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

Abstract

The present invention relates to antimicrobial acrylic artificial hair fibers which comprise chitosan and a nonionic surfactant, wherein: the content of chitosan extracted with diluted acetic acid is 0.005-0.4 wt%, or the content of chitosan extracted with concentrated hydrochloric acid is 0.013-1.3 wt%; the nonionic surfactant is a sorbitan fatty acid ester and a polyoxyethylene triglyceride; the content of the nonionic surfactant is 0.1-0.9 wt%; and the proportion of the sorbitan fatty acid ester in the nonionic surfactant is 20-90 wt%.

Description

Technical Field

[0001] The present invention relates to an antibacterial acrylic artificial hair fiber used for headdress products such as wigs, a headdress product containing the same, and a method for manufacturing the same.

Background Art

[0002] In headdress products such as wigs, human hair or artificial hair has been conventionally used. However, in recent years, it has become difficult to obtain human hair, and the demand for artificial hair has been increasing. Acrylic fibers have been preferably used as artificial hair because their touch, gloss, and volume are similar to those of human hair. For example, Patent Document 1 proposes an artificial hair using a fiber made of an acrylic polymer composed of a halogen-containing vinyl monomer such as acrylonitrile and vinyl chloride, and a vinyl monomer copolymerizable with these. However, the conventional acrylic artificial hair described in Patent Document 1 has low antibacterial properties, and there are problems such as the generation and growth of bacteria when wearing artificial hair for a long time or storing it after wearing. Patent Document 2 proposes an antibacterial acrylic fiber containing chitosan and a quaternary ammonium salt as an acrylic fiber used for clothing.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the case of synthetic fibers, in order to suppress static electricity and the like, an oil agent is applied. However, when an oil agent is applied to an acrylic fiber containing chitosan, the touch deteriorates, and it may be difficult to use it as artificial hair.

[0005] To solve the aforementioned problems, the present invention provides an antibacterial acrylic artificial hair fiber having good antibacterial properties and a smooth texture, 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 nonionic surfactant is a sorbitan fatty acid ester and a polyoxyethylene triglyceride, the content of the nonionic surfactant is 0.10 to 0.90% by weight, and the proportion of sorbitan fatty acid ester in the nonionic surfactant is 20 to 90% by weight.

[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 0.013 to 1.3% by weight, the nonionic surfactant is a sorbitan fatty acid ester and a polyoxyethylene triglyceride, the content of the nonionic surfactant is 0.10 to 0.90% by weight, and the proportion of sorbitan fatty acid ester in the nonionic surfactant is 20 to 90% by weight.

[0008] One or more embodiments of the present invention relate to a headwear product 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, the nonionic surfactant being sorbitan fatty acid ester and polyoxyethylene triglyceride. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide an antibacterial acrylic artificial hair fiber having good antibacterial properties and a smooth texture, as well as a head accessory product containing the same. Furthermore, according to the manufacturing method of the present invention, an antibacterial acrylic-based artificial hair fiber with good antibacterial properties and a smooth texture 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 while improving their tactile feel as artificial hair. As a result, they have found that by using a nonionic surfactant as an oil agent, specifically a certain proportion of sorbitan fatty acid ester and polyoxyethylene triglyceride, 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 a smooth tactile feel can be obtained. Furthermore, the antibacterial acrylic artificial hair fiber of one or more preferred embodiments of the present invention has deodorizing properties by using a combination of chitosan and a specific proportion of sorbitan fatty acid ester and polyoxyethylene triglyceride. Furthermore, the antibacterial acrylic artificial hair fiber of one or more preferred embodiments of the present invention has antiviral properties by using a combination of chitosan and a specific proportion of sorbitan fatty acid ester and polyoxyethylene triglyceride. Furthermore, the antibacterial acrylic artificial hair fibers of one or more preferred embodiments of the present invention have deodorizing properties when chitosan is used in combination with a specific proportion of sorbitan fatty acid ester and polyoxyethylene triglyceride.

[0012] In one or more embodiments of the present invention, when a numerical range is indicated by "~", it includes the values ​​at both ends. For example, the numerical range "X~Y" includes the values ​​at both ends, X and Y. Furthermore, when multiple numerical ranges are described in this specification, they shall include numerical ranges obtained by appropriately combining the upper and lower limits of different numerical ranges.

[0013] (Antibacterial acrylic-based artificial hair fiber) The antibacterial acrylic-based artificial hair fibers contain chitosan and nonionic surfactants (sorbitan fatty acid ester and polyoxyethylene triglyceride).

[0014] Chitosan is a deacetylated product of chitin, a natural polymer. For example, it can be obtained by deacetylating chitin obtained from the exoskeleton of crustaceans such as crabs and shrimp by boiling in a concentrated alkali. The degree of deacetylation of chitosan is not particularly limited and may be about 60-99%, but from the viewpoint of deodorizing properties, it is preferably 70-99%, and more preferably 80-99%. The degree of deacetylation of chitosan can be measured by methods such as NMR spectroscopy, infrared absorption spectroscopy (IR), and colloidal titration. The weight-average molecular weight of chitosan is not particularly limited and may be about 10,000-1,000,000, but from the viewpoint of handling properties of aqueous solutions, it is preferably 10,000-500,000, and more preferably 10,000-300,000. In this specification, the weight-average molecular weight of a compound can be measured by gel permeation chromatography (GPC). GPC measurement is performed using chloroform as the mobile phase and on a polystyrene gel column, and the weight-average molecular weight can be determined in terms of polystyrene equivalent.

[0015] Because antibacterial acrylic artificial hair fibers come into contact with the skin and mouth during use, it is preferable from a safety standpoint that the chitosan contains a low amount of allergens. Since chitosan is often purified from raw materials derived from crustaceans, it may contain crustacean protein, which is a type of allergen. The crustacean protein content in chitosan is preferably 9.9 μg or less per gram of chitosan, more preferably 5.0 μg or less, and even more preferably 1.0 μg or less. For example, samples with a protein content of 10 μg or more per gram of food sample weight may be judged to have the possibility of contamination with trace amounts of specific raw materials. The protein content in chitosan can be measured, for example, by the ELISA method. Specifically, the crustacean protein content in chitosan can be measured by the ELISA method using the Crustacean Kit II "Maruha Nichiro" manufactured by Maruha Nichiro Corporation or the FA Test EIA-Crustacean II "Nissui" manufactured by Nissui Pharmaceutical Co., Ltd.

[0016] In antibacterial acrylic artificial hair fibers, the chitosan content extracted with dilute acetic acid is 0.005 to 0.4% 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 and process stability is poor. From the viewpoint of antibacterial properties, the chitosan content extracted with dilute acetic acid is preferably 0.01% by weight or more. From the viewpoint of having excellent antibacterial properties as well as excellent deodorizing properties, the chitosan content 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 viewpoint of improving stretchability and gloss, the chitosan content extracted with dilute acetic acid is preferably 0.35% by weight or less, more preferably 0.3% by weight or less, even more preferably 0.25% by weight or less, and particularly preferably 0.2% 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 the antibacterial acrylic artificial hair fiber, the content of chitosan extracted with concentrated hydrochloric acid is 0.013 to 1.3% 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 viewpoint of antibacterial property, the content of chitosan 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 excellent antibacterial property and excellent deodorant performance, the content of chitosan extracted with concentrated hydrochloric acid is 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 0.09% by weight or more. The content of chitosan extracted with concentrated hydrochloric acid is preferably 1.0% by weight or less, more preferably 0.8% by weight or less, even more preferably 0.7% by weight or less, even more preferably 0.6% by weight or less, even more preferably 0.5% by weight or less, and particularly preferably 0.4% 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] (Content of chitosan extracted with concentrated hydrochloric acid) 1) 0.2 g of the pulverized fiber sample is heated under reflux with 10 mL of 12N hydrochloric acid to decompose chitosan, and then diluted to 20 mL with water to obtain a chitosan decomposition solution. 2) After adding 2 mL of the chitosan decomposition solution and 3.8 g of sodium borate to 30 mL of water, it is neutralized to pH 7 with 12N hydrochloric acid and diluted to 50 mL. 3) 1 mL of the solution obtained in 2) is mixed with 9-fluorenylmethyl chloroformate (20 mg / 20 mL acetonitrile solution) as a derivatization reagent, allowed to stand for 24 hours, and then 3 mL of a mixed solvent of acetonitrile:water = 1:1 (containing 0.25% formic acid) is added to obtain an HPLC test solution. 4) From the peak area obtained by HPLC analysis and the calibration curve prepared with glucosamine hydrochloride, the content of chitosan extracted with concentrated hydrochloric acid is determined.

[0021] The sorbitan fatty acid ester is not particularly limited, but for example, an ester of sorbitan and a fatty acid can be used as appropriate. The fatty acid may have, for example, 4 to 30 carbon atoms, preferably 6 to 28, more preferably 8 to 26, even more preferably 10 to 24, and particularly preferably 12 to 20 carbon atoms from the viewpoint of tactile properties. 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. The ester may be a monoester, diester, triester, or tetraester.

[0022] 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.

[0023] 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.

[0024] From the viewpoint of tactile properties, sorbitan fatty acid esters of saturated fatty acids are preferred, sorbitan fatty acid esters of saturated fatty acids having 10 to 24 carbon atoms are more preferred, sorbitan fatty acid esters of saturated fatty acids having 12 to 22 carbon atoms are even more preferred, and it is even more preferable that one or more are selected from the group consisting of sorbitan monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan distearate, sorbitan dilaurate, sorbitan dipalmitate, sorbitan tristearate, sorbitan trilaurate, and sorbitan tripalmitate, and it is even more preferable that one or more are selected from the group consisting of sorbitan monostearate, sorbitan monolaurate, and sorbitan monopalmitate. A single sorbitan fatty acid ester may be used alone, or two or more may be used in combination.

[0025] Polyoxyethylene triglycerides are not particularly limited and include, for example, 2-ethylcaproic acid polyoxyethylene triglyceride, laurate polyoxyethylene triglyceride, myristate polyoxyethylene triglyceride, palmitate polyoxyethylene triglyceride, stearate polyoxyethylene triglyceride, crotonic acid polyoxyethylene triglyceride, palmitoleate polyoxyethylene triglyceride, linoleic acid polyoxyethylene triglyceride, linolenic acid polyoxyethylene triglyceride, oleic acid polyoxyethylene triglyceride, polyoxyethylene coconut oil, polyoxyethylene castor oil, and polyoxyethylene hydrogenated castor oil. Polyoxyethylene triglycerides may be used individually or in combination of two or more types.

[0026] In polyoxyethylene triglycerides, the average number of moles of oxyethylene groups added is not particularly limited, but may be, for example, 10 to 200 moles, preferably 25 to 200 moles, more preferably 50 to 200 moles, and even more preferably 50 to 150 moles.

[0027] From the viewpoint of easily dispersing sorbitan fatty acid esters uniformly, the polyoxyethylene triglyceride is preferably one or more selected from the group consisting of polyoxyethylene coconut oil, polyoxyethylene castor oil, and polyoxyethylene hydrogenated castor oil, with polyoxyethylene castor oil and / or polyoxyethylene hydrogenated castor oil being more preferred. The average number of moles of ethyleneoxy groups added in polyoxyethylene castor oil and / or polyoxyethylene hydrogenated castor oil is preferably 50 to 200 moles, and more preferably 100 to 150 moles.

[0028] In antibacterial acrylic artificial hair fibers, the content of nonionic surfactants (total content of sorbitan fatty acid ester and polyoxyethylene triglyceride) is 0.10 to 0.90% by weight. If the content of nonionic surfactants is less than 0.10% by weight, process stability and processability will decrease due to static electricity generation. If the content of nonionic surfactants exceeds 0.90% by weight, the feel will deteriorate. The content of nonionic surfactants 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. In this specification, the content of nonionic surfactants (hereinafter also referred to as oil adhesion amount) can be measured as follows.

[0029] (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

[0030] The proportion of sorbitan fatty acid ester in the nonionic surfactant (oil) (i.e., relative to the total weight of sorbitan fatty acid ester and polyoxyethylene triglyceride) is 20 to 90% by weight, and the proportion of polyoxyethylene triglyceride is 10 to 80% by weight. If the proportion of sorbitan fatty acid ester is less than 20% by weight, or if the proportion of polyoxyethylene triglyceride exceeds 80% by weight, the tactile feel deteriorates. If the proportion of sorbitan fatty acid ester exceeds 90% by weight, or if the proportion of polyoxyethylene triglyceride is less than 10% by weight, the sorbitan fatty acid ester cannot be uniformly dispersed. From the viewpoint of tactile feel, the proportion of sorbitan fatty acid ester is preferably 25% by weight or more, more preferably 30% by weight or more, even more preferably 35% by weight or more, and particularly preferably 40% by weight or more. In this specification, the proportion of sorbitan fatty acid ester can be measured as follows.

[0031] (Percentage of sorbitan fatty acid esters) In antibacterial acrylic artificial hair fibers, the proportion of sorbitan fatty acid ester in the nonionic surfactant (oil) can be calculated by dissolving and dispersing the fiber in acetone, precipitating the resin components with chloroform, concentrating the soluble components, adding deuterated chloroform to the resulting concentrate to remove insoluble components, and analyzing the soluble components by 1H NMR.

[0032] In antibacterial acrylic artificial hair fibers, the HLB of the nonionic surfactant, specifically sorbitan fatty acid ester or polyoxyethylene triglyceride, is not particularly limited. For example, from the viewpoint of gloss, it may be 13.0 or higher, 13.5 or higher, 14.0 or higher, 14.5 or higher, or 15.0 or higher. Also, from the viewpoint of emulsification, the HLB of the sorbitan fatty acid ester or polyoxyethylene triglyceride may be 19 or less. In this specification, the HLB (hydrophilic-lipophilic balance) of the nonionic surfactant is determined by the Griffin method.

[0033] In antibacterial acrylic artificial hair fibers, the melting point of the nonionic surfactant, specifically sorbitan fatty acid ester or polyoxyethylene triglyceride, is not particularly limited, but from the viewpoint of gloss, it may be 25°C or lower, 22°C or lower, or 20°C or lower. In this specification, the melting point of the nonionic surfactant is determined by visual inspection or the like.

[0034] 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, and 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 one or more chlorine-containing monomers selected from the group consisting of vinyl chloride and vinylidene chloride, and 0.5 to 5% by weight of sulfonic acid group-containing vinyl monomers. In the acrylic copolymer, a acrylonitrile content of 29.5 to 79.5% by weight results in good heat resistance. In the acrylic copolymer, a content of 20 to 70% by weight of one or more chlorine-containing monomers selected from the group consisting of vinyl chloride and vinylidene chloride results in good flame retardancy. The hydrophilicity of the acrylic copolymer increases when it contains 0.5 to 5% by weight of a sulfonic acid group-containing vinyl monomer. More preferably, the acrylic copolymer contains 34.5 to 74.5% by weight of acrylonitrile, 25 to 65% by weight of one or more chlorine-containing 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. 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. The acrylic copolymer contains 39.5 to 69.5% by weight of nitrile, 30 to 60% by weight of vinyl chloride, and 0.5 to 5% by weight of a sulfonic acid group-containing vinyl monomer; more preferably, it contains 39.5 to 59.5% by weight of acrylonitrile, 40 to 60% by weight of vinyl chloride, and 0.5 to 5% by weight of a sulfonic acid group-containing vinyl monomer; particularly preferably, it contains 39.5 to 49.5% by weight of acrylonitrile, 50 to 60% by weight of vinyl chloride, and 0.5 to 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.

[0035] The sulfonic acid group-containing vinyl monomer is not particularly limited, but for example, 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 can be used. The sulfonic acid group-containing vinyl monomer may be used alone or in combination of two or more types.

[0036] 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 impair the effects of the present invention. Examples of additives include colorants such as gloss modifiers, organic pigments, inorganic pigments, and dyes, light stabilizers, heat stabilizers, fiber consolidators, deodorizers, and fragrances. From the viewpoint of tactile feel and the stability of the chitosan-containing oil, the antibacterial acrylic artificial hair fiber preferably contains only sorbitan fatty acid ester and polyoxyethylene triglyceride, which are nonionic surfactants, as the oil. If the antibacterial acrylic artificial hair fiber contains other oils, from the viewpoint of tactile feel, it is preferable that the total content of these oils, sorbitan fatty acid ester, and polyoxyethylene triglyceride is 0.90% by weight or less.

[0037] 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.

[0038] From the viewpoint of excellent antibacterial properties, antibacterial acrylic artificial hair fibers preferably have an antibacterial activity value of 2.2 or higher, more preferably 3.0 or higher, and even more preferably 4.0 or higher, as measured in accordance with JIS L 1902:2015. From the viewpoint of excellent antibacterial properties even after washing, antibacterial acrylic artificial hair fibers preferably have an antibacterial activity value of 4.0 or higher, and more preferably 4.5 or higher, as measured in accordance with JIS L 1902:2015 after washing. Antibacterial acrylic artificial hair fibers have high antibacterial properties against bacteria such as Staphylococcus aureus.

[0039] From the viewpoint of excellent odor control, antibacterial acrylic artificial hair fibers preferably have a volatilization amount of isovaleric acid generated by the growth of bacteria such as Staphylococcus aureus of 150 μg or less, more preferably 100 μg or less, and even more preferably 70 μg or less per 1 kg of fiber. Isovaleric acid is known as an odor component generated from the scalp. In this specification, the volatilization amount of isovaleric acid generated by the growth of bacteria can be measured specifically as described in the examples.

[0040] From the viewpoint of achieving a smoother feel, the antibacterial acrylic artificial hair fiber preferably has an average coefficient of friction (MIU) of 0.00365 or less, more preferably 0.00350 or less, and even more preferably 0.00320 or less. In this specification, the average coefficient of friction can be measured using a friction feel tester (Kato Tech Co., Ltd., KES-SE-STP) as described in the examples.

[0041] From the viewpoint of excellent antiviral properties, antibacterial acrylic artificial hair fibers preferably have an antiviral activity value of 3.0 or higher, more preferably 3.5 or higher, and even more preferably 4.0 or higher, as measured in accordance with JIS L 1922:2016. From the viewpoint of excellent antiviral properties even after washing, antibacterial acrylic artificial hair fibers preferably have an antiviral activity value of 2.0 or higher, and more preferably 3.0 or higher, as measured in accordance with JIS L 1922:2016, after 10 washes. Antibacterial acrylic artificial hair fibers exhibit high virality against, for example, influenza A virus.

[0042] Antibacterial acrylic artificial hair fibers have excellent deodorizing properties, 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. In this specification, deodorizing properties can be measured specifically as described in the examples.

[0043] (Manufacturing method) Antibacterial acrylic artificial hair fibers can be produced, for example, by wet spinning a spinning solution containing an acrylic copolymer, and then applying chitosan and nonionic surfactants (sorbitan fatty acid ester and polyoxyethylene triglyceride) to the yarn before drying.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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, sorbitan fatty acid ester, and polyoxyethylene triglyceride 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 by the desired acetic acid in the resulting acrylic fiber, or preferably about 1.5 times the amount of chitosan extracted by 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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 wet stretching process may be performed after the water washing process described later, or primary stretching and water washing may be performed simultaneously.

[0055] 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.

[0056] Next, in the oil application step, chitosan, sorbitan fatty acid ester, and polyoxyethylene triglyceride (nonionic surfactant) are applied to the yarn using a chitosan-containing oil composition in which chitosan, sorbitan fatty acid ester, and polyoxyethylene triglyceride (nonionic surfactant) are dissolved or dispersed in water. In the oil application step, one or more organic solvents selected from the group consisting of dimethyl sulfone, ε-caprolactam, ethylene carbonate, and sulfolane may be applied to the yarn to improve the curl-setting properties with hot water.

[0057] The chitosan-containing oil composition may contain, for example, 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. In the chitosan-containing oil composition, the weight ratio of sorbitan fatty acid ester to polyoxyethylene triglyceride is sorbitan fatty acid ester: polyoxyethylene triglyceride = 20 to 90:10 to 80. In fibers, the ratio of polyoxyethylene triglyceride to sorbitan fatty acid ester is approximately the same as the ratio of polyoxyethylene triglyceride to sorbitan fatty acid ester in the chitosan-containing oil composition.

[0058] 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 sorbitan fatty acid ester, and 0.5 to 10% by weight of polyoxyethylene triglyceride (however, the total amount of sorbitan fatty acid ester and polyoxyethylene triglyceride is 0.5 to 10% by weight), with the remainder being water. Alternatively, the chitosan-containing oil composition 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 sorbitan fatty acid ester, 0.5 to 10% by weight of polyoxyethylene triglyceride (however, the total amount of sorbitan fatty acid ester and polyoxyethylene triglyceride is 0.5 to 10% by weight), and 0.1 to 5% by weight of dimethyl sulfone, with the remainder being water.

[0059] 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.

[0060] Next, the acrylic fibers are dried in a 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 (also referred to as 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, for example, preferably 1 to 4 times, more preferably 1 to 3 times, and even more preferably 1 to 2 times. The total stretching ratio, including wet 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.

[0061] 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 140-200°C.

[0062] (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]

[0063] One or more embodiments of the present invention will be described below with reference to examples, but the present invention is not limited to the following embodiments.

[0064] The measurement and evaluation methods used in the examples and comparative examples are as follows.

[0065] (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.

[0066] (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.

[0067] (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.

[0068] (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

[0069] (Percentage of sorbitan fatty acid esters in the fiber) The ratio of sorbitan fatty acid ester to polyoxyethylene triglyceride in the chitosan-containing oil composition was determined, and this was used as the ratio of sorbitan fatty acid ester in the fiber. If the blending ratio of sorbitan fatty acid ester to polyoxyethylene triglyceride in the chitosan-containing oil composition is unknown, the fiber can be dissolved and dispersed in acetone, the resin can be precipitated with chloroform, the soluble components can be concentrated, deuterated chloroform can be added to the resulting concentrate to remove insoluble components, and the soluble components can be analyzed by 1H NMR to calculate the ratio of sorbitan fatty acid ester in the mixture of sorbitan fatty acid ester and polyoxyethylene triglyceride in the fiber.

[0070] (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.

[0071] (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.

[0072] (Antiviral) The antiviral activity value was measured according to JIS L 1922:2016, the test method for antiviral properties of textile products. Influenza A virus (H3N3) was used for the test. The samples were washed according to the "Standard Washing Method for SEK Mark Textile Products" specified by the Japan Textile Evaluation Technology Council. An antiviral activity value of 2 or higher indicates antiviral properties.

[0073] (Deodorizing properties) The deodorizing effect on isovaleric acid was evaluated using the following method. 1) A 0.03% aqueous solution of isovaleric acid was prepared. 2) After adding 0.2 mL of isovaleric acid aqueous solution to the surface of 1 g of sample, it was placed in a 1 L sampling bag and the cut portion was sealed. 3) After degassing the inside of the bag with a vacuum pump, 0.5 L of high-purity nitrogen gas was injected through an integrated flow meter and the bag was sealed. 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 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 analysis software, and the gas concentration was determined using a pre-prepared calibration curve. 5) The gas concentration was determined similarly using a control instead of the sample. As the control, we used AFRELLE (modacrylic fiber, manufactured by Kaneka Corporation, hereinafter also simply referred to as "AFRELLE"), a headwear product. 6) The deodorization rate was 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

[0074] (Tactile sensation) [Rating 1] Three individuals with over three years of experience in the aesthetic evaluation of wigs conducted sensory evaluations using fiber bundle samples with a total fineness of 1.2 million to 1.3 million dtex, and judged the tactile feel according to the following three-level criteria. A (Very Good): Rated to have a better texture than AFRELLE. B (Good): Evaluated as having a similar feel to AFRELLE. C (Poor): Rated as having a worse texture than AFRELLE. [Rating 2] Using a friction tester (Kato Tech Co., Ltd., KES-SE-STP), the average friction coefficient MIU between fibers was measured according to the following procedure, and the tactile feel was judged based on the MIU according to the following three-level criteria. <Average coefficient of friction MIU> 1) A 30cm, 4.0g fiber bundle was fixed to the sample stage so that it was 3cm wide. 2) A 12cm, 0.8g fiber bundle was fixed to the bottom of the arm. 3) A 25g weight was placed on the arm and set on the fiber bundle on the sample stage. 4) The arm was slid with the settings SENS:H and SPEED:0.5mm / sec to measure the frictional force, and the average friction coefficient MIU was calculated. <Judgment> A (Excellent): MIU is 0.00320 or less B (Very Good): MIU is above 0.00320 and below 0.00350 C (Good): MIU is between 0.00350 and 0.00365. D (Defective): MIU exceeds 0.00365

[0075] (Example 1) An acrylic polymer consisting of 46% by weight acrylonitrile, 52% by weight vinyl chloride, and 2% by weight sodium styrene sulfonate was dissolved in dimethyl sulfoxide (DMSO) to prepare a spinning solution with a resin 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 0.05% by weight of chitosan, 0.025% by weight of acetic acid, 1.6% by weight of sorbitan monostearate, 2.4% by weight of polyoxyethylene (average number of added moles approximately 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 93.9% 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).

[0076] (Example 2) An acrylic fiber with a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 1.6% by weight of sorbitan monostearate, 2.4% by weight of polyoxyethylene (average number of added moles about 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 93.3% by weight of distilled water.

[0077] (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, 1.6% by weight of sorbitan monostearate, 2.4% by weight of polyoxyethylene (average number of added moles approximately 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 89.5% by weight of distilled water.

[0078] (Example 4) An acrylic fiber with a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 0.6% by weight of sorbitan monostearate, 0.9% by weight of polyoxyethylene (average number of added moles about 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 95.8% by weight of distilled water.

[0079] (Example 5) An acrylic fiber with a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 2.4% by weight of sorbitan monostearate, 3.6% by weight of polyoxyethylene (average number of added moles about 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 91.3% by weight of distilled water.

[0080] (Example 6) An acrylic fiber with a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 1.2% by weight of sorbitan monostearate, 4.8% by weight of polyoxyethylene (average number of added moles about 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 91.3% by weight of distilled water.

[0081] (Example 7) An acrylic fiber with a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 2.8% by weight of sorbitan monostearate, 1.2% by weight of polyoxyethylene (average number of added moles about 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 93.3% by weight of distilled water.

[0082] (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 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 3.6% by weight of sorbitan monostearate, 0.4% by weight of polyoxyethylene (average number of added moles approximately 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 93.3% by weight of distilled water.

[0083] (Example 9) An acrylic fiber with a single fiber fineness of about 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, 1.6% by weight of sorbitan monostearate, 2.4% by weight of polyoxyethylene (average number of added moles about 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 92.5% by weight of distilled water.

[0084] (Example 10) An acrylic fiber with a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 2.0% by weight of sorbitan monolaurate, 2.0% by weight of polyoxyethylene (average number of added moles about 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 93.3% by weight of distilled water.

[0085] (Comparative Example 1) The chitosan-containing oil composition used was one comprising 5.0% by weight of chitosan, 2.5% by weight of acetic acid, 1.6% by weight of sorbitan monostearate, 2.4% by weight of polyoxyethylene (average number of added moles approximately 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 86.5% by weight of distilled water. The chitosan-containing oil composition was impregnated in the same manner as in Example 1 and dried at 140°C. Subsequently, when attempting to stretch the material was made, stretching was not possible.

[0086] (Comparative Example 2) Except for using a chitosan-containing oil composition consisting of 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 0.3% by weight of sorbitan monostearate, 0.5% by weight of polyoxyethylene (average number of added moles approximately 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 96.5% 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.

[0087] (Comparative Example 3) An acrylic fiber with a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 4.0% by weight of sorbitan monostearate, 6.0% by weight of polyoxyethylene (average number of added moles about 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 87.3% by weight of distilled water.

[0088] (Comparative Example 4) An acrylic fiber with a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1, except that the chitosan-containing oil composition used consisted of 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 0.6% by weight of sorbitan monostearate, 5.4% by weight of polyoxyethylene (average number of added moles about 170) hydrogenated castor oil, 2.0% by weight of dimethyl sulfone, and 91.3% by weight of distilled water.

[0089] (Comparative Example 5) When a chitosan-containing oil composition was used, consisting of 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 4.0% by weight of sorbitan monostearate, 2.0% by weight of dimethyl sulfone, and 93.3% by weight of distilled water, the dispersibility of the oil was poor.

[0090] (Comparative 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 0.5% by weight of chitosan, 0.25% by weight of acetic acid, 5.0% by weight of ethylene oxide-propylene oxide block polyether (molar ratio of ethylene oxide / propylene oxide = 20 / 80, weight-average molecular weight 2400), 2.0% by weight of dimethyl sulfone, and 92.3% by weight of distilled water.

[0091] (Comparative 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 acetic acid, 6.0% by weight of polyethylene glycol 400 (PEG400), 2.0% by weight of dimethyl sulfone, and 90.5% by weight of distilled water.

[0092] The chitosan content, oil adhesion amount, sorbitan fatty acid ester ratio, antibacterial properties, deodorizing properties, tactile feel, 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. In Table 1 below, the sorbitan fatty acid ester ratio in the oil tank is the weight percentage of sorbitan fatty acid ester relative to the total weight of sorbitan fatty acid ester and polyoxyethylene triglyceride in the oil tank.

[0093] [Table 1]

[0094] As can be seen from Table 1, the acrylic fibers of the examples had high antibacterial properties and a smooth texture, resulting in a good tactile feel. Furthermore, the acrylic fibers of Examples 2 to 4, which contained 0.02% by weight or more of chitosan extracted with dilute acetic acid, or 0.04% 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, indicating good deodorizing properties. When the deodorizing properties of the acrylic fibers of Examples 2 and 9 were evaluated as described above, the deodorization rates of the acrylic fibers of Examples 2 and 9 were 63% and 74%, respectively, indicating good deodorizing properties. Furthermore, when the antiviral properties of the acrylic fiber of Example 9 were evaluated as described above, the antiviral activity values ​​after 0 washes and 10 washes were 4.5 and 3.0, respectively, indicating good antiviral properties, especially antiviral properties after 10 washes.

[0095] On the other hand, in Comparative Example 1, where the content of chitosan extracted with dilute acetic acid exceeded 0.4% by weight, or the content of chitosan extracted with concentrated hydrochloric acid exceeded 1.3% by weight, stretching could not be performed after the application of chitosan, resulting in poor process stability. In Comparative Example 2, where the total content of oil-based surfactants, i.e., sorbitan fatty acid ester and polyoxyethylene triglyceride, was less than 0.1% by weight, static electricity was generated, resulting in poor process stability and processability. In Comparative Example 3, where the total content of oil-based surfactants, i.e., sorbitan fatty acid ester and polyoxyethylene triglyceride, exceeded 0.9% by weight, the texture was poor. In Comparative Example 4, where the proportion of sorbitan fatty acid ester was less than 20% by weight, the texture was poor. In Comparative Example 5, which used only sorbitan fatty acid ester, it could not be dispersed in water. In Comparative Examples 6 and 7, where ethylene oxide / propylene oxide block polyether or PEG400 was used as the nonionic surfactant, the texture was poor.

[0096] The present invention is not particularly limited, but preferably includes 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 nonionic surfactants are sorbitan fatty acid esters and polyoxyethylene triglycerides. The content of the aforementioned nonionic surfactant is 0.10 to 0.90% by weight. An antibacterial acrylic artificial hair fiber wherein the proportion of sorbitan fatty acid ester in the nonionic surfactant is 20 to 90% by weight. [2] Contains chitosan and a nonionic surfactant, The chitosan content extracted with concentrated hydrochloric acid is 0.013 to 1.3% by weight. The nonionic surfactants are sorbitan fatty acid esters and polyoxyethylene triglycerides. The content of the aforementioned nonionic surfactant is 0.10 to 0.90% by weight. An antibacterial acrylic artificial hair fiber wherein the proportion of sorbitan fatty acid ester in the nonionic surfactant is 20 to 90% by weight. [3] The antibacterial acrylic artificial hair fiber according to [1] or [2], wherein the sorbitan fatty acid ester is one or more selected from the group consisting of sorbitan monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan distearate, sorbitan dilaurate, sorbitan dipalmitate, sorbitan tristearate, sorbitan trilaurate, and sorbitan tripalmitate. [4] The antibacterial acrylic artificial hair fiber according to any one of [1] to [3], wherein the polyoxyethylene triglyceride is one or more selected from the group consisting of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil. [5] 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 [4]. [6] An antibacterial acrylic artificial hair fiber as described in any of [1] to [5], having a single fiber fineness of 10 to 150 dtex. [7] An antibacterial acrylic artificial hair fiber described in any of [1] to [6], having an antibacterial activity value of 2.2 or higher as measured in accordance with JIS L 1902:2015. [8] An antibacterial acrylic artificial hair fiber as described in any of [1] to [7], having an average coefficient of friction (MIU) of 0.00365 or less. Headwear products containing antibacterial acrylic artificial hair fibers as described in any of [9] [1] to [8].

[10] 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 [9]. A method for producing antibacterial acrylic artificial hair fibers as described in any of [1] to [8], A method for producing antibacterial acrylic artificial hair fibers, comprising wet spinning a spinning solution containing an acrylic copolymer, and before the resulting yarn dries, applying chitosan and a nonionic surfactant to the yarn, wherein the nonionic surfactant is a sorbitan fatty acid ester and a polyoxyethylene triglyceride.

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

[11] , comprising applying chitosan and a nonionic surfactant to yarn after wet stretching.

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

[11] or

[12] , 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 0.013 to 1.3% by weight. The nonionic surfactants are sorbitan fatty acid esters and polyoxyethylene triglycerides. The content of the nonionic surfactant is 0.10 to 0.90% by weight. An antibacterial acrylic artificial hair fiber wherein the proportion of sorbitan fatty acid ester in the nonionic surfactant is 20 to 90% by weight.

2. The antibacterial acrylic artificial hair fiber according to claim 1, wherein the sorbitan fatty acid ester is one or more selected from the group consisting of sorbitan monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan distearate, sorbitan dilaurate, sorbitan dipalmitate, sorbitan tristearate, sorbitan trilaurate, and sorbitan tripalmitate.

3. The antibacterial acrylic artificial hair fiber according to claim 1, wherein the polyoxyethylene triglyceride is one or more selected from the group consisting of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil.

4. 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.

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

6. 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.

7. The antibacterial acrylic artificial hair fiber according to claim 1, wherein the average coefficient of friction (MIU) is 0.00365 or less.

8. A head accessory product comprising an antibacterial acrylic artificial hair fiber according to any one of claims 1 to 7.

9. The headwear product according to claim 8, 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.

10. A method for producing antibacterial acrylic artificial hair fibers according to any one of claims 1 to 7, A method for producing antibacterial acrylic artificial hair fibers, comprising wet spinning a spinning solution containing an acrylic copolymer, and before the resulting yarn dries, applying chitosan and a nonionic surfactant to the yarn, wherein the nonionic surfactant is a sorbitan fatty acid ester and a polyoxyethylene triglyceride.

11. A method for producing antibacterial acrylic artificial hair fibers according to claim 10, comprising applying chitosan and a nonionic surfactant to the yarn after wet stretching.

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

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