JP2013076188A - Method for producing antimicrobial acrylic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an antimicrobial acrylic fiber excellent in dye affinity and durability.SOLUTION: There is provided a method for producing an antimicrobial acrylic fiber in which an acrylic fiber containing an anionic copolymer component of 0.60 mass% or more and 2.10 mass% or less is impregnated into a treatment liquid containing a quaternary ammonium salt as an antibacterial agent component and the quaternary ammonium salt is ion exchanged with the anionic copolymer component to adhere the antibacterial agent component onto the fiber. It is preferable that fibers which have been dry heat treated to be in the compacted state be impregnated with the treatment liquid containing the quaternary ammonium salt.

Description

  The present invention relates to a method for producing an acrylic fiber imparted with antibacterial function.

  With an increasing number of consumers seeking a rich and comfortable living environment, cleaner and more comfortable clothing and textile products for bedding home products are widely distributed. In particular, for underwear applications, antibacterial fiber products imparted with antibacterial properties are widely distributed for the purpose of suppressing the growth of various bacteria by human sweat and preventing the generation of unpleasant odors. The characteristic required for these antibacterial products is that the antibacterial component is maintained without the antibacterial component being eluted or removed from the fiber.

  As a method for imparting antibacterial properties to fibers, for example, a method of adding silver or a silver compound to a polymer forming the fibers (see Patent Document 1), or crystalline fine particles carrying silver (Patent Document 2). A method for imparting antibacterial properties to a fiber has been proposed.

  Separately, with respect to the antibacterial agent, a method for producing an acrylic fiber in which chitosan is kneaded into the fiber (see Patent Document 3), or a fiber surface is imparted by submerged treatment using a quaternary ammonium salt as an antibacterial agent Thus, a method for obtaining an antibacterial product (see Patent Document 4) has been proposed.

  However, when the above silver is used as an antibacterial agent, there is a problem that the silver is denatured by the exposure treatment and the antibacterial property is lost. In addition, there is a problem that it is necessary to control the particle diameter in the technology for maintaining the antibacterial property of silver by supporting silver on the crystal fine particles. In addition, when an antibacterial agent as an active ingredient is kneaded into a fiber, the ingredients may aggregate to cause clogging in the spinneret hole, which may cause deterioration in operability. Moreover, although the method of applying an antibacterial agent to the fiber surface is simple and excellent in productivity, there is a problem in durability such that an active ingredient is removed by washing or the like. In addition, since some quaternary ammonium salts contain corrosive chloride ions, there is a problem that rust occurs in spinning and spinning apparatuses.

Japanese Patent Laid-Open No. 3-199418 JP 2010-18895 A Japanese Patent Laid-Open No. 10-140418 JP 59-130371 A

  When adding antibacterial properties to acrylic fibers, the surface of the antibacterial component by treatment in the bath is poor in durability, such as when the active component falls off when washing, etc., and quaternary ammonium containing chloride ions When salt is used as an antibacterial agent, there are problems such as corroding the device in a high-order processing step.

  Then, the objective of this invention is providing the manufacturing method of the antibacterial acrylic fiber excellent in dyeability and durability.

  Another object of the present invention is to prevent corrosion of the apparatus in a high-order processing step because anion exchange is performed even when a quaternary ammonium salt containing chloride ions is used as an antibacterial agent component. An object of the present invention is to provide a method for producing an antibacterial acrylic fiber capable of forming

  The present invention is intended to solve the above problems, and the method for producing an antibacterial acrylic fiber of the present invention is an acrylic containing 0.60% by mass or more and 2.10% by mass or less of an anionic copolymer component. The fiber is impregnated with a treatment liquid containing a quaternary ammonium salt as an antibacterial agent component, and the quaternary ammonium salt is ion-exchanged with the anionic copolymer component to fix the antibacterial agent component to the fiber. It is a manufacturing method of antibacterial acrylic fiber.

  According to the preferable aspect of the manufacturing method of the antibacterial acrylic fiber of this invention, the content rate with respect to the fiber of the said quaternary ammonium salt is 0.27 mass% or more and 0.45 mass% or less.

  According to a preferred aspect of the method for producing an antibacterial acrylic fiber of the present invention, the impregnation with the treatment liquid containing the quaternary ammonium salt is performed in a fiber-densified state after the dry heat treatment of the fiber. is there.

  According to the present invention, it is possible to obtain an antibacterial acrylic fiber that is easy to manufacture and excellent in dyeability and durability. Further, even when a quaternary ammonium salt containing chloride ions is used as an antibacterial agent component, since anion exchange is performed, it is possible to prevent corrosion of the apparatus in high-order processing.

  Thus, since the antibacterial acrylic fiber obtained by this invention has the antibacterial performance excellent in washing durability, even if the process which a textiles receives in a use environment is made, it can maintain an antibacterial performance. In addition, since the color developability is the same as that of existing acrylic fibers, there are no restrictions at the time of blending. Further, even if a chloride-based quaternary ammonium salt is selected as the antibacterial agent, there is no problem such as generation of rust on peripheral equipment in high-order processing.

  In the present invention, an acrylic fiber containing an anionic copolymer component is impregnated in a treatment solution containing a quaternary ammonium salt as an antibacterial agent component, and the quaternary ammonium salt is added to the anionic copolymer. This is a method for producing an antibacterial acrylic fiber that is ion-exchanged with a component to fix the antibacterial component to the fiber.

  The acrylic fiber used in the present invention is a fiber made of an acrylic polymer containing acrylonitrile in an amount of 85% by mass or more, preferably 90% by mass or more. When the acrylonitrile in the acrylic polymer is less than 85% by mass, the heat resistance as the acrylic fiber is inferior.

  Examples of the anionic copolymerization component copolymerized with acrylonitrile used in the present invention include methallyl sulfonic acid soda, styrene sulfonic acid soda, vinyl sulfonic acid soda, allyl sulfonic acid soda, 2-acrylamido-2-methylpropane. Ionic unsaturated monomers such as sodium sulfonate and isoprene sulfonate are preferably selected. Of these, sodium methallyl sulfonate and sodium styrene sulfonate are preferably used.

  Content with respect to the acrylic fiber of an anionic copolymer component is 0.6-2.1 mass%, Preferably it is 0.9-1.5 mass%. When the above content is 0.6% by mass or less, a decrease in antibacterial properties is caused, and when the content exceeds 2.1% by mass, the stretchability is reduced, and adhesion between single yarns is likely to occur.

  In the present invention, other unsaturated monomers copolymerized with acrylonitrile include acrylic acid esters such as methyl acrylate and ethyl acrylate, methacrylic acid esters such as ethyl methacrylate and isopropyl methacrylate, styrene and vinyl acetate, and the like. Is mentioned. The proportion of copolymerization allowed is preferably 6-13% by weight. If the copolymerization ratio is less than 6% by mass, the spinnability decreases, and if it exceeds 13% by mass, the pilling detachment (anti-pilling property) tends to deteriorate.

  The cross section of the acrylic fiber used in the present invention is applied to an arbitrary cross section such as a β-shaped cross section, a circular cross section, a flat shape, a Y shape, and a C shape formed in wet spinning. Further, the single fiber fineness of the acrylic fiber is preferably in the range of 0.5 to 5.6 dtex and can be used for textile products.

  The acrylic fiber used in the present invention is produced by wet spinning. The polymerization method of the spinning dope used for wet spinning may be any of suspension polymerization method, emulsion polymerization method, solution polymerization method, etc., but dimethyl sulfoxide (hereinafter, referred to as DMSO) may be used as an organic solvent from the chain transfer constant. Solution polymerization selected with.) Is preferably used.

  The polymer concentration used in the solution polymerization is preferably 20 to 25% by mass, more preferably 21 to 23% by mass. When the polymer concentration is less than 20% by mass, the resulting fiber is devitrified, and the gloss is lost and the color developability is lowered. Further, when the polymer concentration exceeds 25% by mass, the spinnability tends to be remarkably deteriorated.

  The obtained polymer solution is used as a spinning dope and discharged from a spinneret into a poor solvent containing water as a main component and solidified. Examples of the solvent in the spinning bath used at this time include DMSO, dimethylformamide, and dimethylacetamide. From the viewpoint of solvent recovery, the use of the same solvent as the solvent for the polymerization stock solution may further increase the chain transfer constant. DMSO is preferably used.

  The spinning draft when the spinning dope is discharged into the spinning bath is preferably in the range of 1.5 to 2.2. When the spinning draft is less than 1.5, the yarn is loosened between the die and the take-up roller, and yarn breakage due to yarn swinging due to turbulent flow in the bath tends to occur. On the other hand, if the spinning draft exceeds 2.2, the yarn may be cut from the die surface due to excessive tension. The coagulated yarn is preferably stretched 3.5 to 5.0 times in a bath having a concentration of 55 to 75% by weight, preferably a DMSO concentration of 60 to 70. When the draw ratio is less than 3.5 times, the spinning operability is lowered, and when the draw ratio exceeds 5.0 times, the strength is increased.

  The drawn yarn is preferably removed from the solvent in warm water at a temperature of 40 to 60 ° C., and then preferably kept at a shrinkage rate of 5% or less under dry heat at a temperature of 150 to 165 ° C. However, dry densification tension heat treatment is performed. When the shrinkage rate exceeds 5%, or when the heat treatment temperature is lower than 150 ° C., it is difficult to maintain the effect of increasing the fiber orientation of the fibers by preferably setting the spinning draft to 1.5 to 2.2. In addition, the drying densification and the tension heat treatment are usually performed in a hot air dryer without separation, but a method of separation may be used.

  The antibacterial agent used in the present invention is a quaternary ammonium salt. Quaternary ammonium salts are long-chain alkyl groups such as benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, cetrimonium bromide, didecyldimethylammonium chloride and domifene bromide because of their excellent antibacterial activity. Those having the following are preferably used.

  About these antibacterial agent components, it can mix with water or another process oil agent in arbitrary ratios, and can impregnate and give a fiber as an adjustment oil agent (treatment liquid). At this time, the proportion of the antibacterial agent in the active ingredient of the adjusting oil is preferably 60 to 70%. As an application method, the fibers (bundles) are passed through an oil bath provided with a guide. Thereby, anion exchange between the fiber surface and the antibacterial component occurs, and the antibacterial component is fixed to the fiber surface. The amount of fiber (bundle) that has traveled in the oil bath is quantified by squeezing at a constant pressure with a nip roller, so the amount of fiber (bundle) taken out is fixed. Adjusted. The concentration range of the antibacterial component in the oil bath is preferably 1.6 to 2.8%. If it deviates from this range, the antibacterial performance may not be obtained, or the excess part taken out may fall off during high-order processing, and the equipment may be corroded. The process oil is applied to reduce the friction of the yarn against the metal (make it slippery), and improves the passability of the roller card (machine that opens the yarn) in high-order processing.

  In addition, the antibacterial oil agent can be supplied to the oil agent bath so that the oil agent bath liquid surface becomes constant according to the carry-out amount by the fibers. In addition, the application is preferably performed after the fibers are dried and densified. If the fiber structure is applied before densification, which is still in a sparse structure, there is a problem that the dyeing seat is blocked by the penetration of the antibacterial agent not only on the fiber surface but also into the fiber inner layer, thereby affecting the dyeability. In the manufacturing process, it can be distinguished before and after passing through the dry heat treatment machine before the dry densification and the densification still in a sparse structure. The fiber bundle in the swollen state before the dry heat treatment is assumed to be “still in a sparse structure”.

  Since the quaternary ammonium salt used in the present invention is weak against heat (the thermal decomposition temperature of benzalkonium chloride is 135 ° C, the dry heat temperature is 150 ° C or higher), if it is carried out before the densification treatment, the antibacterial performance is affected. To do. Another advantage is that the concentration of the bath is easy because it passes through the oil bath in a dry heat state (a state of low water content) and the amount of water brought in is small.

  After the antibacterial oil agent is applied, the antibacterial acrylic fiber intended in the present invention is obtained by drying the fiber after crimping.

  The amount of quaternary ammonium salt attached to the fiber in the present invention is 0.27% by mass or more in order to give sufficient antibacterial performance, and 0.45% by mass or less in order to prevent dyeing and dropping off in the spinning process. It is preferable that

  In order to obtain antibacterial properties in the spun yarn obtained by spinning the antibacterial acrylic fiber of the present invention and other fibers, the antibacterial acrylic fiber of the present invention is preferably blended at 40% by mass or more. . Examples of fibers mixed with the antibacterial acrylic fiber of the present invention include cotton, rayon, wool, and polyester. Target applications include socks, mats around water, underwear, jerseys, and blankets.

  Next, the method for producing the antibacterial acrylic fiber of the present invention will be specifically described with reference to examples.

(Measurement method of antimicrobial component)
Using 2 g of acrylic fiber to which an antibacterial agent component has been added as a measurement sample, an antibacterial oil adhering to the fiber is extracted with an extraction solvent using a Soxhlet extractor. As the extraction solvent, a mixed solution of methanol and chloroform (mixing ratio 3: 1) is used. The extract is collected in an aluminum tray (A) having a known mass, and the solvent is distilled off. The mass of the oil agent adhering is measured by measuring (B) the mass of the aluminum tray, and the oil agent adhesion rate is calculated based on the table below.
Oil agent adhesion rate = (B−A) / 2 × 100
Since the component composition of the oil used is known, the adhesion rate (content) of the antibacterial agent component is calculated from the component ratio of the antibacterial agent component.

(1) Antibacterial performance measurement For the evaluation method of antibacterial performance, JIS 1902 (2011) (antibacterial test method / antibacterial effect of textile products) in the certification standard for antibacterial and deodorant processed textile products of the Fiber Evaluation Technology Council The bacteriostatic activity value was determined by a test method (bacterial solution absorption method).

Antibacterial evaluation after washing was also carried out using the same method, and the washing method was in accordance with the “SEK Mark Textile Product Washing Manual” established by the Council. Moreover, about the frequency | count of washing, it implemented 10 times by the predetermined frequency. About the calculated | required bacteriostatic activity value, it determined in the following three steps and made excellent ((double-circle)) and good ((circle)) effective.
Excellent (◎): Bacteriostatic activity value ≧ 3.0
Good (◯): Bacteriostatic activity value = 2.2 to 2.9
Poor (x): Bacteriostatic activity value <2.2
(2) Evaluation of rusting property 10 g of the obtained raw cotton wraps a wire (hard steel wire) used in a card machine used in high-order processing, puts it in a wire net tube, and a constant temperature and humidity machine (temperature 30 ° C, (70% RH) for 7 days. Thereafter, the degree of occurrence of the wire surface taken out was visually evaluated as follows, and grade 3 or higher was regarded as acceptable.
1st grade: Large rusting (rusts on 50% or more of wire surface)
Second grade: During rusting (rusts on 5% or more of wire surface)
3rd grade: Small rusting (rusts less than 5% of wire surface)
Grade 4: No rusting (3) Dyeability evaluation The antibacterial acrylic fiber 250g obtained according to the present invention was opened into a fiber web and used as a sample cotton. Bath temperature using the following dyeing solution The temperature was raised to 100 ° C. in 80 minutes, and dyeing was performed at 100 ° C. for 30 minutes as it was.

<Dyeing liquid>
Astrzon Goldden Yellow GL-E 1.00 owf%
Astrzon Red F3BL 0.48 owf%
Malachite Green 0.22 owf%
Dyeing assistant (leveling agent cationogen L 1.00 owf%, sodium acetate 0.50 owf%, acetic acid 0.60 owf%).

Acrylic fiber with no antibacterial component and only spinning oil is dyed under the same conditions, and this is used as a control cotton to compare the difference in L value with the sample cotton. Excellent (◎) and good (○) were accepted.
Excellent (◎): | L value (control cotton) -L value (sample cotton) | <1.0
Good (◯): | L value (control cotton) −L value (sample cotton) | = 1.0 to 2.0
Bad (×): | L value (control cotton) −L value (sample cotton) | ≧ 2.0
(Examples 1-2, Comparative Examples 1-3)
For Example 1, acrylonitrile was selected as the raw material monomer, methallyl sulfonic acid sodium soda was selected as the anionic copolymer component, and methyl acrylate was selected as the other copolymer component, and acrylonitrile / sodium methallyl sulfonate / methyl acrylate were each massed. The solution was polymerized by dissolving in DNSO at a ratio of 91.8 / 1.2 / 7.0 as a percentage, and the DMSO solution of the produced polymer was used as the spinning dope. This spinning stock solution was discharged using a die into a coagulation bath that was a DMSO aqueous solution having a concentration of 64% and a bath temperature of 48 ° C., and wet spinning was performed. The coagulated yarn is stretched 5.0 times and dried and densified while being washed with water and maintaining a shrinkage of 5% or less under dry heat at a temperature of 160 ° C. The densified fiber bundle was imparted by selecting benzalkonium chloride as the antibacterial agent component and passing it through the adjusted antibacterial oil agent to cause ion exchange on the fiber surface. The adjusted oil agent bath concentration was 3.1%. The mass component ratio was 1.9% for antibacterial component, 1.2% for nonionic surfactant spinning oil, and 96.9% for water. The temperature of the oil agent bath was 40 ° C., and the immersion time was passed through the oil agent bath through a guide at a spinning speed of 73.0 m / min for 1.8 seconds (dip method).

  Based on the composition ratio and production conditions described in Table 1, antibacterial acrylic fibers having a single fiber fineness of 1.0 dtex were produced. In Comparative Example 1, the antibacterial oil agent is applied before drying and densification, in Comparative Example 2, the antibacterial oil agent is applied to the fiber bundle by spraying, and in Comparative Example 3, the ratio of the anionic copolymer component is 0.5% by mass. Except for the above, the same production method as in the example was selected.

  The produced antibacterial acrylic fibers were evaluated in the above (1) to (3), and the results are shown in Table 2. As a result, the antibacterial acrylic fiber according to the present invention has antibacterial performance excellent in washing durability and is excellent in color development. Moreover, the corrosivity to the peripheral apparatus in high-order processing can be suppressed from rust evaluation.

Claims (3)

  An acrylic fiber containing 0.60% by mass or more and 2.10% by mass or less of an anionic copolymer component is impregnated in a treatment solution containing a quaternary ammonium salt as an antibacterial agent component, and the quaternary ammonium salt is added. A method for producing an antibacterial acrylic fiber, characterized by ion-exchange with the anionic copolymer component and fixing an antibacterial agent component to the fiber.   The antibacterial acrylic fiber according to claim 1, wherein the content of the quaternary ammonium salt with respect to the fiber is 0.27% by mass or more and 0.45% by mass or less.   A method for producing an antibacterial acrylic fiber, wherein the impregnation with a treatment liquid containing a quaternary ammonium salt is performed in a fiber-densified state after the dry heat treatment of the fiber.