanesulfonate and sodium parasulfophenyl methallyl ether can be used.

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 can be used. A concentrated aqueous solution of an inorganic substance such as nitric acid, rodane 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.

The method for incorporating the non-elutable antibacterial agent into the acrylic fiber includes adding the non-eluting antibacterial agent to the fiber together with the process oil during the fiber production process, adding it to the spinning solution in advance, and incorporating the fiber in the washing tank. There is a way. In particular, a preferred method of incorporating the chitosan acrylic fiber is a method of immersing and passing a coagulated yarn or a wet yarn produced in a wet spinning method into a solution containing chitosan, and more specifically, a method of producing a wet acrylic fiber. A method of washing the chitosan with an aqueous chitosan aqueous solution and then neutralizing the chitosan after washing the solvent containing the solvent contained in the coagulated yarn in the step with the chitosan is used.

The method of mixing the acrylic fiber containing the non-elutable antibacterial agent at a mixing ratio of 20 to 60% by weight includes mixing at the raw cotton stage, mixing at carding in the spinning process,
Alternatively, any method such as mixing at the time of knitting or weaving may be used.

The antibacterial fiber product in the present invention includes a fiber composite such as a knitted fabric, a woven fabric, a nonwoven fabric, and a pile. 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, but ordinary acrylic fiber, cotton, rayon, wool, hemp,
Known fibers such as silk and polyester can be used.

[0022]

The present invention will be described more specifically with reference to the following examples. In Examples, “% by weight” is simply expressed as “%”.

(Reduced Viscosity of Polymer) The reduced viscosity ηred of the acrylonitrile polymer is determined by measuring the viscosity of a polymer solution obtained by dissolving the 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 bacteriostatic activity value of Staphylococcus aureus was determined by a bacterial count method (revised JIS-L1902 unified test and quantification method) determined by the Textile Sanitary Processing Council. A bacteriostatic activity value of 2.2 or more was used as a criterion for antibacterial activity. The washing method was determined by the council (JIS-L
0217, 103).

(Evaluation of Whiteness) As an evaluation of the whiteness of textile products,
The following three grades were evaluated by visual judgment. 〇: good whiteness, Δ: slightly yellowish, ×: poor whiteness (yellowish)

(Measurement of Chitosan Content) 0.2 g of the weighed sample fiber was placed in a 70% aqueous solution of zinc chloride 1
The solution was dissolved in 0 ml to obtain a solution. 2 ml of dimethylacetamide was added to this solution,
Left for hours. Further, 1 ml of Erich reagent (p-dimethylaminobenzaldehyde 1% ethanol solution) was added. Two hours later, the absorbance of the solution at a wavelength of 435 nm was measured to prepare a calibration curve. The concentration of chitosan was determined from the calibration curve and converted to the content of chitosan.

(Examples 1-4, Comparative Examples 1-4) An acrylonitrile polymer (acrylonitrile / vinyl acetate = 93/7 weight ratio) 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 stock solution 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 the stretched yarn is subsequently subjected to chitosan (Kyowa Technos Co., Ltd.). Company Flownack C) 0.5%
It was led to a bath filled with an aqueous solution of acetic acid, and was dehydrated so that the amount of water adhering to the fiber weight was 100%. Then 15
Dry densification was performed with a hot roller at 0 ° C. Further 2.5
Relaxation treatment was performed in pressurized steam of kg / cm ² to obtain an acrylic fiber (single fiber fineness: 2.2 dTex) containing 0.1% by weight of chitosan. This fiber was cut into 51 mm, and blended with a 2.2 dTex fiber length 51 mm non-chitosan-free acrylic fiber at a different mixing ratio,
After producing the 22nd spun yarn, a knitted fabric having a twill fabric was produced. Table 1 shows the evaluation results of antibacterial properties and whiteness before and after washing 10 times.

[0028]

[Table 1]

(Examples 5 and 6, Comparative Examples 5 and 6) Example 1
The same operation as described above was performed to obtain an acrylic fiber containing chitosan (single fiber fineness: 2.2 dTex).
A spun yarn of 1 / 26th count was produced at 0%. The spun yarn is constituted as a weft yarn, and the warp yarn does not contain a chitosan-containing polyester fiber filament (a fiber fineness of 165 dTe).
x / 50 filaments). Table 2 shows the evaluation results of the antibacterial properties before and after washing 10 times.

[0030]

[Table 2]

Example 7 The same operation as in Example 1 was carried out, and an acrylic fiber containing chitosan (having a single fiber fineness of 0.1 mm) was used.
1dTex). After cutting this fiber into a 3 mm length, it is mixed with the same amount of an acrylic fiber containing no chitosan (single fiber fineness: 0.1 dTex, fiber length: 3 mm), dispersed in water, formed by a circular knitting paper machine, and dried. And weigh 40g
/ M ² was obtained. This thread is placed on a reinforcing material made of a knitted polyester fiber, and the nozzles having a hole diameter of 0.15 mm are used for 15 kg / cm ² , 30 kg / cm ² , and 4 kg.
0 kg / cm ² , 60 kg / cm ² , 60 kg / cm
^The high pressure water jet treatment was performed sequentially at a pressure of ² . After the obtained sheet was dehydrated, it was subjected to shrinkage treatment in boiling water and heat set at 150 ° C. to obtain a nonwoven fabric. When the antibacterial properties before and after washing 10 times were evaluated,
The bacteriostatic activity values before washing and after washing 10 times were respectively 4.
3, 3.9.

Example 8 Except that the shape of the spinning hole was changed,
The same operation as in Example 1 was performed to obtain an acrylic fiber containing chitosan having an aspect ratio (an aspect ratio of a fiber cross section) of 10 (filament single fiber fineness: 11 dTex). After cutting this fiber to a length of 51 mm, it is mixed with the same amount of chitosan-free acrylic fiber (single fiber fineness: 7.7 dTex, fiber length: 51 mm) to produce a 100 g / m thick sliver for pile. did. This sliver is processed into sliver knitting by a sliver knitting machine, polished, and has a basis weight of 700 g / m ² and a pile length of 18 mm.
Got a high pile. When performing print dyeing using a cationic dye and evaluating the antibacterial properties, the bacteriostatic activity value is
4.2.

(Examples 9 to 10 and Comparative Examples 7 to 8) The same conditions as in Example 1 except that the content of chitosan was changed by changing the amount of water adhering to the weight of the fiber during dehydration, and the acrylic fiber ( A single fiber fineness of 2.2 dTex) was obtained. After this fiber was cut into 51 mm, an acrylic fiber containing the same amount of chitosan (single fiber fineness: 2.2 d
Tex, a fiber length of 51 mm), and a spun yarn having a count of 1/22 was prepared. This knitted fabric 5
0g, dye (Hodogaya Chemical Co., Ltd. Kachiron Blue)
0.25 g of KGLH), 1 g of acetic acid, and 0.25 g of sodium acetate were added to 1000 g of pure, heated to 100 ° C., kept at 100 ° C. for 30 minutes, washed with water, dehydrated, and dried to perform cationic dyeing. The antibacterial property before washing and 10 times after washing, and the coloring vividness of the knitted fabric after dyeing were evaluated. Table 3 shows the content of chitosan in the chitosan-containing acrylic fiber, the antibacterial properties before and after washing 10 times, and the evaluation results of the color clarity.

[0034]

[Table 3]

[0035]

The antibacterial fiber product of the present invention is effective against bacteria required for antibacterial and deodorant fiber products, and can be used in post-processing such as dyeing and bleaching of fibers, washing, ironing, etc. The antibacterial performance does not deactivate due to the heat treatment, and it is excellent in texture, whiteness, and clearness of coloring, and has an effect of not generating harmful substances in all processes from production to disposal.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Hideo Kuwaki 1-8-30 Temmabashi, Kita-ku, Osaka-shi, Osaka Prefecture F-term in Mitsubishi Rayon Co., Ltd. Osaka Branch 4L033 AA05 AB01 AC10 AC15 CA02 4L035 BB03 BB07 BB72 CC07 CC20 DD19 EE11 FF10 MB03 4L038 AA11 AB10 BA48 CA06 DA08

Claims (4)

[Claims] An antibacterial fiber product containing an acrylic fiber containing 0.05 to 2.0% by weight of a non-eluting antibacterial agent in a mixing ratio of 20 to 60% by weight. 2. The antibacterial fiber product according to claim 1, wherein the non-elutable antibacterial agent is a natural antibacterial agent. 3. The antibacterial fiber product according to claim 1, wherein the non-elutable antibacterial agent is chitosan. 4. The bacteriostatic activity value of 2.2 or more.
An antibacterial textile product as described.