JP3949773B2 - Antibacterial fiber - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antibacterial acrylic fiber that can be used for apparel, interior, materials, and the like, and a method for producing the same.
[0002]
[Prior 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 odors, and as a textile product for clothing, infants, and elderly people, and recently, consumption that strongly demands health and comfort. In response to consumer needs, it is widely distributed throughout the city as a product for general consumers.
[0003]
Various antibacterial agents are used for such antibacterial fibers, and there are various methods for complex treatment of the antibacterial agents on the fiber products. For example, as an antibacterial agent, a technique using an inorganic metal material typified 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 Patent Laid-Open No. 55-115440), a method using a derivative of a quaternary ammonium salt (Japanese Patent Laid-Open No. 59-130371), a method using a halodiallyl urea compound such as trichlorocarbanilide (Japanese Patent Laid-Open No. Hei 2- 259169), as other compounds, cyabendazole compounds (JP-A 61-616), phenolic compounds (JP 60-252713, etc.), fatty acid ester compounds Sho 63-6173, etc.) are known.
[0004]
[Problems to be solved by the invention]
However, among the above prior arts, the fiber in which silver and copper compounds are combined has a problem that when subjected to an exposure treatment, the silver and copper compounds are denatured and the antibacterial properties are lost.
[0005]
In contrast, fibers using quaternary ammonium salt derivatives are effective against many bacteria, and are preferably used for antibacterial fiber products. However, since chloride ions are usually used as the counter anion of the quaternary ammonium salt, there has been a problem that rust occurs in the spinning device, spinning device, dyeing device, knitting machine, and the like.
[0006]
This invention solves the said subject at the time of using a quaternary ammonium salt, and provides the antibacterial fiber which has the outstanding antibacterial effect without the problem of generation | occurrence | production of rust, such as spinning and a spinning apparatus.
[0007]
[Means for Solving the Problems]
The antibacterial fiber of the present invention that solves the above-mentioned problems is 0.05% by weight or more of a quaternary ammonium salt containing a cation represented by the following general formula [1] having a carboxylic acid anion as a counter anion with respect to the fiber. It is characterized by containing 5.0% by weight or less .
[R ₁ R ₂ (CH ₃ ) ₂ N] ⁺ [1]
(In the above general formula [1], R ₁ and R ₂ may be the same or different, and both are alkyl groups having 8 to 18 carbon atoms.)
[0008]
Since the antibacterial fiber of the present invention does not use chlorine ions as a counter anion of a quaternary ammonium salt, it exhibits an excellent antibacterial effect while preventing the occurrence of rust in spinning devices, spinning devices, dyeing devices, knitting machines, and the like.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The fiber in the present invention refers to fibers such as acrylic fiber, cotton, rayon, wool, hemp, silk, and polyester. Of these, acrylic fibers are preferable, and acrylonitrile-based polymers containing 50% by weight or more of acrylonitrile are particularly preferable. By setting the amount of acrylonitrile within the above range, a fiber having excellent dyeing clarity and color developability and excellent thermal properties and other physical properties can be obtained.
[0010]
The acrylonitrile-based polymer is composed of acrylonitrile and an unsaturated monomer polymerizable with the acrylonitrile. Examples of such unsaturated monomers include acrylic acid, methacrylic acid, or alkyl esters thereof, vinyl acetate, acrylamide, vinyl chloride, and depending on the purpose, vinyl benzene sulfonic acid soda, methallyl sulfonic acid soda, acrylamidomethyl. An ionic unsaturated monomer such as sodium propane sulfonate can be used.
[0011]
The antibacterial fiber of the present invention contains a quaternary ammonium salt using an organic acid anion as a counter anion. Various organic acid anions are used, and carboxylate anions are particularly preferable. That is, the organic acid represented by R— (COOH) _n (R represents an alkyl group, aryl group, etc. and derivatives thereof, and n represents 1 to 5) is preferable. Examples of such organic acids include acetic acid, lactic acid, propionic acid, butyric acid, valeric acid, stearic acid, oxalic acid, malonic acid, succinic acid, gluconic acid, glutaric acid, adipic acid, acrylic acid, maleic acid, fumaric acid, Examples include glycolic acid, benzoic acid, phthalic acid, salicylic acid, and gallic acid.
[0012]
In order to obtain sufficient antibacterial performance, the content of the quaternary ammonium salt in the present invention is preferably 0.05% by weight or more. In addition, when acrylic fiber is used, in order to prevent the quaternary ammonium salt from dropping off in the spinning process without deteriorating its excellent dyeability, the content should be 5.0% by weight or less. Is preferred.
[0013]
In the present invention, any cation part of the quaternary ammonium may be used, but a structure represented by the following general formula [1] is preferable.
[R ₁ R ₂ (CH ₃ ) ₂ N] ⁺ [1]
(In the above general formula [1], R ₁ and R ₂ may be the same or different, and both are alkyl groups having 8 to 18 carbon atoms.)
When the antibacterial fiber of the present invention is used as a fiber composite such as a spun yarn, a fabric or a nonwoven fabric, it is preferably mixed in an amount of 20% by weight or more in order to obtain antibacterial properties. The fiber to be mixed with the antibacterial fiber of the present invention may be selected according to the purpose of use, and is not particularly limited, but examples thereof include known acrylic fibers, cotton, rayon, wool, hemp, silk, polyester, and other known fibers. It is done.
[0014]
Next, the manufacturing method of the antimicrobial fiber of this invention is demonstrated.
[0015]
In the present invention, the quaternary ammonium salt is attached to the fiber together with the process oil agent during the fiber production process, {circle around (2)} added in advance to the spinning dope, and {circle around (3)} attached to the fiber in the washing tank, 4) It can be applied by a method of applying to the surface after making the fiber product. Among these, the method of making it adhere with a process oil agent in a fiber manufacturing process is desirable. This is because the fixing rate of the quaternary ammonium salt to the fiber is good. The quaternary ammonium salt may fall off in the subsequent spinning process when it is added to the spinning dope or attached in the washing tank, and when it is applied to the textile product, the quaternary ammonium salt is washed. Salt may fall off and antibacterial performance may be reduced.
[0016]
Hereinafter, the present invention will be described by taking acrylic fiber as an example. Solvent for dissolving and spinning the acrylonitrile-based polymer described above is not particularly limited as long as the polymer is dissolved at a spinnable concentration, but is not limited to organic solvents such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, nitric acid, Examples include concentrated aqueous solutions of inorganic substances such as rhodan salt soda and zinc chloride. An organic solvent such as dimethylacetamide, dimethylformamide, or dimethylsulfoxide is preferably used because it is advantageous for forming microvoids in the acrylic fiber yarn before drying and densification described later.
[0017]
In the present invention, it is preferable to add a quaternary ammonium salt to acrylic fibers at a stage called a coagulated yarn, a washed yarn, and a drawn yarn before being dried and densified. This is because it is effective in preventing the quaternary ammonium salt from dropping and the deactivation of the antibacterial performance in the use environment such as post-processing and washing. Most of the quaternary ammonium salts imparted to the acrylic fibers of the present invention are dropped and deactivated by being taken into microvoids or incomplete fiber structures on the surface of the acrylic fiber yarn before being dried and densified. It is suppressed and antibacterial and deodorizing properties are maintained.
[0018]
A tank made of a solution of a quaternary ammonium salt for treating the yarn before drying and densification can be provided independently of a process oil agent treatment tank for acrylic fibers, or can also serve as a process oil agent treatment tank. . Since a manufacturing process can be simplified, it is preferable to make it common as a mixed solution tank of chitosan and a surfactant containing a quaternary ammonium salt, for example.
[0019]
【Example】
The following examples further illustrate the present invention.
(Method of measuring quaternary ammonium salt content)
Acrylic fiber was dissolved in DMSO-d ₆ so as to be 4% by weight, and ¹ H-NMR was measured. From the area ratio of the peak derived from the acrylonitrile polymer and the peak derived from the quaternary ammonium salt, The content was determined.
[0020]
(Rusting test)
In a 200cc beaker filled with 100g of the obtained raw cotton, 10 iron needles called holer pins are placed and left in a thermostat at 35 ° C and 70% for 1 week. As a result, grade 4 or higher was considered acceptable.
1st class: Maximum rusting 2nd class: Large rusting 3rd class: Small rusting 4th class: Minimum rusting 5th class: No rusting (Reduced viscosity of polymer)
The reduced viscosity ηred of the acrylonitrile-based polymer was measured using a Canon Fenceke viscometer at 25 ° C. with a polymer solution obtained by dissolving acrylonitrile-based polymer in dimethylformamide so as to be 0.5% by weight.
[0021]
(Measurement of antibacterial performance)
The difference in the increase / decrease in the number of bacteria due to Staphylococcus aureus was determined by the method for measuring the number of bacteria defined by the Textile Sanitation Processing Council. Antibacterial activity was defined as a difference in the number of bacteria increase / decrease value of 1.6 or more. The washing method was in accordance with the method established by the council.
[0022]
Example 1
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 that the copolymer concentration would be 25% by weight to obtain a spinning dope.
[0023]
This spinning stock solution was wet-spun into a spinning bath filled with a 30% by weight dimethylacetamide aqueous solution at 40 ° C., stretched 5 times while washing the solvent in boiling water, and then polyoxyethylene (polymerization degree) as a surfactant. 200) was introduced into an oil bath of a process oil in which 0.3% by weight and 0.35% by weight of didecyldimethylammonium adipate as a quaternary ammonium salt were dispersed. Then, it dehydrated so that the amount of moisture attached to the fiber weight would be 100%, and dried and densified with a heat roller at 150 ° C.
[0024]
Further, relaxation treatment was performed in a pressurized steam of 2.5 kg / cm ² to obtain an acrylic fiber having a single fiber fineness of 3d. The amount of attached quaternary ammonium salt in the fiber was measured by the above method and found to be 0.33% by weight.
[0025]
The result of the rust test of this fiber was grade 4.
[0026]
Moreover, this fiber was cut into 51 mm length, and the spun yarn was produced. 50 g of this spun yarn, 0.25 g of dye (Hodogaya Chemical Co., Ltd. Katilon blue KGLH), 1 g of acetic acid, and 0.25 g of sodium acetate were added to 1000 g of pure water, heated to 100 ° C., and held at that temperature for 30 minutes. Thereafter, it was washed with water, dehydrated and dried. When the color clarity was evaluated by naked eye judgment on the spun yarn after dyeing, the excellent color developability of the acrylic fiber was not impaired. As a result of evaluating antibacterial properties, it was 3.5 before washing and 2.8 after 10 washings.
[0027]
(Example 2)
An acrylic fiber was obtained in the same manner as in Example 1 except that didecyldimethylammonium gluconate was used as the quaternary ammonium salt and the concentration of the quaternary ammonium salt in the tank was 1.0% by weight. The content of quaternary ammonium salt in the fiber was 0.87% by weight. The result of the rust test of this fiber was grade 4. Further, when the antibacterial property of the spun yarn was measured in the same manner as in Example 1, it was 3.2 before washing and 3.1 after 10 washings. Further, the excellent color developability of the acrylic fiber was not impaired.
[0028]
(Comparative Example 1)
An acrylic fiber was obtained in the same manner as in Example 1 except that didecyldimethylammonium chloride was used as the quaternary ammonium salt. The content of quaternary ammonium salt in the fiber was 0.32% by weight. The result of the rust test on this fiber was grade 1. The excellent color developability of the acrylic fiber was not impaired.
[0029]
(Comparative Example 2)
Acrylic fibers were obtained in the same manner as in Example 1 except that the concentration of didecyldimethylammonium adipate in the oil bath was 0.03% by weight. The amount of adhered quaternary ammonium salt in this fiber was 0.02% by weight. The result of the rusting test of this fiber was grade 5. As a result of preparing spun yarn and evaluating antibacterial properties in the same manner as in Example 1, it was 0.3 before washing and 0.2 after 10 washings. The excellent color developability of the acrylic fiber was not impaired.
[0030]
(Comparative Example 3)
Acrylic fibers were obtained in the same manner as in Example 1 except that the concentration of didecyldimethylammonium adipate in the oil bath was 7.0% by weight. The amount of adhered quaternary ammonium salt in the fiber was 6.7% by weight. The result of the rust test of this fiber was grade 4. An attempt was made to prepare a spun yarn in the same manner as in Example 1. However, the spun yarn could not be obtained due to the great adhesion of fibers to the roll.
[0031]
(Example 3)
30% acrylic fiber obtained in Example 1 and 70% cotton were mixed to prepare a spun yarn. After cationic dyeing under the same conditions as in Example 1, the antibacterial properties before and after washing 10 times were evaluated to be 2.8 and 1.9, respectively. Further, the excellent color developability of the acrylic fiber was not impaired.
[0032]
【The invention's effect】
As described above, according to the present invention, there are provided antibacterial fibers that are free from problems such as the occurrence of rust in spinning and spinning devices and have an excellent antibacterial effect. The antibacterial fiber of the present invention has an antibacterial effect against all bacteria required for an antibacterial and deodorant fiber product, and the effect is in the environment where fiber products such as fiber dyeing, bleaching, washing, ironing, etc. are used. Even if the process is received, it does not drop.

Claims (2)

A quaternary ammonium salt containing a cation represented by the following general formula [1] having a carboxylate anion as a counter anion is contained in an amount of 0.05% by weight or more and 5.0% by weight or less based on the fiber. Antibacterial fiber.
[R ₁ R ₂ (CH ₃ ) ₂ N] ⁺ [1]
(In the above general formula [1], R ₁ and R ₂ may be the same or different, and both are alkyl groups having 8 to 18 carbon atoms.) The antibacterial fiber according to claim 1, wherein the fiber is an acrylic fiber.