Classifications

• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
  • A41G3/00—Wigs
• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
  • A41G3/00—Wigs
  • A41G3/0083—Wigs characterised by their hair filaments
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/10—Other agents for modifying properties
  • D01F1/103—Agents inhibiting growth of microorganisms
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
  • D06M15/03—Polysaccharides or derivatives thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/507—Polyesters
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/53—Polyethers

Definitions

• the present invention relates to an antibacterial acrylic artificial hair fiber used for head ornament products such as wigs, a head ornament product containing the same, and a method for producing the same.
• Patent Literature 1 describes artificial hair using fibers made from acrylic polymers composed of halogen-containing vinyl monomers such as acrylonitrile and vinyl chloride and vinyl monomers copolymerizable therewith. Proposed.
• Patent Document 1 has low antibacterial properties, and there is a problem that bacteria are generated or proliferate when the artificial hair is 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.
• the present invention provides an acrylic artificial hair fiber with good antibacterial properties and gloss, a head ornament product containing the same, and a method for producing the same.
• One or more embodiments of the present invention comprise chitosan and a nonionic surfactant, the content of chitosan extracted with dilute acetic acid is 0.005-0.4% by weight, and the nonionic surfactant is 0.10 to 0.90% by weight, and the nonionic surfactant is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters and polyoxyethylene alkyl ethers. One or more, and the HLB of the nonionic surfactant is 13.0 or more.
• One or more embodiments of the present invention comprise chitosan and a nonionic surfactant, the content of chitosan extracted with concentrated hydrochloric acid is 0.014-1.2% by weight, and the nonionic surfactant is 0.10 to 0.90% by weight, and the nonionic surfactant is selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters and polyoxyethylene alkyl ethers. One or more, and the HLB of the nonionic surfactant is 13.0 or more.
• One or more embodiments of the present invention relate to headdress products characterized by comprising the antibacterial acrylic artificial hair fibers.
• One or more embodiments of the present invention provide a method for producing the antibacterial acrylic artificial hair fiber, wherein a spinning solution containing an acrylic copolymer is wet-spun, and the obtained yarn is dried before the yarn is dried. Chitosan and a nonionic surfactant are imparted to the fibers, and the nonionic surfactant has an HLB of 13.0 or more, and polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid monoester and poly The present invention relates to a method for producing antibacterial acrylic artificial hair fibers, which are at least one selected from the group consisting of oxyethylene alkyl ethers.
• an antibacterial acrylic artificial hair fiber having good antibacterial properties and gloss it is possible to provide an antibacterial acrylic artificial hair fiber having good antibacterial properties and gloss, and a headdress product containing the same. Further, according to the production method of the present invention, an antibacterial acrylic artificial hair fiber having good antibacterial properties and gloss can be obtained by wet spinning.
• the inventors of the present invention have repeatedly studied how to impart antibacterial properties to acrylic artificial hair fibers and improve luster as artificial hair.
• one or more selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters and polyoxyethylene alkyl ethers is used as an oil agent, and a nonionic surfactant having a predetermined HLB is used,
• a nonionic surfactant having a predetermined HLB is used.
• an antibacterial acrylic artificial hair fiber having good antibacterial properties and gloss can be obtained by setting the contents of chitosan and nonionic surfactant within a predetermined range.
• the antimicrobial acrylic artificial hair fibers have deodorant properties.
• the antimicrobial acrylic artificial hair fibers have deodorant properties.
• a numerical range when a numerical range is indicated by " ⁇ ", the values at both ends are included.
• a numerical range of "X to Y” is a range that includes both end values of X and Y.
• Antimicrobial acrylic artificial hair fibers contain chitosan and nonionic surfactants.
• Chitosan is a deacetylated product of chitin, a natural polymer.
• chitin obtained from the exoskeleton of crustaceans such as crabs and shrimps can be deacetylated by boiling in concentrated alkali.
• the degree of deacetylation of chitosan is not particularly limited, and may be about 60 to 99%. For example, from the viewpoint of deodorant properties, it is preferably 70 to 99%, more preferably 80 to 99%. .
• the degree of deacetylation of chitosan can be measured by, for example, NMR spectroscopy, infrared absorption spectroscopy (IR), colloidal titration, and the like.
• the weight-average molecular weight of chitosan is not particularly limited, and may be about 10,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 10,000 to 300,000, from the viewpoint of handling the aqueous solution. preferable.
• the weight average molecular weight of a compound can be measured by gel permeation chromatography (GPC), GPC measurement uses chloroform as a mobile phase, measurement is performed with a polystyrene gel column, and the number weight average Molecular weight and the like can be determined in terms of polystyrene.
• chitosan should preferably have a low allergen content from the viewpoint of safety. Since chitosan is often purified from crustacean-derived raw materials, it may contain crustacean protein, which is a type of allergen.
• the crustacean protein content in chitosan is, for example, preferably 9.9 ⁇ g or less, more preferably 5.0 ⁇ g or less, and even more preferably 1.0 ⁇ g or less per 1 g of chitosan.
• a sample containing 10 ⁇ g or more of protein derived from a specific raw material per gram of the weight of food sampled may be judged to possibly contain more than a very small amount of the specific raw material.
• the protein content in chitosan can be measured, for example, by an ELISA method. Specifically, the crustacean protein content in chitosan was determined by ELISA using the Crustacea Kit II "Maruha Nichiro” manufactured by Maruha Nichiro Co., Ltd. or the FA Test EIA-Crustacea II "Nissui” manufactured by Nissui Pharmaceutical Co., Ltd. can be measured.
• the content of chitosan extracted with dilute acetic acid is 0.005-0.4% 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, the film will be difficult to stretch, resulting in poor process stability.
• the content of chitosan extracted with dilute acetic acid is preferably 0.01% by weight or more.
• 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, from the viewpoint of excellent antibacterial properties and excellent deodorant performance.
• 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, from the viewpoint of improving stretchability and gloss.
• the content of chitosan extracted with dilute acetic acid can be measured and calculated as follows.
• the content of chitosan in the antibacterial acrylic artificial hair fiber may be expressed as the content of chitosan obtained by extracting chitosan with dilute acetic acid as described above and extracting chitosan with dilute acetic acid, as described later. It may be expressed as the content of chitosan extracted and extracted with concentrated hydrochloric acid. In the case of extraction with concentrated hydrochloric acid, most of the chitosan in the fiber can be extracted.
• the content of chitosan extracted with concentrated hydrochloric acid is 0.014-1.2% 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, the film will be difficult to stretch, resulting in poor process stability.
• the content of chitosan extracted with concentrated hydrochloric acid is preferably 0.015% by weight or more, more preferably 0.02% by weight or more.
• the content of chitosan extracted with concentrated hydrochloric acid is more preferably 0.04% by weight or more, and more preferably 0.06% 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, more preferably 0.8% by weight, from the viewpoint of improving stretchability and gloss. % or less, and even more preferably 0.7 wt % or less.
• the content of chitosan extracted with concentrated hydrochloric acid can be measured and calculated as follows.
• 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.
• the HLB hydrophilic-lipophilic balance
• 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. .
• the HLB of the nonionic surfactant may be 19 or less.
• the polyoxyethylene sorbitan fatty acid ester is not particularly limited as long as it has an HLB of 13.0 or more.
• a sorbitan fatty acid monoester to which an oxyethylene group is added can be used as appropriate.
• the average number of added moles of oxyethylene groups is preferably 5-100, more preferably 10-50.
• the fatty acid may have 4 to 30 carbon atoms, preferably 6 to 28 carbon atoms, more preferably 8 to 26 carbon atoms, still more preferably 10 to 24 carbon atoms, and particularly preferably 12 to 22 carbon atoms.
• the carbon chains of fatty acids may be straight or branched.
• Fatty acids may be saturated fatty acids or unsaturated fatty acids.
• saturated fatty acids examples include lauric acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, behenic acid, tetracosanoic acid, hexacosanoic acid, and octacosanoic acid.
• unsaturated fatty acids include palmitoleic acid, oleic acid, vaccenic acid, nervonic acid, linoleic acid, eicosadienoic acid, linolenic acid, mead acid, and arachidonic acid.
• 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.
• Polyoxyethylene sorbitan monooleate preferably has an average addition mole number of oxyethylene groups of 10 to 100, more preferably 15 to 30.
• Polyoxyethylene sorbitan monolaurate preferably has an average addition mole number of oxyethylene groups of 10 to 100, more preferably 15 to 100.
• the polyoxyethylene fatty acid monoester is not particularly limited as long as it has an HLB of 13.0 or higher.
• a monoester of fatty acid and polyoxyethylene glycol can be used as appropriate.
• the average number of added moles of oxyethylene groups is preferably 5-100, more preferably 10-50.
• the fatty acid may have 4 to 30 carbon atoms, preferably 6 to 28 carbon atoms, more preferably 8 to 26 carbon atoms, still more preferably 10 to 24 carbon atoms, and particularly preferably 12 to 20 carbon atoms.
• the carbon chains of fatty acids may be straight or branched.
• Fatty acids may be saturated fatty acids or unsaturated fatty acids. Saturated fatty acids and saturated fatty acids include, for example, those described above.
• polyoxyethylene fatty acid monoesters include polyoxyethylene monolaurate, polyoxyethylene monocaprate, polyoxyethylene monopalmitate, polyoxyethylene monostearate, and polyoxyethylene monooleate.
• Polyoxyethylene monolaurate is preferable, and polyoxyethylene monolaurate having an average number of added moles of oxyethylene groups of 5 to 15 is more preferable from the viewpoint of improving glossiness.
• the polyoxyethylene alkyl ether is not particularly limited as long as it has an HLB of 13.0 or more.
• the average number of added moles of oxyethylene groups is preferably 5-100, more preferably 10-30.
• the number of carbon atoms in the alkyl moiety may be 4-30, preferably 6-28, more preferably 8-26.
• the carbon chain of the alkyl moiety may be linear or branched.
• Polyoxyethylene alkyl ethers include, specifically, polyoxyethylene-(2-ethyl)hexyl ether, polyoxyethylene lauryl ether, polyoxyethylene palmityl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like.
• Polyoxyethylene-(2-ethyl)hexyl ether is preferable from the viewpoint of improving glossiness, and polyoxyethylene-(2-ethyl ) is more preferably a hexyl ether.
• the melting point of the nonionic surfactant is not particularly limited, but from the viewpoint of gloss, it is preferably 25° C. or less, more preferably 22° C. or less, and 20° C. or less. and particularly preferably 18° C. or lower. In this specification, the melting point of the nonionic surfactant is determined by a visual method or the like.
• the content of the nonionic surfactant in the antibacterial acrylic artificial hair fiber is 0.10-0.90% by weight. If the content of the nonionic surfactant is less than 0.10% by weight, the process stability and workability deteriorate due to the generation of static electricity. When the content of the nonionic surfactant exceeds 0.90% by weight, the separability of the fiber bundles deteriorates, and the processability deteriorates.
• the content of the 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 0.80% by weight or less. 50% by weight or less is particularly preferred.
• the content of the nonionic surfactant (oil agent) (hereinafter also referred to as the oil agent adhesion amount) can be measured as follows.
• the acrylic copolymer constituting the antibacterial acrylic artificial hair fiber is not particularly limited.
• an acrylic copolymer containing less than 95% by weight of acrylonitrile and more than 5% by weight of other monomers may be used. and preferably acrylic copolymers containing less than 80% by weight of acrylonitrile and greater than 20% by weight of other monomers can be used.
• 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% of a sulfonic acid group-containing vinyl monomer. More preferably, it contains ⁇ 5% by weight.
• the content of acrylonitrile in the acrylic copolymer is 29.5 to 79.5% by weight, the heat resistance is improved.
• the content of vinyl chloride and/or vinylidene chloride in the acrylic copolymer is 20 to 70% by weight, flame retardancy is improved.
• Hydrophilicity increases when the acrylic copolymer contains 0.5 to 5% by weight of the 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 vinyl chloride and/or vinylidene chloride, and 0.5% of a sulfonic acid group-containing vinyl monomer.
• the acrylic copolymer preferably contains vinyl chloride from the standpoint of better tactile sensation.
• the sulfonic acid group-containing vinyl monomer is not particularly limited, but examples include allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and sodium salts thereof. metal salts such as and amine salts can be used.
• the sulfonic acid group-containing vinyl monomer may be used alone or in combination of two or more.
• the antibacterial acrylic artificial hair fibers contain other additives for improving the fiber properties, if necessary, as long as the effects of the present invention are not impaired. It's okay.
• additives include coloring agents such as gloss modifiers, organic pigments, inorganic pigments, and dyes, light stabilizers, heat stabilizers, fiber sizing agents, deodorants, and fragrances.
• the antibacterial acrylic artificial hair fiber contains an oil agent selected from the group consisting of polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid monoesters and polyoxyethylene alkyl ethers. It preferably contains only one or more nonionic surfactants.
• the antibacterial acrylic artificial hair fiber contains other oils, from the viewpoint of separation of the fiber bundle, the other oils and HLB are 13.0 or more, and polyoxyethylene sorbitan fatty acid ester, polyoxyethylene
• the total content of one or more nonionic surfactants selected from the group consisting of fatty acid monoesters and polyoxyethylene alkyl ethers is preferably 0.90% by weight or less.
• the antibacterial acrylic artificial hair fiber preferably has a single fiber fineness of 10 to 100 dtex, more preferably 20 to 95 dtex, and even more preferably 25 to 85 dtex, from the viewpoint of being suitably used as artificial hair. , 30 to 75 dtex, particularly preferably 35 to 65 dtex.
• the antibacterial acrylic artificial hair fiber preferably has an antibacterial activity value of 2.2 or more, more preferably 3.0 or more, measured according to JIS L 1902:2015, from the viewpoint of excellent antibacterial properties. , 4.0 or more.
• the antibacterial acrylic artificial hair preferably has an antibacterial activity value of 4.0 or more, measured according to JIS L 1902:2015, from the viewpoint of being excellent in antibacterial properties even after washing, and preferably 4.5 or more. more preferred.
• Antibacterial acrylic artificial hair fibers have high antibacterial properties against bacteria such as Staphylococcus aureus.
• the volatilization amount of isovaleric acid generated by the growth of bacteria is preferably 150 ⁇ g or less per 1 kg of fiber, and preferably 100 ⁇ g or less. is more preferable, and 70 ⁇ g or less is even more preferable.
• Isovaleric acid is known as an odor component generated from the scalp.
• the volatilization amount of isovaleric acid generated by the growth of bacteria can be specifically measured as described in Examples.
• the antibacterial acrylic artificial hair fiber preferably has a gloss L BNT of 50.0 or more according to the definition of Bossa Nova Technologies, from the viewpoint of good gloss, and preferably 65.0 or more. is more preferred.
• L BNT is calculated using the SAMBA Hair System manufactured by Bossa Nova Technologies, by applying a light source to a fiber bundle attached to a curved surface, measuring the intensity of specularly reflected light and diffusely reflected light, and using the following formula 2.
• the antibacterial acrylic artificial hair fiber has excellent deodorant properties.
• the deodorant rate for isovaleric acid is preferably 60% or more, more preferably 70% or more, and 80% or more. is more preferred, and 90% or more is particularly preferred.
• Isovaleric acid is known as an odor component generated from the scalp.
• the deodorizing property can be measured by the following method.
• (Deodorant) 1) Prepare a 0.03% aqueous solution of isovaleric acid. 2) After adding 0.2 mL of an isovaleric acid aqueous solution to the surface of 1 g of the sample, the sample is placed in a 1 L sampling bag and the cut portion is closed. 3) After the inside of the bag is degassed with a vacuum pump, 0.5 L of high-purity nitrogen gas is injected through an integrating flowmeter, and the bag is sealed.
• the antibacterial acrylic artificial hair is obtained by wet-spinning a spinning solution containing an acrylic copolymer, and before drying, the yarn has chitosan and HLB of 13.0 or more, and polyoxyethylene sorbitan fatty acid ester, It can be produced by applying one or more nonionic surfactants selected from the group consisting of polyoxyethylene fatty acid monoesters and polyoxyethylene alkyl ethers.
• a spinning solution can be obtained, for example, by dissolving an acrylic copolymer in an organic solvent.
• the organic solvent is not particularly limited, and a good solvent for acrylic copolymers can be used as appropriate.
• Good solvents include, for example, methylsulfoxide (DMSO), dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and acetone. From the viewpoint of versatility, acetone may be used. From the viewpoint of high safety, dimethylsulfoxide may be used.
• the spinning solution may contain small amounts of water, eg 1.5-4.8% by weight water. Thereby, the formation of voids can be suppressed.
• the spinning solution preferably contains 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, and more preferably 0.3 parts by weight or more of the epoxy group-containing compound with respect to 100 parts by weight of the acrylic copolymer. is more preferred.
• Including an epoxy group-containing compound in the spinning solution is preferable from the viewpoint of suppressing odor, coloration of the fiber due to heat, devitrification of the fiber due to hot water, and the like.
• dimethylsulfoxide is used as the organic solvent, it is possible to effectively suppress the generation of foul-smelling components due to the decomposition of dimethylsulfoxide when the acrylic artificial hair fibers are heated.
• the spinning solution preferably contains 5 parts by weight or less of an epoxy group-containing compound with respect to 100 parts by weight of the acrylic copolymer, and more preferably contains 3 parts by weight or less. Preferably, it is more preferably contained in an amount of 1 part by weight or less.
• epoxy group-containing compounds 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, cycloaliphatic type epoxy resins, and the like. can be used. Epoxy group-containing compounds may be used singly or in combination of two or more.
• the epoxy group-containing compound is a glycidyl methacrylate-containing polymer and / Alternatively, it is preferably a glycidyl acrylate-containing polymer, more preferably polyglycidyl methacrylate.
• the weight-average molecular weight of the epoxy group-containing compound is not particularly limited, and may be determined as appropriate, for example, in consideration of solubility in dimethylsulfoxide and elution into the spinning bath.
• 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, the weight average molecular weight is preferably 3000 or more, and an organic compound such as dimethyl sulfoxide is added. From the viewpoint of solubility in solvents, the weight average molecular weight is preferably 100,000 or less.
• the spinning solution may, if necessary, contain other additives for improving fiber properties as long as they do not impair the effects of the present invention.
• the additives include gloss modifiers, organic pigments, inorganic pigments, colorants such as dyes, stabilizers for improving light resistance and heat resistance, and the like.
• the wet spinning may include at least a coagulation step, a water washing step and a drying step. Moreover, it is preferable to include a wet stretching step performed before the water washing step or after the water washing step and before the drying step. From the viewpoint of the durability of chitosan, it is necessary to apply chitosan and a nonionic surfactant before the drying process (hereinafter also referred to as an oil application process).
• the amount of chitosan to be applied is preferably about three times the amount of chitosan extracted with the desired diluted acetic acid in the acrylic fiber obtained, or the amount of chitosan extracted with the desired concentrated hydrochloric acid in the acrylic fiber obtained. About 1 time is preferable.
• the oiling step is performed after the wet stretching step. Moreover, from the viewpoint of fiber strength, it is preferable to include a dry drawing step after the drying step. In addition, if necessary, a thermal relaxation treatment step may be included after the dry stretching step.
• the spinning solution is discharged through a spinning nozzle into a coagulation bath and coagulated to form threads (also referred to as coagulated threads).
• the spinning nozzle can be appropriately used according to the target fiber cross section.
• the cross section of the fiber is not particularly limited, and may be circular, elliptical, irregular, or the like.
• the spinning speed is not particularly limited, it is preferably 2 to 17 m/min from the viewpoint of industrial productivity.
• the nozzle draft is not particularly limited, it is preferably 0.8 to 2.0 from the viewpoint of manufacturing process stability.
• an aqueous solution of a good solvent such as dimethylsulfoxide with a concentration of 20 to 70% by weight can be used.
• the temperature of the coagulation bath can be 5-40°C. If the concentration of the organic solvent in the coagulation bath is too low, coagulation will be accelerated and the coagulation structure will become rough, tending to form voids inside the fibers.
• the acrylic fiber (coagulated yarn) is preferably wet drawn (also referred to as primary drawing) in a drawing bath.
• the drawing bath can be an aqueous solution having a lower concentration of a good solvent such as dimethylsulfoxide than the coagulation bath.
• the temperature of the drawing bath is preferably 30° C. or higher, more preferably 40° C. or higher, and even more preferably 50° C. or higher.
• the draw ratio is not particularly limited, but from the viewpoint of increasing the strength and productivity of the fiber, it is preferably 2 to 8 times.
• the bath stretching step may be performed after the water washing step described below, or the primary stretching and the water washing may be performed at the same time.
• the acrylic fiber is washed with hot water of 30°C or higher to remove a good solvent such as dimethyl sulfoxide from the acrylic fiber.
• the coagulated yarn may be led to warm water of 30° C. or higher, and primary drawing and water washing may be performed simultaneously.
• the primary stretching may be performed after the water washing step.
• the water washing step for example, by using hot water of 70° C. or higher, it becomes easier to remove a good solvent such as dimethylsulfoxide in the acrylic fiber.
• chitosan and a nonionic surfactant (HLB of 13.0 or more and selected from the group consisting of polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid monoester and polyoxyethylene alkyl ether) Chitosan and a nonionic surfactant are imparted to the yarn using a chitosan-containing oil composition in which one or more nonionic surfactants are dissolved or dispersed in water.
• an organic solvent such as dimethylsulfone, ⁇ -caprolactam, ethylene carbonate, and sulfolane may be applied to the yarn in order to improve the curl setting property with hot water.
• 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 nonionic surfactant.
• the chitosan-containing oil composition desirably contains acetic acid, hydrochloric acid, or the like in order to dissolve chitosan.
• the chitosan-containing oil composition is not particularly limited. It may contain 0.1 to 5% by weight of dimethylsulfone and the balance may be water.
• the chitosan-containing oil composition may contain other additives for improving the fiber properties, if necessary, as long as they do not impair the effects of the present invention.
• the additives include fiber sizing agents such as urethane-based polymers and cationic ester polymers.
• the acrylic fibers are dried.
• the drying temperature is not particularly limited, it is, for example, 110 to 190°C.
• the dried fibers are preferably further dry drawn (secondary drawing).
• the stretching temperature for secondary stretching is not particularly limited, but is, for example, 110 to 190°C.
• the draw ratio is not particularly limited, but for example, it is preferably 1 to 4 times, more preferably 1 to 3 times, even more preferably 1 to 2 times.
• the total drawing ratio including bath drawing before drying is preferably 2 to 10 times, more preferably 2 to 8 times, even more preferably 2 to 6 times, and 2 to 4 times. It is particularly preferred to have
• the fibers are preferably relaxed in a thermal relaxation treatment step.
• the relaxation rate is not particularly limited, for example, it is preferably 5% or more, more preferably 10 to 30%.
• the thermal relaxation treatment can be performed at a high temperature, for example, in a dry heat atmosphere of 150 to 200° C. or in a superheated steam atmosphere.
• headdress products examples include, but are not limited to, hair wigs, wigs, weaving, hair extensions, braided hair, hair accessories, and doll hair.
• the antibacterial acrylic artificial hair fibers may be used alone as artificial hair to form headdress products.
• other artificial hair fibers and natural fibers such as human hair and animal hair may be combined to constitute a headdress product.
• other artificial hair fibers include, but are not particularly limited to, polyvinyl chloride fibers, nylon fibers, polyester fibers, regenerated collagen fibers, and the like.
• Chitosan was extracted from the fiber with dilute acetic acid according to the following procedure, and the content of chitosan extracted with dilute acetic acid was determined.
• Reactive Red4 [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 of 1) to prepare a dye solution.
• Chitosan was extracted from the fiber with concentrated hydrochloric acid according to the following procedure, and the content of chitosan 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 chitosan, and then the volume was adjusted 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, the mixture was neutralized to pH 7 with 12N hydrochloric acid and adjusted to a constant volume of 50 mL.
• the antibacterial activity value was measured according to JIS L 1902:2015 antibacterial test/quantitative test for textile products (bacterial liquid absorption method). Staphylococcus aureus was used for the test. In order to prevent shape deterioration of the sample, the test was performed without subjecting the sample to high-pressure steam sterilization. According to the "SEK Mark Textile Product Certification Standards", if the antibacterial activity value is 2.2 or more, it has an antibacterial and deodorizing effect.
• the area of the peak corresponding to isovaleric acid in the total ion chromatogram was determined using the attached analysis software, and the amount of volatilization was determined using a calibration curve prepared in advance. 5) After completion of operation 4, the sample was taken out from the bag and dried at 120°C to determine the dry mass of the sample. 6) From the volatilization amount of isovaleric acid obtained in operation 4 and the dry mass of the sample obtained in operation 5, the volatilization amount of isovaleric acid per 1 kg of dry mass of the fiber was calculated. The lower limit of quantification was 42 ⁇ g/kg.
• gloss [Evaluation 1] Visual evaluation was performed using fiber bundle samples having a total fineness of 1.2 million to 1.3 million dtex by three persons who had been involved in the beauty evaluation of wigs for three years or more, and gloss was determined. AFRELLE was taken as the reference sample. L BNT measured and calculated in gloss evaluation 2 of the reference sample was 56.3. A (very good): Evaluated as gloss better than the reference sample B (good): Evaluated as gloss equivalent to the reference sample C (poor): Evaluated as poorer gloss than the reference sample [Evaluation 2] L BNT was measured and calculated using SAMBA Hair System manufactured by Bossa Nova Technologies, and gloss was evaluated according to the following three-level criteria based on L BNT .
• L BNT was calculated using the SAMBA Hair System manufactured by Bossa Nova Technologies, by applying a light source to a fiber bundle attached to a curved surface, measuring the intensity of specularly reflected light and diffusely reflected light, and using Equation 2 below.
• Example 1 An acrylic copolymer composed of 46% by weight of acrylonitrile, 52% by weight of vinyl chloride, and 2% by weight of sodium styrenesulfonate was dissolved in dimethylsulfoxide (DMSO), and the concentration of the acrylic copolymer was 26%. A resin solution having a concentration of 0.0% by weight and a water concentration of 2.7% by weight was prepared. Next, carbon black, a red dye (C.I Basic Red 46) and a blue dye (C.I Basic Blue 41) as colorants were added to the resin solution at 2.0 parts per 100 parts by weight of the acrylic copolymer. It was added so as to be 1 part by weight, 0.04 part by weight and 0.07 part by weight.
• DMSO dimethylsulfoxide
• 0.8 parts by weight of polyglycidyl methacrylate (weight average molecular weight: 12,000) was added to 100 parts by weight of the acrylic copolymer to prepare a spinning dope.
• This spinning dope was extruded into a coagulation bath of 47 wt% DMSO aqueous solution at 25°C using a spinning nozzle (hole diameter 0.3 mm, number of holes 100), wet spinning at a spinning speed of 2 m/min, and then 90°C. , and stretched 2.1 times in a stretching bath of 50% by weight DMSO in water. Subsequently, it was washed with hot water at 90°C.
• a chitosan-containing oil composition (chitosan 0.1% by weight, acetic acid 0.05% by weight, polyoxyethylene (20) sorbitan monooleate (values in parentheses are oxyethylene groups). Average number of added moles, hereinafter the same; HLB: 15.0, melting point: -25°C) 5.0% by weight, 2.0% by weight of dimethylsulfone, and 92.9% by weight of distilled water) is introduced.
• HLB 15.0
• melting point -25°C
• Chitosan had a degree of deacetylation of 71%.
• Crustacea protein content in chitosan was measured using Crustacea Kit II "Maruha Nichiro” manufactured by Maruha Nichiro Co., Ltd. and FA Test EIA-Crustacea II "Nissui” manufactured by Nissui Pharmaceutical Co., Ltd. was 0.1 ⁇ g or less (below the lower limit of determination) per 1 g of chitosan.
• Example 2 As a chitosan-containing oil composition, chitosan 1.0% by weight, acetic acid 0.5% by weight, polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25°C) 4.4% by weight, An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1, except that a composition comprising 2.0% by weight of dimethylsulfone and 92.1% by weight of distilled water was used.
• Example 3 As a chitosan-containing oil composition, chitosan 3.0% by weight, acetic acid 1.5% by weight, polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25°C) 4.4% by weight, An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1, except that a composition comprising 2.0% by weight of dimethylsulfone and 89.1% by weight of distilled water was used.
• Example 4 As a chitosan-containing oil composition, chitosan 1.0% by weight, acetic acid 0.5% by weight, polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25°C) 3.0% by weight, An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1 except that a composition comprising 2.0% by weight of dimethylsulfone and 93.5% by weight of distilled water was used.
• Example 5 As a chitosan-containing oil composition, chitosan 1.0% by weight, acetic acid 0.5% by weight, polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25°C) 7.0% by weight, An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1 except that a composition comprising 2.0% by weight of dimethylsulfone and 89.5% by weight of distilled water was used.
• Example 6 Chitosan-containing oil composition: 1.0% by weight of chitosan, 0.5% by weight of acetic acid, polyoxyethylene monolaurate (average number of added moles of oxyethylene group: 9, HLB: 13.3, melting point: 10°C) Acrylic fibers having a single fiber fineness of about 46 dtex were prepared in the same manner as in Example 1 except that a composition consisting of 6.0% by weight, 2.0% by weight of dimethylsulfone, and 90.5% by weight of distilled water was used. Obtained.
• Example 7 As the chitosan-containing oil composition, 1.0% by weight of chitosan, 0.5% by weight of acetic acid, polyoxyethylene-(2-ethyl)hexyl ether (average number of added moles of oxyethylene group: 9, HLB: 15, melting point: ⁇ 25° C.) 6.0% by weight, dimethylsulfone 2.0% by weight, and distilled water 90.5% by weight. An acrylic fiber was obtained.
• Example 8 As a chitosan-containing oil composition, chitosan 1.0% by weight, acetic acid 0.5% by weight, polyoxyethylene (20) sorbitan monolaurate (HLB: 16.7, melting point: -14°C) 6.0% by weight, An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1 except that a composition comprising 2.0% by weight of dimethylsulfone and 90.5% by weight of distilled water was used.
• chitosan-containing oil composition As a chitosan-containing oil composition, chitosan 5.0% by weight, acetic acid 2.5% by weight, polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25°C) 4.4% by weight, The chitosan-containing oil composition was impregnated and dried at 140° C. in the same manner as in Example 1 except that a composition comprising 2.0% by weight of dimethylsulfone and 86.1% by weight of distilled water was used. After that, when the drawing was attempted, the drawing could not be performed.
• HLB polyoxyethylene (20) sorbitan monooleate
• chitosan-containing oil composition As a chitosan-containing oil composition, chitosan 1.0% by weight, acetic acid 0.5% by weight, polyoxyethylene (20) sorbitan monooleate (HLB: 15.0, melting point: -25°C) 0.4% by weight, An acrylic fiber having a single fiber fineness of about 46 dtex was produced in the same manner as in Example 1 except that a composition comprising 2.0% by weight of dimethylsulfone and 96.1% by weight of distilled water was used. It was strong and difficult to handle.
• the acrylic fibers of Examples had high antibacterial properties and good gloss.
• the acrylic fibers of Examples 2 to 5 in which the content of chitosan extracted with dilute acetic acid is 0.05% by weight or more, or the content of chitosan extracted with concentrated hydrochloric acid is 0.1% by weight or more, is isocratic.
• the volatilization amount of valeric acid was 70 ⁇ g or less per 1 kg of fiber, and the deodorant property was also good.
• Comparative Example 1 in which the content of chitosan extracted with dilute acetic acid exceeds 0.4% by weight or the content of chitosan extracted with concentrated hydrochloric acid exceeds 1.2% by weight, stretching was performed after applying chitosan. could not be carried out, and the process stability was poor.
• Comparative Example 2 in which the oil agent adhesion amount was less than 0.10% by weight, static electricity was generated, and process stability and workability were poor.
• Comparative Example 3 in which the amount of oil agent adhered exceeds 0.90% by weight, the separability of the fiber bundle is poor, and the workability is poor.
• Comparative Example 4 in which polyoxyethylene sorbitan fatty acid ester having an HLB of 11 was used as the oil agent, gloss was poor.
• the present invention includes, but is not limited to, at least the following embodiments.
• [1] containing chitosan and a nonionic surfactant 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 esters, polyoxyethylene fatty acid monoesters and polyoxyethylene alkyl ethers, The antibacterial acrylic artificial hair fiber, wherein the HLB of the nonionic surfactant is 13.0 or more.
• [2] containing chitosan and a nonionic surfactant 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 esters, polyoxyethylene fatty acid monoesters and polyoxyethylene alkyl ethers, The antibacterial acrylic artificial hair fiber, wherein the HLB of the nonionic surfactant is 13.0 or more.
• the acrylic copolymer constituting the antibacterial acrylic artificial hair fiber contains 29.5 to 79.5% by weight of acrylonitrile and one or more monomers selected from the group consisting of vinyl chloride and vinylidene chloride.
• the antibacterial acrylic artificial hair fiber according to any one of [1] to [6] which has a single fiber fineness of 10 to 150 dtex.
• a headdress comprising the antibacterial acrylic artificial hair fiber according to any one of [1] to [9].
• the headdress product according to [10], wherein the headdress product is one selected from the group consisting of hair wigs, wigs, weaving, hair extensions, braided hair, hair accessories and doll hair.
• a method for producing an antibacterial acrylic artificial hair fiber [13] The method for producing an antibacterial acrylic artificial hair fiber according to [12], wherein chitosan and a nonionic surfactant are applied to the yarn after wet drawing. [14] The method for producing an antibacterial acrylic artificial hair fiber according to [12] or [13], wherein chitosan and a nonionic surfactant are applied, and after drying, the yarn is dry drawn.

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Artificial Filaments (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=86159736

Family Applications (1)

Country Status (3)

Citations (4)

• 2022
  • 2022-09-26 WO PCT/JP2022/035726 patent/WO2023074220A1/ja not_active Ceased
  • 2022-09-26 US US18/703,914 patent/US20240417916A1/en active Pending
  • 2022-09-26 JP JP2023556210A patent/JPWO2023074220A1/ja active Pending

Patent Citations (4)

Also Published As

Similar Documents

Legal Events