JP2000314083A - Antimicrobial acrylonitrile-based fiber and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial acrylonitrile-based fiber excellent in antimicrobial property and free from the loss of the effect, discoloring and coloring in a processing step by including a polyphenol and further a specific quaternary ammonium salt into an anionic dye-dyeable acrylonitrile-based fiber. SOLUTION: An anion dye-dyeable acrylonitrile-based fiber is brought into contact with a mixture of a polyphenol composed of tea catechin with a quaternary ammonium salt represented by the formula [R1, R2, (R3)2N]+ X- (R1 and R2 are each an 8-18C alkyl; R3 is a 1-5C alkyl; X- is a halogen ion, an organic acid anion or an oxo-acid ion) or the formula [R4-CONH-R5-N(R6, R7)-R8]+ Y- [R4 is an 8-12C alkyl or alkenyl; R5 is an 8-18C alkylene; R6 and R7 are each a 4-5C alkyl; R8 is a 1-5C (hydroxy)alkyl; Y- is a halogen ion, NO3-, CH3SO4-, C2H5SO4- or the like] and then subjected to steam relaxation treatment to provide the objective antimicrobial acrylonitrile-based fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly practical antibacterial acrylonitrile fiber containing polyphenol which can be used in a wide variety of applications, such as clothing, bedding, interior decoration and general materials, and a method for producing the same. About.

[0002]

2. Description of the Related Art In recent years, with the maturation and aging of society and the tendency for a rich and comfortable living environment, the maintenance of health,
There is a growing demand for enhancement, and there is a demand for cleaner and more comfortable clothing, bedding, interior products or living materials. One of the methods is to prevent the generation of microorganisms that have an adverse effect on our living environment, suppress their growth and reproduction,
In order to maintain a sanitary and clean living environment, various antibacterial fibers are being developed.

[0003] Various antibacterial agents are used in antibacterial fibers to meet such demands, and there are various methods for treating antibacterial agents on textile products. For example, as an antibacterial agent,
A technique using an inorganic metal material represented by a silver-zeolite system (JP-A-5-272008), a method of adding a copper compound or a metal fine powder such as copper or zinc to a fiber (JP-A-55-115440). JP-A-3-25961), a method using a halodiallyl urea compound such as trichlorocarbanilide (JP-A-2-259169), and a method using a fatty acid ester compound as another compound (JP-A-63-61).
No. 73) is known.

[0004] However, the composite fiber of silver and copper compounds has a problem that the silver and copper compounds are denatured by the bleaching treatment and the antibacterial properties are lost.

[0005] Against this background, natural antibacterial agents have recently attracted attention. For example, hinokitiol extracted from cypress or cypress is said to have antibacterial, antifungal and insect repellent functions, and it is known that hinokitiol is attached to fibers to impart antibacterial properties. There are problems such as the generation of a smell of water and lack of washing resistance.

Further, a method of impregnating a fiber with a tea extract containing tea leaf tannin as a main component together with a synthetic resin binder and heating to impart washing durability (Japanese Patent Laid-Open No. Hei 8-296).
No. 173) is known, but there is a problem that antibacterial properties are reduced because the antibacterial agent is masked by using a synthetic resin binder.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art, and has an object to be effective against many bacteria required for antibacterial fibers. An object of the present invention is to provide an antibacterial acrylonitrile-based fiber which is free from lapse, discoloration, and coloring due to light, heat, processing agent, and the like in a fiber processing step, and a method for producing the same.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present invention has been completed. That is, an object of the present invention is to provide an antibacterial acrylonitrile-based fiber in which the anionic dye-dyeable acrylonitrile-based fiber contains polyphenol, or the aniline dyeable acrylonitrile-based fiber further comprises a quaternary ammonium salt. Can be achieved by an antibacterial acrylonitrile-based fiber characterized by containing

The polyphenol is a tea catechin, and the quaternary ammonium salt is represented by the general formula [1]:
Alternatively, the antibacterial acrylonitrile-based fiber [2] can achieve better results.

[0010]

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[0011]

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As a method for obtaining such an antibacterial acrylonitrile-based fiber, a fiber which has undergone a primary densification step in the process of producing an anionic dye-dyeable acrylonitrile-based fiber is treated with polyphenol or polyphenol and the general formula [1] or [ [2] A method for producing an antibacterial acrylonitrile fiber, comprising contacting a mixture of quaternary ammonium salts represented by the formula [2], followed by steam relaxation heat treatment.

Further, a quaternary ammonium salt represented by the general formula [1] or [2] is brought into contact with the fiber which has undergone the primary densification step in the production process of the acrylonitrile fiber dyeable with an anionic dye, There is also a method for producing an antibacterial acrylonitrile-based fiber, which is characterized by contacting with polyphenol after a relaxation heat treatment.

Further, the acrylonitrile-based fiber product dyeable with an anionic dye may be added to polyphenol or polyphenol.
A quaternary ammonium salt represented by the general formula [1] or [2], which is treated at a temperature of 90 ° C. or more by a dipping method or a pad steaming method. Laws can also be adopted.

Furthermore, tea catechin is recommended as polyphenol in such a production method.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the antibacterial acrylonitrile-based fiber having the specific performance as described above, the acrylonitrile-based fiber is not limited as long as it is formed by a so-called anionic dye-dyeable acrylonitrile-based copolymer obtained by copolymerizing an amino group-containing monomer. However, it is preferably at least 60% by weight, more preferably 80% by weight.
% By weight of acrylonitrile and 0.5 to 10% by weight of an amino group-containing monomer and, if necessary, vinyl esters such as vinyl acetate; vinyl halides such as vinyl chloride, vinyl bromide and vinylidene chloride; Vinylidenes;
(Meth) such as methyl acrylate and methyl methacrylate
It is desirable to use acrylonitrile-based fibers formed from acrylonitrile-based copolymers of acrylic acid alkyl esters; acrylamide, styrene, and the like.

The amino group-containing monomer which is related to the aforementioned “anion dye dyeability” is not particularly limited.
For example, the use of at least one of the monomers represented by the general formulas [3] and [4] gives good results in the present invention.

[0018]

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[0019]

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In the present invention, the polyphenol contained in the fiber is a compound having a plurality of phenol skeletons having a plurality of hydroxyl groups such as tannic acid, tannin, catechin, gallocatechin, etc., and having a molecular weight of 200 to 10,000. Degree of polyphenol is used, and especially, a molecular weight of 200 to
About 2,000 polyphenols are preferably used. If the molecular weight is too large, there will be a problem in solubility and it will be difficult to incorporate it into the fiber. If it is too small, the washing durability will decrease. Such polyphenols are contained in coffee (chlorogenic acid), onion (quercetin), purple yam (anthocyanin), beans (isoflavones), green tea (catechins), etc., and have a polyphenol component. A crudely extracted, isolated and purified, or a mixture thereof is suitably used.

Among them, in the present invention, polyphenol
Preferably, the rutile is derived from tea catechin. Tea catechin is a component contained in green tea (sencha, deep steamed tea, kabuse tea, gyokuro, bancha, etc.), semi-fermented tea (u-long tea, etc.), fermented tea (black tea), etc., and the main component is (+ ) -Catechin, (-)-epicatechin, (-)-epicatechin gallate, (+)-gallocatechin, (-)-epigallocatechin, (-)-epigallocatechin gallate are known. . These do not need to be separated into individual components, but rather a preparation containing a rich mixture of tea catechins (particularly 2).
0% by weight or more, preferably 25% by weight or more) can be suitably used as it is. Commercially available tea catechins include 30% by weight, 60% by weight, and 80% by weight products. For example, tea teakin (trade name) manufactured by Makise Sangyo Co., Ltd.
Corresponds to this. Needless to say, it is also possible to use an extract obtained by extracting tea leaves using water or alcohol as an extraction solvent.

The amount of the agent to be applied to the acrylonitrile fiber is 0.05 to 10.0 as polyphenol.
% By weight, preferably 0.05 to 5.0% by weight.
If the amount is less than the above range, the antibacterial property of the fiber is insufficient depending on the application, and if it exceeds the value, the cost is high for the antibacterial property, which is industrially disadvantageous.

The antimicrobial acrylonitrile fiber of the present invention must contain a polyphenol, but when a quaternary ammonium salt is also contained, the washing resistance of the polyphenol, the flexibility of the fiber, and the like are obtained. Extremely effective. Such a quaternary ammonium salt is represented by the general formula [1] or [2]. Examples of the general formula [1] include didecyldimethylammonium chloride, dihydroxyethyldecylethylammonium chloride, N-hydroxyethyl N, N-dimethyl N-stearylamidoethylammonium ethylsulfonate, didecyldimethylammonium adipate
And didecyldimethylammonium gluconate.

Examples of the general formula [2] include stearyl amide propyl dimethyl hydroxyethyl ammonium nitrate, cetyl amide propyl dimethyl hydroxyethyl ammonium nitrate, and stearyl amide・ Propyl dimethyl hydroxyethyl ammonium chloride, cetyl amide propyl dimethyl dimethyl hydroxyethyl ammonium chloride, stearyl amide propyl dimethyl dimethyl hydroxyethyl ammonium bromide,
Stearyl amide ethyl diethyl diethyl hydroxyethyl ammonium acetate, stearyl amide
Ethyl diethyl hydroxyethyl ammonium phosphate, stearyl amide propyl dimethyl ethyl ammonium ethyl sulfate, cetyl
Amido-propyl-dimethyl-ethyl-ammonium-ethyl sulfate, stearyl-amido-propyl-diethyl-methyl-ammonium-methyl sulfate, cetyl-amido-propyl-diethyl-methyl-ammonium-methyl sulfate, stearyl Amido propyl trimethyl ammonium methyl sulfate, cetyl amide ethyl diethyl methyl ammonium methyl sulfate, stearyl amide ethyl
Trimethyl ammonium methyl sulfate and the like can be mentioned. The amount of the drug adsorbed on the acrylonitrile-based fiber (given amount) is 0.2 to 3.0% omf, preferably 0.7 to 2.0% omf, and is one of the above-mentioned drugs. In some cases, several drugs are mixed.

Next, a method for producing the antibacterial acrylonitrile fiber of the present invention will be described. There are roughly three production methods, the first of which is to use polyphenol or polyphenol and a general formula [1] or [ 2] is to contact a mixture of quaternary ammonium salts represented by the formula (1), followed by a steam relaxation heat treatment. 2] 4
After contacting a quaternary ammonium salt, followed by a steam relaxation heat treatment, and then contacting with polyphenol.
Third, an anionic dye-dyeable acrylonitrile-based fiber product is treated with a polyphenol or a mixture of polyphenol and a quaternary ammonium salt represented by the general formula [1] or [2] by a dipping method or a pad steam method. This is a method of treating at a temperature of 90 ° C. or more.

As will be understood from the above, the first and second methods carry out the treatment after the step called the primary densification step in the production steps of the anionic dye-dyeable acrylonitrile fiber, The third method is to treat what has passed through to the end of the manufacturing process, that is, what is called raw cotton or a processed fiber product. The term “finish of the manufacturing process” as used herein does not necessarily mean “first densification”
It is not necessary to go through all the heat treatments for relaxation.
Subsequent densification is omitted, and a final product obtained by performing a steam relaxation heat treatment is also included. In addition, the treatment may be performed only with polyphenol, or a combination treatment of polyphenol and a quaternary ammonium salt may be performed. In the case of the combined treatment of the drugs, a mixture of both drugs may be applied at the same time literally, or if the treatment is performed individually, the quaternary ammonium salt is first used, and then the polyphenol is used.

The term “after the primary densification step” in the production steps of the anionic dye-dyeable acrylonitrile fiber means after the dry densification step performed after spinning, drawing and washing in wet spinning. In the primary densification step, a certain amount of water (20 to 100% by weight relative to dry fiber) derived from voids in the fiber remains in the drawn tow or filament. It refers to the step of crushing the holes and densifying the fibers. For this purpose, a tunnel dryer or a drum dryer is used to gradually remove water under a high-temperature humidity control condition, or a roller dryer is used to rapidly crush under high-temperature dry heat and a certain tension condition. There are methods. When the polyphenol and / or quaternary ammonium salt treatment is performed after spinning and prior to the primary densification step, the fiber structure still has the innumerable holes described above and contains water, so that There is a problem that it is hard to be fixed inside the fiber and falls off in each step up to drying and densification, causing process contamination and abnormal drainage.

Further, if the chemical treatment is carried out immediately before the primary densification step, water in the fiber is replaced with the chemical, so that it is difficult to apply the chemical and the concentration of the chemical must be increased. .

The means for contacting the tow or filament after the primary densification step in the acrylonitrile fiber production process of the present invention with the polyphenol and / or quaternary ammonium salt of the present invention is not limited, and the dip → nip, spray, etc. Any method may be used. An example of a prescription using a crimper-preheating tank or the like is as follows. That is,
A target amount for adsorbing the specific agent of the present invention to the tow or filament is added to the treatment tank solution, and then the agent is targeted to the tow or filament by squeezing it to a constant value using a crimper or the like. Amount is given (adsorbed), and then a steam relaxation heat treatment is performed using a key or the like to complete the adsorption.

The steam relaxation heat treatment described in the present invention means that the tow of the present invention is relaxed in the steam using a car or an autoclave. Also, the steam relaxation may be continuously performed. The steam is not limited, such as saturated steam or superheated steam. However, it is desirable to perform the treatment at 105 ° C. to 140 ° C. in saturated steam. The degree of relaxation is preferably 5 to 30%.

The acrylonitrile fiber product dyeable with an anionic dye according to the present invention may be a fiber product which has undergone the above-described primary densification step and steam relaxation heat treatment, or has been subjected to only the relaxation heat treatment by skipping the primary densification step. The material includes raw cotton (tow, loose hair, etc.), yarn (skein, cheese, etc.), knitted fabric, blanket / bore, non-woven fabric, etc., and the form is not limited.

Further, the treatment by the dipping method in the present invention means that a fiber product targeted by the present invention is prepared by mixing a predetermined amount of polyphenol or polyphenol with a quaternary compound represented by the general formula [1] or [2]. Refers to immersing in a treatment bath containing a mixture of ammonium salts and treating at a predetermined temperature,
Preferably, a method of carrying out the method in the same manner as ordinary dyeing by using an Over-Meier dyeing machine or the like is used.
An example of a prescription using an Over-Meier dyeing machine is as follows. That is, raw cotton (tow, rose hair) and the like are packed in a carrier in the same manner as in the case of ordinary dyeing, and a target amount for adsorbing the specific agent of the present invention to the raw cotton and the like is added to a tank solution. The adsorption is completed by raising the temperature to 90 ° C., or raising the temperature to boil or, if necessary, high-temperature and high-pressure.

The treatment by the pad steam method means that the textile product of the present invention is impregnated with a treatment solution containing a predetermined amount of a chemical, then squeezed with a mangle or centrifugally dehydrated, and further sprayed. Means to apply a predetermined amount of a drug and then to perform a steam treatment. For example, impregnated with a target amount for adsorbing the specific agent of the present invention to a sheet, a blanket, a bore or the like of a sheet, a blanket, or a bore made of the anionic dye-dyeable acrylonitrile-based fiber product of the present invention alone or a blend of the fibers. Apply by mangle squeezing (pickup amount), and then perform steaming at a temperature of 90 ° C. or more to complete the adsorption.

The antimicrobial acrylonitrile fiber of the present invention can be used in various fields where antimicrobial properties are desired. Specifically, for example, undergarments, underwear, lingerie, pajamas, baby products, girdle, brassiere, socks, tights, leotards, trunks, and other general clothing items, setters,
Trainers, souvenirs, sportswear, scarves, handkerchiefs, mufflers, artificial fur, baby products, etc., garments, futons, pillows, cushions, stuffed animals, etc. Bedclothes such as sheets, blankets, sweat pads, etc., carpets, mats, stuffed animals, masks, incontinence shorts, wet tissues and other sanitary materials, car sheets, interior goods such as interiors, toilet covers , Toilet mats, toilet articles such as pet toilets, gas treatment filters, etc., insoles, slippers, gloves, towels, rags, rubber glove linings, boots linings, deodorants, supporters, interlining And nonwoven fabrics.

The antibacterial acrylonitrile fiber of the present invention can be used in the above-mentioned fields by using the antibacterial fiber alone or in combination with various other fibers.
As other fibers to be used in combination, publicly-used natural fibers, organic fibers, semi-synthetic fibers, and synthetic fibers are used. In addition, inorganic fibers, glass fibers, and the like may be used depending on applications. The materials that can be used together are not limited to fibers, but films and laminates.
Non-fibrous materials such as plastics and rubbers can be used, for example, by embedding or embedding in a film to form a structure. Particularly preferred other fibers are wool, cotton,
Natural fibers such as silk and hemp, synthetic fibers such as vinylon, polyester, polyamide, and acrylic fibers or viscos;
Acetate fibers, fibrous fibers and the like.

[0036]

The antibacterial acrylonitrile fiber according to the present invention is:
For anionic dyeable acrylonitrile fiber,
Without using a fixing agent such as a synthetic resin, a polyphenol having a high antibacterial property is brought into contact after the primary densification step in the production process of the fiber and then subjected to a steam relaxation heat treatment, or a dipping method or a pad steam. By contacting the acrylonitrile fiber at a temperature of 90 ° C. or higher which is higher than the secondary rearrangement temperature of the acrylonitrile fiber, the fiber is fixed (bonded to the amino group in the fiber) or retained (loose bond to the amino group in the fiber or amino). Present around the group). Also,
When the quaternary ammonium salt of the present invention is used in combination, it is introduced from the comonomer used in the production of the raw material copolymer for the acrylonitrile fiber, or from a polymerization catalyst such as an acid sulfite as a reducing agent for a redox catalyst. It is considered that the polyphenol is easily penetrated into amino groups in the fiber by its affinity with the sulfonic acid. And because it penetrates and diffuses into the interior of the fiber, unlike general adhesion or fixation to the fiber surface, there is less falling off due to repeated washing, there is no decrease in antibacterial performance, and also in the processing process to various products It is speculated that lapse, discoloration and coloring due to light, heat, processing chemicals, etc. are reduced.

[0037]

The present invention will be described in detail with reference to the following examples, which are illustrative only and do not limit the scope of the present invention. Parts and percentages in the examples are on a weight basis unless otherwise specified. The antimicrobial performance, washing conditions, and polypheno-
The measurement was performed by the following method.

(1) Antibacterial performance Test strain: Staphylococcus aureus Test method: Based on the unified test method determined by the Evaluation Committee for New Functions of Textile Products, pouring a bouillon suspension of the test bacteria into a test cloth, The number of viable cells after culturing at 37 ° C. for 18 hours in a closed container was measured, and the difference between the number of cells B of the standard cloth and the number C of cells of the sample cloth relative to the number A of the inoculated cells was determined as follows. Bacterial activity value. Generally, a bacteriostatic activity value of 2.2 or more is considered to have antibacterial activity. Increase / decrease value difference = (logB−logA) − (logC−log
gA)

(2) Washing conditions According to JIS-L-0217 method 103 (for household washing machines), washing is repeated using a standard detergent of JAFET (manufactured by the Evaluation Council for New Functions of Textile Products). (3) Polyphenol measurement method Ethyl gallate was dissolved in pure water, and
Make a solution of 0.25 mg / 100 ml. 25 ml
In a volumetric flask, take 5 ml each of the above-prepared ethyl gallate solution, and then dissolve 100 mg of ferrous sulfate heptahydrate 100 mg and rossel salt 500 mg in 100 ml.
And make up to volume with 1/15 M pH 7.5 phosphate buffer. The absorbance of the various concentrations of ethyl gallate is measured at a wavelength of 540 nm using water as a control, and a calibration curve is prepared. Here, 1 mg of ethyl gallate corresponds to 1.5 mg of polyphenol.

The hot water retention is 200 g of 3 g of sample fiber.
After hot water treatment of boiling for 30 minutes in pure water,
Using the hot water treatment liquid as the test liquid, the amount of polyphenols dropped off by the above-described measurement method was quantified, and the amount retained was expressed as a ratio (%) to the amount before the hot water treatment by calculation. The same applies to the washing resistance. After washing the sample fiber five times under the above-mentioned washing conditions, the amount of polyphenol retained in the fiber is quantified and expressed as a ratio (%) to the amount before washing treatment. .

Examples 1 to 6 Anionic dyeable acrylonitrile based on 85.6% of acrylonitrile, 11.2% of vinyl acetate and 3.2% of N, N-dimethylaminoethyl methacrylate according to a conventional method. The polymer was dissolved in an aqueous solution of rodan soda having a concentration of 45% to prepare a spinning stock solution having a polymer concentration of 12%. The stock solution was extruded into a 10% aqueous solution of rodan soda at -3 ° C, washed with water, stretched, and dried in a high-humidity condition at a humidity of 70% RH and a temperature of 120 ° C using a tunnel drier to obtain a primary densified tow. (Raw fiber A) was prepared.

The tow was used as a tea catechin-derived polyphenol preparation, tea techin MKS- manufactured by Makise Sangyo Co., Ltd.
10 (60% by weight of polyphenol) and an aqueous solution of a quaternary ammonium salt shown in Table 1 and dehydrated to a moisture content of 25% omf.
× 9 minutes for a steam relaxation heat treatment. The antimicrobial acrylonitrile fiber samples of Examples 1 to 6 were obtained by oiling, drying and varicut in a conventional manner. Amount of polyphenol adhering to fiber (% omf) and amount of quaternary ammonium salt applied (% o
mf) can be obtained by calculation from the respective concentrations in the immersion liquid, the concentration of the residual solution, and the water content (% omf) of the tow to be treated.

[0043]

[Table 1]

COMPARATIVE EXAMPLE 1 A primary densified tow (88.8% acrylonitrile and 11.2% vinyl acetate) was prepared according to Examples 1 to 6 using an acrylonitrile-based polymer (the polymer is not dyeable by an anionic dye). Raw fiber B) was prepared. This tow is used for tea tekin MKS-10 (polypheno-manufactured by Makise Sangyo Co., Ltd.).
Immersed in a 1.2% by weight aqueous solution of water (60% by weight) and dehydrated to a water content of 25% omf.
It was subjected to a steam relaxation heat treatment for 9 minutes. A sample of Comparative Example 1 was obtained by oiling, drying and varicut in a conventional manner.

Various characteristic values of the samples of Examples 1 to 6 and Comparative Example 1 were evaluated, and the results are shown in Table 1. As can be seen from Table 1, using an anionic dye-dyeable fiber,
Further, it is apparent that the use of a quaternary ammonium salt is excellent in hot water retention, washing resistance, and antimicrobial durability. The fiber of Comparative Example 1, which is not dyeable by an anionic dye, is completely washable and has poor antibacterial properties.

Examples 7 to 9 Using a crimper preheating tank, 1.5% omf of each of the quaternary ammonium salts shown in Table 2 was applied to the raw fiber A of the primary densified tow at 80 ° C. for 9 minutes at 120 ° C. Steam relax heat treatment. Next, tea tekin MK manufactured by Makise Sangyo Co., Ltd.
Immersion in a 1.7% aqueous solution of S-10 at 80 ° C.
The antibacterial acrylonitrile fibers of Examples 7 to 9 were obtained by dehydration to 7%, followed by drying and cutting. The hot water retention, washing resistance and antibacterial properties were determined in the same manner as described above. These results are shown in Table 2.

[0047]

[Table 2]

Comparative Example 2 A raw material fiber A of primary densified tow was used at 80 ° C. using a crimper preheating tank at 80 ° C. for tea teak MKS- manufactured by Makise Sangyo Co., Ltd.
10 in a 1.7% aqueous solution at 80 ° C.
And subjected to steam relaxation heat treatment at 120 ° C. for 9 minutes. Then, stearyl amide propyl dimethyl hydroxyethyl ammonium nitrate was applied at 80 ° C. at 1.5% omf, dried and cut to obtain Comparative Example 2. Hot water retention by the same method as described above,
Washing resistance and antibacterial properties were required. These results are shown in Table 2. The treatment of the quaternary ammonium salt and polyphenol in Comparative Example 2 was performed in the reverse order to that in Example 7 and the like, but the entries in the table were the same as those in Example 7 and the like.

As can be seen from Table 2, the fibers which have undergone the primary densification step of dyeing anionic dyes are first contacted with a quaternary ammonium salt, then subjected to steam relaxation heat treatment, and then contacted with polyphenol to retain hot water. It is clear that the rate, washing resistance and antibacterial properties are excellent. It is also apparent that, even if the order of the treatment is reversed, even for an anionic dye-dyeable fiber, the adhesion amount of polyphenol is reduced and various properties are not excellent.

Examples 10 to 16 Using a polymer having the same composition as in Examples 1 to 6, spinning, washing, drawing, primary densification, steam relaxation heat treatment, oil agent, drying, and varicut were performed in the same manner. Acrylonitrile-based fibrous raw cotton (raw material fiber C) was obtained. To 100 g of the raw material fiber C, an amount of 0.3% omf is obtained when the whole amount of tea techin MKS-10 manufactured by Makise Sangyo Co., Ltd. , 1.0% omf, and 0,0% if stearyl amide propyl dimethyl dimethyl hydroxyethyl ammonium nitrate is completely adhered.
Immerse in a bath containing 0.2, 0.4, 0.6 and 0.8% omf at a bath ratio of 1:30 or 1:10,
The temperature was raised to 98 ° C. over 20 minutes, and an adsorption treatment was performed at 98 ° C. × 30 minutes. This is the immersion method. The polyphenol concentration in the remaining bath solution was measured to determine the amount of fibers attached. Further, the hot water retention was determined by the same method as described above.
Since the above-mentioned ammonium nitrate has a strong affinity with the raw material fiber C, it is provided in an intended amount.
Table 3 shows the results.

[0051]

[Table 3]

Comparative Example 3 Using a polymer having the same composition as in Comparative Example 1,
Acrylonitrile fiber (raw fiber D) was obtained in the same manner as in Example 6. The raw material fiber D was subjected to an adsorption treatment in the same manner as in Example 15, and the adhesion amount of polyphenol fiber, the retention rate of hot water, and other various properties were determined.

As is clear from Table 3, it is clear that the use of fibers dyeable with an anionic dye and the use of quaternary ammonium salts provide excellent hot water retention and other properties. On the other hand, it can be seen that Comparative Example 3 using a fiber which is not dyeable by an anionic dye is extremely loose such that the adhesion of polyphenol does not withstand hot water. Instead of immersing in a bath at a bath ratio of 1:30, 0.35% by weight of MKS-10 and stearyl amide propyl dimethyl dimethyl hydroxyethyl quaternary ammonium salt were used.
20% aqueous solution containing 1.2% ammonium nitrate
Dip for 10 seconds at ℃ ℃ 50% om with mangle
f, and the fiber treated in the same manner as in Example 13 except that steam treatment was performed at 100 ° C. for 40 minutes, the quaternary ammonium salt was 0.5% omf, and the polyphenol adhesion amount was 0.10% o.
mf, the hot water retention rate was 73%, the washing resistance was 80%, and the bacteriostatic activity value was 4.7 after 5 washes.

Example 17 15% of antibacterial acrylonitrile fiber of Example 16 / K691-5 × V7455 manufactured by Nippon Exlan Industries, Ltd.
% / C881-3 × V64 manufactured by Nippon Exlan Industrial Co., Ltd.
A 1 / 4.5 count semi-worsted yarn consisting of a 30% blend was prepared. The antibacterial property of the worsted thread is expressed as a bacteriostatic activity value after washing 5 times.
8. Light resistance after 40 hours of carbon arc in coloration is 4th grade, fastness of 8 weeks exposure test of fluorescent lamp is 5th grade, 80 ° C 4
00 hour heat resistance 5th grade, 120 ° C 8 hour heat resistance 4
Both grades were excellent performance.

[0055]

Industrial Applicability With the advent of the present invention, it is possible to provide an antibacterial acrylonitrile-based fiber free from aging, discoloration, and coloring due to light, heat, processing chemicals, etc. in the processing step while maintaining excellent antibacterial properties, and to manufacture the fiber industrially. It is a remarkable effect of the present invention that a method for producing the present invention can be provided in an advantageous manner. The fibers of the present invention having such excellent advantages can be processed into yarns, knitted fabrics, blankets, bores, non-woven fabrics, etc., for comfortable clothing, bedding, interior products, living materials, industrial materials, and clothing. Widely used in application fields such as fiber materials.

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Claims (8)

[Claims] 1. An antibacterial acrylonitrile fiber in which the acrylonitrile fiber dyeable with an anionic dye contains polyphenol. 2. The antibacterial acrylonitrile-based fiber according to claim 1, wherein the acrylonitrile-based fiber dyeable with an anionic dye further contains a quaternary ammonium salt. 3. The antibacterial acrylonitrile fiber according to claim 1, wherein the polyphenol is tea catechin. 4. The antibacterial acrylonitrile-based fiber according to claim 2, wherein the quaternary ammonium salt has the general formula [1] or [2]. Embedded image Embedded image 5. A quaternary ammonium salt represented by the general formula [1] or [2], wherein a fiber which has undergone a primary densification step in the process of producing an anionic dye-dyeable acrylonitrile fiber is polyphenol or polyphenol and a general formula [1] or [2]. A method for producing an antibacterial acrylonitrile-based fiber, which comprises bringing a mixture of the above into contact and then subjecting the mixture to a steam relaxation heat treatment. 6. A quaternary ammonium salt represented by the general formula [1] or [2] is brought into contact with a fiber which has undergone a primary densification step in a process for producing an anionic dye-dyeable acrylonitrile fiber, and then a steam is prepared. A method for producing an antibacterial acrylonitrile-based fiber, wherein the fiber is brought into contact with polyphenol after a relaxation heat treatment. 7. An acrylonitrile fiber product dyeable with an anionic dye is immersed in a phenol or a mixture of polyphenol and a quaternary ammonium salt represented by the general formula [1] or [2], or immersed in a pat-steam method. Gives 90
A method for producing an antibacterial acrylonitrile-based fiber, characterized in that the fiber is treated at a temperature of at least ℃. 8. The method for producing an antibacterial acrylonitrile fiber according to claim 5, wherein the polyphenol is tea catechin.