Antibacterial acrylic artificial hair fiber, headwear product containing the same, and method for manufacturing the same.

Abstract

One or more embodiments of the present invention relate to antimicrobial acrylic artificial hair fibers which contain chitosan and a nonionic surfactant, wherein: the content of chitosan extracted with dilute acetic acid is 0.005 to 0.4% by weight; the content of chitosan extracted with concentrated hydrochloric acid is 0.014 to 1.2% by weight; the content of the nonionic surfactant is 0.10 to 0.90% by weight; the nonionic surfactant is composed of one or more substances that are selected from the group consisting of a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene fatty acid monoester and a polyoxyethylene alkyl ether; and the nonionic surfactant has an HLB of 13.0 or more.

Description

[Technical Field]

[0001] The present invention relates to antibacterial acrylic artificial hair fibers used in headwear products such as wigs, headwear products containing the same, and a method for manufacturing the same. [Background technology]

[0002] Traditionally, human hair and synthetic hair have been used in headwear products such as wigs, but in recent years, human hair has become difficult to obtain, and the demand for synthetic hair has increased. Acrylic fibers have been suitably used as synthetic hair because their feel, luster, and volume are very similar to human hair. For example, Patent Document 1 proposes synthetic hair using fibers made of acrylic polymers composed of halogen-containing vinyl monomers such as acrylonitrile and vinyl chloride, and vinyl monomers copolymerizable with these. However, conventional acrylic artificial hair described in Patent Document 1 has low antibacterial properties, and there was a problem with bacteria growing and multiplying when the artificial hair was worn for a long period of time or stored after wearing. Patent Document 2 proposes an antibacterial acrylic fiber containing chitosan and a quaternary ammonium salt as an acrylic fiber for use in clothing. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2002-227028 [Patent Document 2] Japanese Patent Application Publication No. 10-158978 [Overview of the project] [Problems that the invention aims to solve]

[0004] In the case of synthetic fibers, oils are often applied to suppress static electricity, but when oils are applied to acrylic fibers containing chitosan, the gloss deteriorates, making it difficult to use them as artificial hair.

[0005] To solve the aforementioned problems, the present invention provides an acrylic-based artificial hair fiber having good antibacterial properties and gloss, a headwear product containing the same, and a method for manufacturing the same. [Means for solving the problem]

[0006] One or more embodiments of the present invention relate to an antibacterial acrylic artificial hair fiber comprising chitosan and a nonionic surfactant, wherein the content of chitosan extracted with dilute acetic acid is 0.005 to 0.4% by weight, the content of the nonionic surfactant is 0.10 to 0.90% by weight, the nonionic surfactant is one or more selected from the group consisting of polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid monoester, and polyoxyethylene alkyl ether, and the HLB of the nonionic surfactant is 13.0 or higher.

[0007] One or more embodiments of the present invention relate to an antibacterial acrylic artificial hair fiber comprising chitosan and a nonionic surfactant, wherein the content of chitosan extracted with concentrated hydrochloric acid is 0.014 to 1.2% by weight, the content of the nonionic surfactant is 0.10 to 0.90% by weight, the nonionic surfactant is one or more selected from the group consisting of polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid monoester, and polyoxyethylene alkyl ether, and the HLB of the nonionic surfactant is 13.0 or higher.

[0008] One or more embodiments of the present invention relate to a head accessory product characterized by containing the antibacterial acrylic artificial hair fiber.

[0009] One or more embodiments of the present invention relate to a method for producing antibacterial acrylic artificial hair fibers, wherein a spinning solution containing an acrylic copolymer is wet-spun, and chitosan and a nonionic surfactant are applied to the yarn before it dries, and the nonionic surfactant has an HLB of 13.0 or higher and is one or more selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide antibacterial acrylic artificial hair fibers with good antibacterial properties and gloss, and headwear products containing the same. Furthermore, according to the manufacturing method of the present invention, antibacterial acrylic artificial hair fibers with good antibacterial properties and luster can be obtained by wet spinning. [Modes for carrying out the invention]

[0011] The inventors of the present invention have conducted extensive research to impart antibacterial properties to acrylic artificial hair fibers and improve their luster as artificial hair. As a result, they have found that by using one or more nonionic surfactants selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers as an oil, and having a predetermined HLB, and by setting the content of chitosan and the nonionic surfactant within a predetermined range, an antibacterial acrylic artificial hair fiber with good antibacterial properties and luster can be obtained. Furthermore, in one or more preferred embodiments of the present invention, the antibacterial acrylic artificial hair fiber has deodorizing properties. Furthermore, in one or more preferred embodiments of the present invention, the antibacterial acrylic artificial hair fiber has deodorizing properties.

[0012] In one or more embodiments of the present invention, when a numerical range is indicated by "~", both end values are included. For example, the numerical range of "X~Y" is a range that includes both end values of X and Y. Also, in this specification, when a plurality of numerical ranges are described, it is assumed to include numerical ranges obtained by appropriately combining the upper and lower limits of different numerical ranges.

[0013] (Antibacterial acrylic artificial hair fiber) The antibacterial acrylic artificial hair fiber contains chitosan and a nonionic surfactant.

[0014] Chitosan is a deacetylated product of chitin, which is a natural polymer. For example, chitin obtained from the exoskeletons of crustaceans such as crabs and shrimps can be deacetylated by boiling treatment in concentrated alkali or the like. The deacetylation degree of chitosan is not particularly limited and may be about 60 to 99%. For example, from the viewpoint of deodorizing properties, it is preferably 70 to 99%, and more preferably 80 to 99%. The deacetylation degree of chitosan can be measured, for example, by NMR spectroscopy, infrared absorption spectroscopy (IR), and colloidal titration method. The weight average molecular weight of chitosan is not particularly limited and may be about 10,000 to 1,000,000. From the viewpoint of the handling property of the aqueous solution, it is preferably 10,000 to 500,000, and more preferably 10,000 to 300,000. In this specification, the weight average molecular weight of a compound can be measured by gel permeation chromatography (GPC). The GPC measurement is performed using chloroform as the mobile phase, the measurement is carried out with a polystyrene gel column, and the number weight average molecular weight and the like can be determined in terms of polystyrene.

[0015] Since antibacterial acrylic artificial hair fibers are likely to come into contact with the skin and mouth during use, from the perspective of safety, it is preferable that chitosan has a low allergen content. Since chitosan is often purified from raw materials derived from crustaceans, it may contain crustacean proteins, which are a type of allergen. The content of crustacean protein in chitosan is preferably 9.9 μg or less, more preferably 5.0 μg or less, and even more preferably 1.0 μg or less per 1 g of chitosan. For example, for a sample with a protein content of 10 μg or more per 1 g of food sampling weight derived from a specific raw material or the like, it may be determined that there is a possibility that a trace amount of a specific raw material is mixed in. The protein content in chitosan can be measured, for example, by the ELISA method. Specifically, the content of crustacean protein in chitosan can be measured by the ELISA method using the Crustacean Kit II "Maruha Nichiro" manufactured by Maruha Nichiro Co., Ltd. or the FA Test EIA-Crustacean II "Nissui" manufactured by Nissui Pharmaceutical Co., Ltd.

[0016] In antibacterial acrylic artificial hair fibers, the content of chitosan extracted with dilute acetic acid is 0.005 to 0.4% by weight. If the content of chitosan is too low, the antibacterial property is poor. On the other hand, if the content of chitosan is too high, it becomes difficult to stretch and the process stability is poor. From the perspective of antibacterial property, the content of chitosan extracted with dilute acetic acid is preferably 0.01% by weight or more. From the perspective of excellent antibacterial property and excellent deodorant performance, the content of chitosan extracted with dilute acetic acid is preferably 0.02% by weight or more, more preferably 0.03% by weight or more, even more preferably 0.05% by weight or more, and particularly preferably 0.06% by weight or more. From the perspective of improving stretchability and gloss, the content of chitosan extracted with dilute acetic acid is preferably 0.4% by weight or less, more preferably 0.3% by weight or less. In this specification, the content of chitosan extracted with dilute acetic acid can be measured and calculated as follows.

[0017] (Content of chitosan extracted with dilute acetic acid) 1) Dissolve 1.87 g of glycine and 1.46 g of sodium chloride in pure water to make a 250 g solution, and then add 0.1 M hydrochloric acid until the pH reaches 3.2 to prepare a buffer solution. 2) Dissolve 150 mg of Reactive Red 4 in pure water to make a 100 g solution, and dilute 5 g of this solution 50 times with the buffer solution from step 1) to prepare the dye solution. 3) Add 3.0 g of fiber and 20 g of 0.1% by weight acetic acid aqueous solution to a glass bottle and heat at 90°C for 1 hour to prepare the extract. 4) After the extract has cooled, immediately mix 5 mL of dye solution with 0.5 mL of the extract and measure the absorbance at 578 nm using a UV-Vis spectrophotometer. At this time, use a mixture of 0.5 mL of buffer solution and 5 mL of dye solution as a reference. 5) Using a mixture of 0.5 mL of buffer solution and 5 mL of dye solution as a reference, a calibration curve was created from the absorbance at 578 nm using a mixture of 0.5 mL of chitosan aqueous solution (prepared to 0.0025% by weight) and 5 mL of dye solution. Based on this calibration curve and the absorbance values ​​from 4), the chitosan concentration in the extract was calculated, and the content of chitosan extracted with dilute acetic acid was determined.

[0018] The chitosan content in antibacterial acrylic artificial hair fibers may be expressed as the content of chitosan extracted with dilute acetic acid, as described above, or as the content of chitosan extracted with concentrated hydrochloric acid, as described later. Note that when extracted with concentrated hydrochloric acid, almost all of the chitosan in the fiber can be extracted.

[0019] In antibacterial acrylic artificial hair fibers, the chitosan content extracted with concentrated hydrochloric acid is 0.014 to 1.2% by weight. If the chitosan content is too low, the antibacterial properties are poor. On the other hand, if the chitosan content is too high, it becomes difficult to stretch, resulting in poor process stability. From the viewpoint of antibacterial properties, the chitosan content extracted with concentrated hydrochloric acid is preferably 0.015% by weight or more, and more preferably 0.02% by weight or more. From the viewpoint of having excellent antibacterial properties as well as excellent deodorizing properties, the chitosan content extracted with concentrated hydrochloric acid is even more preferably 0.04% by weight or more, even more preferably 0.06% by weight or more, even more preferably 0.08% by weight or more, and particularly preferably 0.1% by weight or more. The content of chitosan extracted with concentrated hydrochloric acid is preferably 1.0% by weight or less, more preferably 0.9% by weight or less, even more preferably 0.8% by weight or less, and even more preferably 0.7% by weight or less, from the viewpoint of improving stretchability and gloss. In this specification, the content of chitosan extracted with concentrated hydrochloric acid can be measured and calculated as follows.

[0020] (Chitosan content extracted with concentrated hydrochloric acid) 0.2 g of fiber sample was heated under reflux in 10 mL of 12N hydrochloric acid to decompose the chitosan, and then diluted to 20 mL with water to obtain a chitosan hydrolysate. 2 mL of the chitosan hydrolysate and 3.8 g of sodium borate were added to 30 mL of water, and then the solution was neutralized to pH 7 with 12N hydrochloric acid and diluted to 50 mL. 1 mL of the resulting solution was mixed with the derivatization reagent 9-fluorenylmethyl chloroformate (20 mg / 20 mL acetonitrile solution), allowed to stand, and then 3 mL of a mixed solvent of acetonitrile:water = 1:1 (containing 0.25% formic acid) was added to prepare the HPLC test solution. The chitosan content extracted with concentrated hydrochloric acid was determined from the peak area obtained by HPLC analysis and a calibration curve prepared using glucosamine hydrochloride.

[0021] The nonionic surfactant is one or more selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers. The nonionic surfactant has an HLB of 13.0 or higher. In this specification, the HLB (hydrophilic-lipophilic balance) of the nonionic surfactant is determined by the Griffin method. An HLB of 13.0 or higher for the nonionic surfactant makes it easier to suppress the aggregation of chitosan on the fiber surface and improves gloss. The HLB of the nonionic surfactant is preferably 13.5 or higher, more preferably 14.0 or higher, even more preferably 14.5 or higher, and particularly preferably 15.0 or higher. Furthermore, from the viewpoint of emulsification, the HLB of the nonionic surfactant may be 19 or lower.

[0022] The polyoxyethylene sorbitan fatty acid ester is not particularly limited, as long as its HLB is 13.0 or higher. For example, a sorbitan fatty acid monoester with an oxyethylene group added can be used as appropriate. The average number of moles of oxyethylene groups added is preferably 5 to 100, more preferably 10 to 50. The number of carbon atoms in the fatty acid may be 4 to 30, preferably 6 to 28, more preferably 8 to 26, even more preferably 10 to 24, and particularly preferably 12 to 22. The carbon chain of the fatty acid may be linear or branched. The fatty acid may be saturated or unsaturated.

[0023] Examples of saturated fatty acids include lauric acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, behenic acid, tetracosanoic acid, hexacosanoic acid, and octacosanoic acid.

[0024] Examples of unsaturated fatty acids include palmitoleic acid, oleic acid, vaccenic acid, nervonic acid, linoleic acid, eicosadienoic acid, linolenic acid, meadic acid, and arachidonic acid.

[0025] From the viewpoint of improving gloss, the polyoxyethylene sorbitan fatty acid ester is more preferably one or more selected from the group consisting of polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan monolaurate. The average number of added moles of oxyethylene groups in the polyoxyethylene sorbitan monooleate is preferably 10 to 100, and more preferably 15 to 30. The average number of added moles of oxyethylene groups in the polyoxyethylene sorbitan monolaurate is preferably 10 to 100, and more preferably 15 to 100.

[0026] The polyoxyethylene fatty acid monoester is not particularly limited, as long as its HLB is 13.0 or higher. For example, a monoester of a fatty acid and polyoxyethylene glycol can be used as appropriate. The average number of moles of oxyethylene groups added is preferably 5 to 100, more preferably 10 to 50. The number of carbon atoms in the fatty acid may be 4 to 30, preferably 6 to 28, more preferably 8 to 26, even more preferably 10 to 24, and particularly preferably 12 to 20. The carbon chain of the fatty acid may be linear or branched. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid. Examples of saturated fatty acids include those mentioned above. Specifically, polyoxyethylene fatty acid monoesters include polyoxyethylene monolaurate, polyoxyethylene monocaprate, polyoxyethylene monopalmitate, polyoxyethylene monostearate, polyoxyethylene monooleate, etc. From the viewpoint of improving gloss, polyoxyethylene monolaurate is preferred, and polyoxyethylene monolaurate with an average number of moles of oxyethylene groups added of 5 to 15 is more preferred.

[0027] The polyoxyethylene alkyl ether is not particularly limited, as long as its HLB is 13.0 or higher. The average number of moles of oxyethylene groups added is preferably 5 to 100, more preferably 10 to 30. In the polyoxyethylene alkyl ether, the number of carbon atoms in the alkyl group may be 4 to 30, preferably 6 to 28, more preferably 8 to 26. The carbon chain of the alkyl group may be linear or branched. Specifically, examples of polyoxyethylene alkyl ethers include polyoxyethylene-(2-ethyl)hexyl ether, polyoxyethylene lauryl ether, polyoxyethylene palmityl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc. From the viewpoint of improving gloss, polyoxyethylene-(2-ethyl)hexyl ether is preferred, and polyoxyethylene-(2-ethyl)hexyl ether with an average number of moles of oxyethylene groups added of 5 to 20 is more preferred.

[0028] In antibacterial acrylic artificial hair fibers, the melting point of the nonionic surfactant is not particularly limited, but from the viewpoint of gloss, it is preferably 25°C or lower, more preferably 22°C or lower, even more preferably 20°C or lower, and particularly preferably 18°C ​​or lower. In this specification, the melting point of the nonionic surfactant is determined by visual inspection or the like.

[0029] In antibacterial acrylic artificial hair fibers, the content of nonionic surfactant is 0.10 to 0.90% by weight. If the content of nonionic surfactant is less than 0.10% by weight, process stability and processability will decrease due to static electricity generation. If the content of nonionic surfactant exceeds 0.90% by weight, the separation of fiber bundles will deteriorate, and processability will decrease. The content of nonionic surfactant is preferably 0.80% by weight or less, more preferably 0.70% by weight or less, even more preferably 0.60% by weight or less, and particularly preferably 0.50% by weight or less. The content of nonionic surfactant (oil agent) (hereinafter also referred to as oil agent adhesion amount) can be measured as follows.

[0030] (Amount of oil residue) Cut approximately 2g of the sample (fiber) (sample weight W0) into 12-15cm lengths and pack them into a stainless steel tube (oil extraction tube) with a hole of approximately 1mm at the bottom. Next, prepare 35mL of a mixture of ethanol and cyclohexane (weight ratio) as the oil extract, and add approximately 20mL to the oil extraction tube. Adjust the lid of the oil extraction tube so that the extraction rate is approximately 1 drop / 1-1.5 seconds, and begin oil extraction. At this time, use a tray (empty tray weight W1) heated to 120°C by a heater as a receiving tray for the dripping liquid, and set it so that the dripping liquid falls into it. Once the dripping is complete, remove the lid and use a stainless steel rod to push the fibers inside the oil extraction tube to squeeze out the extract. Repeat this operation using the remaining extract (approximately 15mL). After extraction is complete, place the tray in a 90°C oven, remove it after 5 minutes, measure the total tray weight (W2) of the tray after the extract has dried and only the oil remains, and calculate the amount of oil adhering (weight %) using the following formula 1. [Formula 1] Amount of oil coating (weight %) = (W2 - W1) / W0 × 100

[0031] The acrylic copolymer constituting the antibacterial acrylic artificial hair fiber is not particularly limited. For example, an acrylic copolymer containing less than 95% by weight of acrylonitrile and more than 5% by weight of other monomers can be used, preferably an acrylic copolymer containing less than 80% by weight of acrylonitrile and more than 20% by weight of other monomers can be used. Specifically, it is more preferable that the acrylic copolymer contains 29.5 to 79.5% by weight of acrylonitrile, 20 to 70% by weight of vinyl chloride and / or vinylidene chloride, and 0.5 to 5% by weight of sulfonic acid group-containing vinyl monomer. When the acrylic copolymer has an acrylonitrile content of 29.5 to 79.5% by weight, it exhibits good heat resistance. When the acrylic copolymer has a vinyl chloride and / or vinylidene chloride content of 20 to 70% by weight, it exhibits good flame retardancy. The inclusion of 0.5 to 5% by weight of sulfonic acid group-containing vinyl monomer in the acrylic copolymer increases its hydrophilicity. More preferably, the acrylic copolymer contains 34.5 to 74.5% by weight of acrylonitrile, 25 to 65% by weight of vinyl chloride and / or vinylidene chloride, and 0.5 to 5% by weight of a sulfonic acid group-containing vinyl monomer; even more preferably, it contains 39.5 to 74.5% by weight of acrylonitrile, 25 to 60% by weight of vinyl chloride, and 0.5 to 5% by weight of a sulfonic acid group-containing vinyl monomer; and even more preferably, it contains 39.5 to 6% by weight of acrylonitrile. The acrylic copolymer contains 9.5% by weight of vinyl chloride, 30-60% by weight of vinyl chloride, and 0.5-5% by weight of a sulfonic acid group-containing vinyl monomer; more preferably, it contains 39.5-59.5% by weight of acrylonitrile, 40-60% by weight of vinyl chloride, and 0.5-5% by weight of a sulfonic acid group-containing vinyl monomer; particularly preferably, it contains 39.5-49.5% by weight of acrylonitrile, 50-60% by weight of vinyl chloride, and 0.5-5% by weight of a sulfonic acid group-containing vinyl monomer. From the viewpoint of superior tactile feel, it is preferable that the acrylic copolymer contains vinyl chloride.

[0032] The sulfonic acid group-containing vinyl monomer is not particularly limited, but examples include allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and their sodium salts and other metal salts and amine salts. The sulfonic acid group-containing vinyl monomer may be used alone or in combination of two or more types.

[0033] In one or more embodiments of the present invention, the antibacterial acrylic artificial hair fiber may contain other additives to improve fiber properties as needed, provided that they do not hinder the effects of the present invention. Examples of additives include gloss modifiers, organic pigments, inorganic pigments, and colorants such as dyes, light stabilizers, heat stabilizers, fiber consolidators, deodorizers, and fragrances. From the viewpoint of gloss and the stability of the chitosan-containing oil, the antibacterial acrylic artificial hair fiber preferably contains only one or more nonionic surfactants selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers as the oil. If the antibacterial acrylic artificial hair fiber contains other oils, from the viewpoint of fiber bundle separation, it is preferable that the HLB between the other oils and the other oils is 13.0 or higher, and that the total content of one or more nonionic surfactants selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers is 0.90% by weight or less.

[0034] From the viewpoint of suitably using the antibacterial acrylic artificial hair fiber as artificial hair, the single fiber fineness is preferably 10 to 100 dtex, more preferably 20 to 95 dtex, even more preferably 25 to 85 dtex, even more preferably 30 to 75 dtex, and particularly preferably 35 to 65 dtex.

[0035] The antibacterial acrylic artificial hair fiber preferably has an antibacterial activity value of 2.2 or more, more preferably 3.0 or more, and even more preferably 4.0 or more, when measured in accordance with JIS L 1902:2015, from the viewpoint of excellent antibacterial properties. The antibacterial acrylic artificial hair preferably has an antibacterial activity value of 4.0 or more, more preferably 4.5 or more, when measured in accordance with JIS L 1902:2015, from the viewpoint of excellent antibacterial properties even after washing. The antibacterial acrylic artificial hair fiber has high antibacterial properties against bacteria such as Staphylococcus aureus, for example.

[0036] From the viewpoint of excellent deodorant properties, the volatile amount of isovaleric acid generated by the growth of bacteria such as Staphylococcus aureus in the antibacterial acrylic artificial hair fiber is preferably 150 μg or less, more preferably 100 μg or less, and even more preferably 70 μg or less per 1 kg of the fiber. Isovaleric acid is known as an odor component generated from the scalp. In this specification, the volatile amount of isovaleric acid generated by the growth of bacteria can be specifically measured as described in the examples.

[0037] In the case of black, the antibacterial acrylic artificial hair fiber preferably has a gloss L BNT of 50.0 or more, more preferably 65.0 or more, from the viewpoint of good gloss. L BNT is calculated by the following formula 2 by measuring the intensities of specular reflection light and diffuse reflection light when a light source is applied to a fiber bundle attached to a curved surface using the SAMBA Hair System manufactured by Bossa Nova Technologies. [Formula 2] L BNT = 100 × {S in / (D + S out )} × (1 / W visual ) S in : Central specular reflection light intensity S out : Off-center specular reflection light intensity D: Diffuse reflection light intensity W visual[percent]: width of reflected light

[0038] Antibacterial acrylic artificial hair fibers have excellent deodorizing properties, and for example, a deodorizing rate of 60% or more against isovaleric acid is preferred, more preferably 70% or more, even more preferably 80% or more, and particularly preferred to be 90% or more. Isovaleric acid is known as an odor component that originates from the scalp. In this specification, deodorizing properties can be measured by the following method.

[0039] (Deodorizing properties) 1) Prepare a 0.03% aqueous solution of isovaleric acid. 2) Add 0.2 mL of isovaleric acid aqueous solution to the surface of 1 g of sample, then place it in a 1 L sampling bag and seal the cut portion. 3) After degassing the inside of the bag with a vacuum pump, inject 0.5 L of high-purity nitrogen gas through an integrated flow meter and seal the bag. 4) After standing for 2 hours at room temperature (20±5℃), volatile organic compounds contained in 0.1 L of nitrogen gas in the bag are collected using a cartridge containing 2,6-diphenyl-p-phenylene oxide, and analyzed using a gas chromatograph-mass spectrometer. The area of ​​the peak corresponding to isovaleric acid in the total ion chromatogram is determined using analysis software, and the gas concentration is calculated using a pre-prepared calibration curve. 5) The gas concentration is determined similarly using a control instead of the sample. As the control, AFRELLE (modacrylic fiber, manufactured by Kaneka Corporation, hereinafter also simply referred to as "AFRELLE"), a headwear product, is used. 6) The deodorization rate is calculated from the measured gas concentration using the following formula 3. [Formula 3] Deodorization rate [%] = {1 - (Sample gas concentration [ppm]) / (Control gas concentration [ppm])} × 100

[0040] (Manufacturing method) Antibacterial acrylic artificial hair can be produced, for example, by wet spinning a spinning solution containing an acrylic copolymer, and before drying, by applying chitosan and one or more nonionic surfactants selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers, with an HLB of 13.0 or higher to the yarn.

[0041] The spinning solution can be obtained, for example, by dissolving an acrylic copolymer in an organic solvent. The organic solvent is not particularly limited, and any good solvent for the acrylic copolymer can be used as appropriate. Examples of good solvents include methyl sulfoxide (DMSO), dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and acetone. From the viewpoint of versatility, acetone may be used. From the viewpoint of high safety, dimethyl sulfoxide may be used. The spinning solution may contain a small amount of water, for example, 1.5 to 4.8% by weight of water. This can suppress the formation of voids.

[0042] The spinning solution preferably contains 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, and even more preferably 0.3 parts by weight or more, of the epoxy group-containing compound per 100 parts by weight of the acrylic copolymer. Including the epoxy group-containing compound in the spinning solution is preferable because it can suppress odor, discoloration of the fibers due to heat, and devitrification of the fibers due to hot water. In particular, when dimethyl sulfoxide is used as the organic solvent, the generation of malodorous components due to the decomposition of dimethyl sulfoxide when the acrylic artificial hair fibers are heated can be effectively suppressed. Furthermore, from the viewpoint of spinnability, fiber quality, and cost, the spinning solution preferably contains 5 parts by weight or less, more preferably 3 parts by weight or less, and even more preferably 1 part by weight or less, of the epoxy group-containing compound per 100 parts by weight of the acrylic copolymer.

[0043] Examples of epoxy group-containing compounds that can be used include glycidyl methacrylate-containing polymers, glycidyl acrylate-containing polymers, epoxidized vegetable oils, glycidyl ether-type epoxy resins, glycidyl amine-type epoxy resins, glycidyl ester-type epoxy resins, and cyclic aliphatic-type epoxy resins. The epoxy group-containing compound may be used individually or in combination of two or more types.

[0044] From the viewpoint of epoxy equivalent (weight of resin containing 1 equivalent of epoxy groups), suppression of fiber discoloration, solubility in dimethyl sulfoxide, and reduction of elution into the spinning bath, the epoxy group-containing compound is preferably a glycidyl methacrylate-containing polymer and / or a glycidyl acrylate-containing polymer, and more preferably a polyglycidyl methacrylate.

[0045] The weight-average molecular weight of the epoxy group-containing compound is not particularly limited and may be determined appropriately, for example, considering its solubility in dimethyl sulfoxide and its elution into the spinning bath. When the epoxy group-containing compound is a glycidyl methacrylate-containing polymer and / or a glycidyl acrylate-containing polymer, for example, from the viewpoint of reducing elution into the spinning bath, it is preferable that the weight-average molecular weight be 3000 or more, and from the viewpoint of solubility in organic solvents such as dimethyl sulfoxide, it is preferable that the weight-average molecular weight be 100000 or less.

[0046] The spinning solution may, if necessary, contain other additives to improve fiber properties, as long as they do not hinder the effects of the present invention. Examples of such additives include gloss modifiers, colorants such as organic pigments, inorganic pigments, and dyes, and stabilizers to improve light resistance and heat resistance.

[0047] The wet spinning process may include at least a coagulation step, a washing step, and a drying step. It is also preferable to include a wet drawing step performed before the washing step or after the washing step and before the drying step. From the viewpoint of chitosan durability, it is necessary to apply chitosan and a nonionic surfactant before the drying step (hereinafter also referred to as the oil application step). The amount of chitosan applied is preferably about three times the amount of chitosan extracted from the desired dilute acetic acid in the resulting acrylic fiber, or preferably about one time the amount of chitosan extracted from the desired concentrated hydrochloric acid in the resulting acrylic fiber. It is preferable to perform the oil application step after the wet drawing step. Furthermore, from the viewpoint of fiber strength, it is preferable to include a dry drawing step performed after the drying step. Furthermore, if necessary, a heat relaxation treatment step performed after the dry drawing step may be included.

[0048] First, in the solidification process, the spinning solution is discharged into the solidification bath through a spinning nozzle and solidified to form a yarn (also referred to as solidified yarn). The spinning nozzle can be used as appropriate according to the desired fiber cross-section. The fiber cross-section is not particularly limited and may be circular, elliptical, irregularly shaped, or any other cross-section.

[0049] The spinning speed is not particularly limited, but from the viewpoint of industrial productivity, for example, it is preferably 2 to 17 m / min. The nozzle draft is not particularly limited, but from the viewpoint of manufacturing process stability, for example, it is preferably 0.8 to 2.0.

[0050] The coagulation bath can be an aqueous solution of a good solvent, such as dimethyl sulfoxide, with a concentration of 20-70% by weight. The temperature of the coagulation bath can be 5-40°C. If the organic solvent concentration in the coagulation bath is too low, coagulation will proceed too quickly, resulting in a coarse coagulation structure and a tendency to form voids inside the fibers.

[0051] Next, in the wet stretching process, it is preferable that the acrylic fibers (coagulated yarn) be wet stretched (also referred to as primary stretching) in a stretching bath. The stretching bath can be an aqueous solution with a lower concentration of a good solvent such as dimethyl sulfoxide than that of the coagulation bath. The temperature of the stretching bath is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. The stretching ratio is not particularly limited, but from the viewpoint of increasing the strength and productivity of the fibers, it is preferably 2 to 8 times. When primary stretching is performed using a water bath, the bath stretching process may be performed after the water washing process described later, or primary stretching and water washing may be performed simultaneously.

[0052] Next, in the washing process, the acrylic fibers are washed with hot water at 30°C or higher to remove beneficial solvents such as dimethyl sulfoxide from the acrylic fibers. Alternatively, the coagulated yarn may be guided to hot water at 30°C or higher, and primary stretching and washing may be performed simultaneously. Alternatively, primary stretching may be performed after the washing process. In the washing process, for example, using hot water at 70°C or higher makes it easier to remove beneficial solvents such as dimethyl sulfoxide from the acrylic fibers.

[0053] Next, in the oil application step, chitosan and a nonionic surfactant (one or more nonionic surfactants selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers, with an HLB of 13.0 or higher) are dissolved or dispersed in water to apply chitosan and a nonionic surfactant to the yarn. In the oil application step, organic solvents such as dimethyl sulfone, ε-caprolactam, ethylene carbonate, and sulfolane may be applied to the yarn to improve the curl-setting properties with hot water.

[0054] The chitosan-containing oil composition may, for example, contain 0.05 to 5% by weight of chitosan and 0.5 to 10% by weight of a nonionic surfactant. It is desirable that the chitosan-containing oil composition also contains acetic acid or hydrochloric acid to dissolve the chitosan. The chitosan-containing oil composition is not particularly limited, but for example, it may contain 0.05 to 5% by weight of chitosan, 0.025 to 10% by weight of acetic acid, 0.5 to 10% by weight of a nonionic surfactant, and 0.1 to 5% by weight of dimethyl sulfone, with the remainder being water.

[0055] The chitosan-containing oil composition may optionally contain other additives to improve fiber properties, provided that they do not hinder the effects of the present invention. Examples of such additives include fiber binding agents such as urethane polymers and cationic ester polymers.

[0056] Next, the acrylic fibers are dried in the drying process. The drying temperature is not particularly limited, but is, for example, 110 to 190°C. The dried fibers are preferably further dry-stretched (secondary stretching). The stretching temperature for secondary stretching is not particularly limited, but is, for example, 110 to 190°C. The stretching ratio is not particularly limited, but is preferably 1 to 4 times, more preferably 1 to 3 times, and even more preferably 1 to 2 times. The total stretching ratio, including bath stretching before drying, is preferably 2 to 10 times, more preferably 2 to 8 times, even more preferably 2 to 6 times, and particularly preferably 2 to 4 times.

[0057] After dry stretching, the fibers are preferably relaxed in a heat relaxation treatment process. The relaxation rate is not particularly limited, but is preferably 5% or more, and more preferably 10-30%. The heat relaxation treatment can be carried out at a high temperature, for example, in a dry heat atmosphere or a superheated steam atmosphere at 150-200°C.

[0058] (headdress products) Headwear products are not particularly limited, but examples include hair wigs, hairpieces, weaving, hair extensions, braided hair, hair accessories, and doll hair. Antibacterial acrylic artificial hair fibers may be used alone as artificial hair to construct headwear products. Alternatively, headwear products may be constructed by combining antibacterial acrylic artificial hair fibers with other artificial hair fibers, as well as natural fibers such as human hair and animal hair. Other artificial hair fibers are not particularly limited, but examples include polyvinyl chloride fibers, nylon fibers, polyester fibers, and regenerated collagen fibers. [Examples]

[0059] The present invention will be described below with reference to one or more embodiments, but the present invention is not limited to the following embodiments.

[0060] The measurement and evaluation methods used in the examples and comparative examples are as follows.

[0061] (Single fiber fineness) The fiber fineness was measured using a motorbike-type fiber fineness analyzer, "DENIER COMPUTER Type DC-11" (manufactured by Saatch), and the average of the measurements from 30 samples was calculated to determine the single fiber fineness.

[0062] (Content of chitosan extracted with dilute acetic acid) The following procedure was used to extract chitosan from the fibers using dilute acetic acid, and the content of the chitosan extracted with dilute acetic acid was determined. 1) 1.87 g of glycine [Fujifilm Wako Pure Chemical Industries] and 1.46 g of sodium chloride [Fujifilm Wako Pure Chemical Industries] were dissolved in pure water to make a 250 g solution, and then 0.1 M hydrochloric acid [Fujifilm Wako Pure Chemical Industries] was added until the pH reached 3.2 to prepare a buffer solution. 2) 150 mg of Reactive Red 4 [MP Biomedicals, LLC] was dissolved in pure water to make a 100 g solution, and 5 g of this solution was diluted 50 times with the buffer solution from 1) to prepare the dye solution. 3) 3.0 g of fiber and 20 g of 0.1 wt% acetic acid aqueous solution were added to a glass bottle and heated at 90°C for 1 hour to prepare the extract. 4) After allowing the extract to cool, 5 mL of dye solution and 0.5 mL of extract were immediately mixed, and the absorbance at 578 nm was measured using a UV-Vis spectrophotometer [Shimadzu Corporation, UV-1800]. At this time, a mixture of 0.5 mL of buffer solution and 5 mL of dye solution was used as a reference. 5) Using a mixture of 0.5 mL of buffer solution and 5 mL of dye solution as a reference, a calibration curve was created from the absorbance at 578 nm using a mixture of 0.5 mL of chitosan aqueous solution (prepared to 0.0025% by weight) and 5 mL of dye solution. Based on this calibration curve and the absorbance values ​​from 4), the chitosan concentration in the extract was calculated, and the content of chitosan extracted with dilute acetic acid was determined.

[0063] (Chitosan content extracted with concentrated hydrochloric acid) The following procedure was used to extract chitosan from the fibers using concentrated hydrochloric acid, and the chitosan content extracted with concentrated hydrochloric acid was determined. 1) 0.2 g of the pulverized fiber sample was heated under reflux with 10 mL of 12N hydrochloric acid to decompose the chitosan, and then diluted to 20 mL with water to obtain a chitosan decomposition solution. 2) To 30 mL of water, 2 mL of chitosan hydrolysate and 3.8 g of sodium borate were added, then the solution was neutralized to pH 7 with 12N hydrochloric acid and the volume was adjusted to 50 mL. 3)1 mL of the solution obtained in 2) was mixed with the derivatization reagent 9-fluorenylmethyl chloroformate (20 mg / 20 mL acetonitrile solution), and after standing for 24 hours, 3 mL of a mixed solvent of acetonitrile:water = 1:1 (containing 0.25% formic acid) was added to prepare the HPLC test solution. 4) The chitosan content extracted with concentrated hydrochloric acid was determined from the peak area obtained by HPLC analysis and a calibration curve created using glucosamine hydrochloride.

[0064] (Amount of oil residue) Approximately 2 g of the sample (fiber) (sample weight W0) was cut into 12-15 cm lengths and packed into a stainless steel tube (oil extraction tube) with a hole of approximately 1 mm at the bottom. Next, 35 mL of a mixture of ethanol and cyclohexane (weight ratio) was prepared as the oil extract, and approximately 20 mL was added to the oil extraction tube. The lid of the oil extraction tube was adjusted so that the extraction rate was approximately 1 drop / 1-1.5 seconds, and the oil extraction was started. At this time, a tray (empty tray weight W1) heated to 120°C by a heater was used as a receiving tray for the dripping liquid, and the tube was set up so that the dripping liquid fell into it. Once the dripping was complete, the lid was removed, and the fibers inside the oil extraction tube were pressed with a stainless steel rod to squeeze out the extract. This operation was repeated using the remaining extract (approximately 15 mL). After extraction was complete, the tray was placed in a 90°C oven, removed after 5 minutes, and the total tray weight (W2) was measured after the extract had dried and all of the oil remained. The amount of oil adhering to the tray (weight %) was then calculated using the following formula 1. [Formula 1] Amount of oil coating (weight %) = (W2 - W1) / W0 × 100

[0065] (Antibacterial) The antibacterial activity value was measured according to JIS L 1902:2015 Antibacterial Testing and Quantitative Testing of Textile Products (Bacterial Solution Absorption Method). Staphylococcus aureus was used in the test. To prevent alteration of the sample's shape, the test was conducted without autoclaving the sample. According to the "SEK Mark Textile Product Certification Standards," an antibacterial activity value of 2.2 or higher indicates antibacterial and deodorizing effects.

[0066] (odor resistance) The amount of isovaleric acid volatilized by bacterial growth was measured using the following procedure. 1) A test bacterial suspension was prepared by mixing 10 mL of 2xYT medium, 5.0 mL of 2% L-leucine, 4.8 mL of sterile water, and 0.2 mL of microbial suspension (Staphylococcus aureus, turbidity OD600 = 1.0). 2) The fiber sample was cut into pieces approximately 3 cm in length, 0.4 g was placed in a 50 mL vial, 100 μL of the test bacterial solution was added, and the sample was allowed to stand at 37°C for 72 hours to culture the microorganisms. 3) After 72 hours of incubation, the entire sample volume was removed from each vial, and each sample was placed in a 5L sampling bag, with the cut portion sealed. After degassing the bag with a vacuum pump, 2L of high-purity nitrogen gas was injected and the bag was sealed. 4) After standing at room temperature for 2 hours, volatile organic compounds contained in 1 L of nitrogen gas in the bag were collected using a cartridge containing 2,6-diphenyl-p-phenylene oxide and analyzed using a gas chromatograph-mass spectrometer. The area of ​​the peak corresponding to isovaleric acid in the total ion chromatogram was determined using the accompanying analysis software, and the amount of volatilization was determined using a pre-prepared calibration curve. 5) After completing step 4, the sample was removed from the bag and dried at 120°C, and the dry mass of the sample was determined. 6) The amount of isovaleric acid volatilized per 1 kg of dry fiber mass was calculated from the amount of isovaleric acid volatilized in step 4 and the dry mass of the sample obtained in step 5. The limit of quantification was 42 μg / kg.

[0067] (Glossy) [Rating 1] Three individuals with over three years of experience in wig aesthetic evaluation performed a visual evaluation of fiber bundle samples with a total fineness of 1.2 million to 1.3 million dtex to determine gloss. AFRELLE was used as the reference sample. The gloss of the reference sample was measured and calculated in gloss evaluation 2. BNT The result was 56.3. A (Excellent): Evaluated as having better gloss than the reference sample. B (Good): Evaluated as having the same gloss as the reference sample. C (Poor): Samples evaluated as having worse gloss than the reference sample. [Rating 2] Using the SAMBA Hair System from Bossa Nova Technologies BNT Measure and calculate L BNT Based on this, gloss was evaluated using the following three-level criteria. <L BNT > L BNTThe intensity of specular and diffuse reflected light was measured by shining a light source onto a fiber bundle attached to a curved surface using the SAMBA Hair System manufactured by Bossa Nova Technologies, and the intensity was calculated using the following formula 2. [Formula 2] L BNT =100 × {S in / (D+S out )} × (1 / W visual ) S in :Center specular reflection light intensity S out :Off-center specular reflection light intensity D: Diffuse reflected light intensity W visual [percent]: width of reflected light <Judgment> A (Very Good): L BNT ≥65.0 B (good): 50.0≦L BNT <65.0 C (defective):L BNT <50.0

[0068] (Example 1) An acrylic copolymer consisting of 46% by weight of acrylonitrile, 52% by weight of vinyl chloride, and 2% by weight of sodium styrene sulfonate was dissolved in dimethyl sulfoxide (DMSO) to prepare a resin solution with an acrylic copolymer concentration of 26.0% by weight and a water concentration of 2.7% by weight. Next, carbon black, a red dye (CI Basic Red 46), and a blue dye (CI Basic Blue 41) were added to the resin solution as colorants in amounts of 2.1 parts by weight, 0.04 parts by weight, and 0.07 parts by weight, respectively, per 100 parts by weight of the acrylic copolymer. Furthermore, 0.8 parts by weight of polyglycidyl methacrylate (weight-average molecular weight 12000) was added per 100 parts by weight of the acrylic copolymer to prepare a spinning stock. The spinning stock was extruded into a coagulation bath of a 47% by weight DMSO aqueous solution at 25°C using a spinning nozzle (pore size 0.3 mm, number of pores 100) and wet-spun at a spinning speed of 2 m / min. After that, it was stretched 2.1 times in a stretching bath of a 50% by weight DMSO aqueous solution at 90°C. Subsequently, it was washed with 90°C hot water. Next, the primary drawn yarn after washing was immersed for 1 to 3 seconds in an oil bath (60°C) containing a chitosan-containing oil composition (consisting of 0.1% by weight of chitosan, 0.05% by weight of acetic acid, 5.0% by weight of polyoxyethylene (20) sorbitan monooleate (the number in parentheses indicates the average number of moles of oxyethylene groups added, the same applies below; HLB: 15.0, melting point: -25°C), 2.0% by weight of dimethyl sulfone, and 92.9% by weight of distilled water) to impregnate the yarn with the chitosan-containing oil composition. After drying at 140°C, the yarn was stretched three times and subjected to a 27% relaxation treatment at 155°C to obtain acrylic fibers with a single fiber fineness of approximately 46 dtex. The degree of deacetylation of the chitosan was 71%. The crustacean protein content in chitosan was measured using the Crustacean Kit II "Maruha Nichiro" manufactured by Maruha Nichiro Corporation and the FA Test EIA-Crustacean II "Nissui" manufactured by Nissui Pharmaceutical Co., Ltd. In both measurements, the content was 0.1 μg or less per gram of chitosan (below the limit of quantification).

[0069] (Example 2) An acrylic fiber with a single fiber fineness of approximately 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 1.0% by weight of chitosan, 0.5% by weight of acetic acid, 4.4% by weight of polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25℃), 2.0% by weight of dimethyl sulfone, and 92.1% by weight of distilled water.

[0070] (Example 3) An acrylic fiber with a single fiber fineness of approximately 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 3.0% by weight of chitosan, 1.5% by weight of acetic acid, 4.4% by weight of polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25℃), 2.0% by weight of dimethyl sulfone, and 89.1% by weight of distilled water.

[0071] (Example 4) An acrylic fiber with a single fiber fineness of approximately 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 1.0% by weight of chitosan, 0.5% by weight of acetic acid, 3.0% by weight of polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25℃), 2.0% by weight of dimethyl sulfone, and 93.5% by weight of distilled water.

[0072] (Example 5) An acrylic fiber with a single fiber fineness of approximately 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 1.0% by weight of chitosan, 0.5% by weight of acetic acid, 7.0% by weight of polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25℃), 2.0% by weight of dimethyl sulfone, and 89.5% by weight of distilled water.

[0073] (Example 6) An acrylic fiber with a single fiber fineness of approximately 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 1.0% by weight of chitosan, 0.5% by weight of acetic acid, 6.0% by weight of polyoxyethylene monolaurate (average number of moles of oxyethylene groups added: 9, HLB: 13.3, melting point: 10℃), 2.0% by weight of dimethyl sulfone, and 90.5% by weight of distilled water.

[0074] (Example 7) An acrylic fiber with a single fiber fineness of approximately 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 1.0% by weight of chitosan, 0.5% by weight of acetate, 6.0% by weight of polyoxyethylene-(2-ethyl)hexyl ether (average number of moles of oxyethylene groups added: 9, HLB: 15, melting point: -25℃), 2.0% by weight of dimethyl sulfone, and 90.5% by weight of distilled water.

[0075] (Example 8) An acrylic fiber with a single fiber fineness of approximately 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 1.0% by weight of chitosan, 0.5% by weight of acetic acid, 6.0% by weight of polyoxyethylene (20) sorbitan monolaurate (HLB: 16.7, melting point: -14℃), 2.0% by weight of dimethyl sulfone, and 90.5% by weight of distilled water.

[0076] (Comparative Example 1) The chitosan-containing oil composition was used in the same manner as in Example 1, except that it consisted of 5.0% by weight of chitosan, 2.5% by weight of acetic acid, 4.4% by weight of polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25℃), 2.0% by weight of dimethyl sulfone, and 86.1% by weight of distilled water. The chitosan-containing oil composition was impregnated in the same manner as in Example 1 and dried at 140℃. Subsequently, when attempting to stretch the material was made, stretching was not possible.

[0077] (Comparative Example 2) Except for using a chitosan-containing oil composition consisting of 1.0% by weight of chitosan, 0.5% by weight of acetic acid, 0.4% by weight of polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25℃), 2.0% by weight of dimethyl sulfone, and 96.1% by weight of distilled water, an acrylic fiber with a single fiber fineness of approximately 46 dtex was prepared in the same manner as in Example 1. However, it generated strong static electricity and was difficult to handle.

[0078] (Comparative Example 3) When acrylic fibers with a single fiber fineness of approximately 46 dtex were prepared in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 1.0% by weight of chitosan, 0.5% by weight of acetic acid, 10% by weight of polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25℃), 2.0% by weight of dimethyl sulfone, and 86.5% by weight of distilled water, the separation properties of the fiber bundles deteriorated.

[0079] (Comparative Example 4) An acrylic fiber with a single fiber fineness of approximately 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 1.0% by weight of chitosan, 0.5% by weight of acetic acid, 6.0% by weight of polyoxyethylene (20) sorbitan trioleate (HLB: 11.0, melting point: -20℃), 2.0% by weight of dimethyl sulfone, and 90.5% by weight of distilled water.

[0080] The chitosan content, oil adhesion amount, antibacterial properties, deodorizing properties, and gloss of the acrylic fibers in the examples and comparative examples were measured and evaluated as described above, and the results are shown in Table 1 below.

[0081] [Table 1]

[0082] As can be seen from Table 1, the acrylic fibers in the examples had high antibacterial properties and good gloss. Furthermore, the acrylic fibers in Examples 2-5, which contained 0.05% by weight or more of chitosan extracted with dilute acetic acid, or 0.1% by weight or more of chitosan extracted with concentrated hydrochloric acid, had an isovaleric acid volatilization amount of 70 μg or less per kg of fiber, and also exhibited good deodorizing properties. On the other hand, in Comparative Example 1, where the chitosan content extracted with dilute acetic acid exceeded 0.4% by weight, or the chitosan content extracted with concentrated hydrochloric acid exceeded 1.2% by weight, stretching could not be performed after the chitosan was applied, resulting in poor process stability. In Comparative Example 2, where the amount of oil applied was less than 0.10% by weight, static electricity was generated, resulting in poor process stability and processability. In Comparative Example 3, where the amount of oil applied exceeded 0.90% by weight, the separation of fiber bundles was poor, resulting in inferior processability. In Comparative Example 4, where a polyoxyethylene sorbitan fatty acid ester with an HLB of 11 was used as the oil, the gloss was poor.

[0083] The present invention is not particularly limited, but includes at least the following embodiments. [1] Contains chitosan and a nonionic surfactant, The chitosan content extracted with dilute acetic acid is 0.005 to 0.4% by weight. The content of the aforementioned nonionic surfactant is 0.10 to 0.90% by weight. The nonionic surfactant is one or more selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers. The aforementioned nonionic surfactant has an HLB of 13.0 or higher, and is an antibacterial acrylic artificial hair fiber. [2] Contains chitosan and a nonionic surfactant, The chitosan content extracted with concentrated hydrochloric acid is 0.014 to 1.2% by weight. The content of the aforementioned nonionic surfactant is 0.10 to 0.90% by weight. The nonionic surfactant is one or more selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers. The aforementioned nonionic surfactant has an HLB of 13.0 or higher, and is an antibacterial acrylic artificial hair fiber. [3] The antibacterial acrylic artificial hair fiber according to [1] or [2], wherein the polyoxyethylene sorbitan fatty acid ester is one or more selected from the group consisting of polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan monolaurate. [4] The antibacterial acrylic artificial hair fiber according to [1] or [2], wherein the polyoxyethylene fatty acid monoester is polyoxyethylene monolaurate. [5] The antimicrobial acrylic artificial hair fiber according to [1] or [2], wherein the polyoxyethylene alkyl ether is polyoxyethylene-(2-ethyl)hexyl ether. [6] The acrylic copolymer constituting the antibacterial acrylic artificial hair fiber comprises 29.5 to 79.5% by weight of acrylonitrile, 20 to 70% by weight of one or more monomers selected from the group consisting of vinyl chloride and vinylidene chloride, and 0.5 to 5% by weight of a sulfonic acid group-containing vinyl monomer, as described in any of [1] to [5]. [7] An antibacterial acrylic artificial hair fiber as described in any of [1] to [6], having a single fiber fineness of 10 to 150 dtex. [8] An antibacterial acrylic artificial hair fiber described in any of [1] to [7], having an antibacterial activity value of 2.2 or higher as measured in accordance with JIS L 1902:2015. [9] Glossy L according to the definition of Bossa Nova Technologies BNT An antibacterial acrylic artificial hair fiber described in any of [1] to [8], wherein the ratio is 50.0 or higher. A head accessory product characterized by containing antibacterial acrylic artificial hair fibers as described in any of [1] to [9].

[11] The headwear product is one selected from the group consisting of hair wigs, hairpieces, weaving, hair extensions, braided hair, hair accessories and doll hair, as described in

[10] . A method for producing antibacterial acrylic artificial hair fibers as described in any of [1] to [9], A spinning solution containing an acrylic copolymer is wet-spun, and before the resulting yarn dries, chitosan and a nonionic surfactant are applied to the yarn. A method for producing antibacterial acrylic artificial hair fibers, wherein the nonionic surfactant has an HLB of 13.0 or higher and is one or more selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers.

[13] A method for producing antibacterial acrylic artificial hair fibers according to

[12] , wherein chitosan and a nonionic surfactant are applied to the yarn after wet stretching.

[14] A method for producing antimicrobial acrylic artificial hair fibers according to

[12] or

[13] , comprising applying chitosan and a nonionic surfactant, drying, and then dry-stretching the yarn.

Claims

1. It contains chitosan and a nonionic surfactant. The chitosan extracted with dilute acetic acid has a content of 0.005 to 0.4% by weight, or the chitosan extracted with concentrated hydrochloric acid has a content of 0.014 to 1.2% by weight. The content of the nonionic surfactant is 0.10 to 0.90% by weight. The nonionic surfactant is one or more selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers. The aforementioned nonionic surfactant has an HLB of 13.0 or higher, and is an antibacterial acrylic artificial hair fiber.

2. The antibacterial acrylic artificial hair fiber according to claim 1, wherein the polyoxyethylene sorbitan fatty acid ester is one or more selected from the group consisting of polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan monolaurate.

3. The antibacterial acrylic artificial hair fiber according to claim 1, wherein the polyoxyethylene fatty acid monoester is polyoxyethylene monolaurate.

4. The antibacterial acrylic artificial hair fiber according to claim 1, wherein the polyoxyethylene alkyl ether is polyoxyethylene-(2-ethyl)hexyl ether.

5. The antibacterial acrylic artificial hair fiber according to claim 1, wherein the acrylic copolymer constituting the antibacterial acrylic artificial hair fiber contains 29.5 to 79.5% by weight of acrylonitrile, 20 to 70% by weight of one or more monomers selected from the group consisting of vinyl chloride and vinylidene chloride, and 0.5 to 5% by weight of a sulfonic acid group-containing vinyl monomer.

6. The antibacterial acrylic artificial hair fiber according to claim 1, wherein the single fiber fineness is 10 to 150 dtex.

7. The antibacterial acrylic artificial hair fiber according to claim 1, wherein the antibacterial activity value measured in accordance with JIS L 1902:2015 is 2.2 or higher.

8. Glossy finish according to the definition of Bossa Nova Technologies. BNT The antibacterial acrylic artificial hair fiber according to claim 1, wherein the ratio is 50.0 or higher.

9. A head accessory product characterized by containing antibacterial acrylic artificial hair fibers according to any one of claims 1 to 8.

10. The headwear product according to claim 9, wherein the headwear product is one selected from the group consisting of hair wigs, hairpieces, weaving, hair extensions, braided hair, hair accessories, and doll hair.

11. A method for producing antibacterial acrylic artificial hair fibers according to any one of claims 1 to 8, A spinning solution containing an acrylic copolymer is wet-spun, and before the resulting yarn dries, chitosan and a nonionic surfactant are applied to the yarn. A method for producing antibacterial acrylic artificial hair fibers, wherein the nonionic surfactant has an HLB of 13.0 or higher and is one or more selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters, and polyoxyethylene alkyl ethers.

12. A method for producing antibacterial acrylic artificial hair fibers according to claim 11, comprising applying chitosan and a nonionic surfactant to the yarn after wet stretching.

13. A method for producing antibacterial acrylic artificial hair fibers according to claim 12, comprising applying chitosan and a nonionic surfactant, drying, and then dry-stretching the yarn.

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