Classifications

• • 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
  • D06M13/322—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 nitrogen
  • D06M13/46—Compounds containing quaternary nitrogen atoms
  • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
• • 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
  • D06M13/165—Ethers
• • 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
• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
  • A41G5/00—Hair pieces, inserts, rolls, pads, or the like; Toupées
  • A41G5/004—Hairpieces, e.g. hair extensions
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/06—Wet spinning methods
• • 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
• • 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
  • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
  • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
  • D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
• • 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
  • 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
  • D06M13/2243—Mono-, di-, or triglycerides
• • 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
• • 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
  • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
• • 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
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/16—Synthetic fibres, other than mineral fibres
  • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
  • D06M2101/28—Acrylonitrile; Methacrylonitrile
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/13—Physical properties anti-allergenic or anti-bacterial
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2503/00—Domestic or personal
  • D10B2503/08—Wigs

Definitions

• the present invention relates to an antibacterial polyacrylonitrile synthetic fiber, a method for producing the same, and a headdress product.
• Patent Document 1 polyacrylonitrile synthetic fibers are given a quaternary ammonium salt and a specific nonionic surfactant. It has been described that the antibacterial properties of polyacrylonitrile synthetic fibers are improved by applying .
• Patent Document 1 when the surfactant disclosed in Patent Document 1 is contained as an antibacterial agent in polyacrylonitrile synthetic fiber, the resulting polyacrylonitrile synthetic fiber has excellent antibacterial properties, but has a problem of poor feel.
• Polyacrylonitrile synthetic fibers are widely used as artificial hair, but polyacrylonitrile synthetic fibers have poor texture and do not meet the characteristics required for artificial hair.
• the present invention has been made in view of the above-mentioned problems, and includes an antibacterial polyacrylonitrile synthetic fiber suitable for use in artificial hair that has excellent antibacterial properties and excellent texture, a method for producing the fiber, and a method for producing the fiber.
• the purpose is to provide headdress products.
• the present inventors applied a quaternary ammonium salt (B) and a specific nonionic surfactant (C) to polyacrylonitrile synthetic fiber (A), and by intensively studying the amount of these attached, The inventors have discovered that the above problems can be solved, and have completed the present invention.
• aspects of the present invention relate to the following antibacterial polyacrylonitrile synthetic fibers, methods for producing the fibers, and headdress products containing the fibers.
• R 1 is an alkyl group having 8 to 18 carbon atoms
• R 2 to R 4 are each independently a methyl group, an alkyl group having 8 to 18 carbon atoms, and a 3-(trihydroxysilyl group).
• a quaternary ammonium salt (B) represented by An antibacterial polyacrylonitrile synthetic fiber in which a nonionic surfactant (C) is attached to a polyacrylonitrile synthetic fiber (A), The nonionic surfactant (C) contains sorbitan fatty acid ester (C1) and poly
• R 1 is an alkyl group having 8 to 18 carbon atoms
• R 2 to R 4 are all methyl groups, or R 1 and R 2 are both alkyl groups having 8 to 18 carbon atoms.
• R 3 and R 4 are both methyl groups, or R 1 is an alkyl group having 8 to 18 carbon atoms, and R 2 is a 3-(trihydroxycysilyl)propyl group.
• R 3 and R 4 are both methyl groups, or R 1 is an alkyl group having 8 to 18 carbon atoms, R 2 is a 3-(trimethoxysilyl)propyl group, and R 3 and R 4 are both methyl groups, n is 1, and X n- is a chloride ion or a dialkyl phosphate ester ion having an alkyl group having 1 to 3 carbon atoms, [1] The antibacterial polyacrylonitrile synthetic fiber described in .
• the content of the sorbitan fatty acid ester (C1) is 20% by mass or more and 90% by mass or less based on the total mass of the nonionic surfactant (C), [1] or [2]
• a headdress product comprising the antibacterial polyacrylonitrile synthetic fiber according to any one of [1] to [5].
• a manufacturing method comprising: drying.
• an antibacterial polyacrylonitrile synthetic fiber suitable for use in artificial hair which has excellent antibacterial properties and has an excellent texture
• a method for producing the fiber and a headdress product containing the fiber.
• the antibacterial polyacrylonitrile synthetic fiber is formed by adhering a quaternary ammonium salt (B), which will be described later, and a nonionic surfactant (C), which will be described later, to a polyacrylonitrile synthetic fiber (A). More specifically, in the antibacterial polyacrylonitrile synthetic fiber, the quaternary ammonium salt (B) and the nonionic surfactant (C) adhere to the surface of the polyacrylonitrile synthetic fiber (A). Forms a film.
• the amount of the quaternary ammonium salt (B) and the nonionic surfactant (C) attached is a specific amount based on the total mass of the antibacterial polyacrylonitrile synthetic fiber.
• Antibacterial polyacrylonitrile synthetic fibers have antibacterial properties because quaternary ammonium salts (B) and nonionic surfactants (C) are attached to antibacterial polyacrylonitrile synthetic fibers in specific amounts. It has the effect of not only being excellent in texture, but also having an excellent tactile feel.
• the acrylonitrile polymer constituting the polyacrylonitrile synthetic fiber (A) is not particularly limited as long as it contains 25% by mass or more of acrylonitrile-derived structural units.
• An acrylonitrile polymer containing 100% by mass and 0 to 75% by mass of structural units derived from other monomers can be used.
• the acrylonitrile polymer may contain 95% by mass or less of structural units derived from acrylonitrile, 5% by mass or more of structural units derived from other monomers, 90% by mass or less of structural units derived from acrylonitrile, It may contain 10% by mass or more of structural units derived from other monomers, 30 to less than 85% by mass of structural units derived from acrylonitrile, and more than 15% by mass of structural units derived from other monomers. It may be included in an amount of % by mass or less.
• Other monomers are not particularly limited as long as they can be copolymerized with acrylonitrile, and examples include unsaturated carboxylic acids such as acrylic acid and methacrylic acid and their salts, and acrylic acids such as methyl acrylate. esters, methacrylic esters such as methyl methacrylate, esters of unsaturated carboxylic acids such as glycidyl methacrylate, vinyl esters such as vinyl acetate and vinyl butyrate, halogen-containing monomers, and sulfonic acid group-containing monomers, etc. Can be mentioned. These may be used alone or in combination of two or more.
• the acrylonitrile polymer contains 30 to 80% by mass of structural units derived from acrylonitrile, 20 to 70% by mass of structural units derived from a halogen-containing monomer, from the viewpoint of heat resistance, flame retardance, and dyeability. It is preferable that the composition contains 0 to 5% by mass of a structural unit derived from a sulfonic acid group-containing monomer.
• the acrylonitrile polymer contains 35 to 75% by mass of structural units derived from acrylonitrile, 25 to 65% by mass of structural units derived from a halogen-containing monomer, and structural units derived from a sulfonic acid group-containing monomer.
• ⁇ may contain 0 to 5% by mass of structural units derived from acrylonitrile, 35 to 75% by mass of structural units derived from acrylonitrile, 24.5 to 64.5% by mass of structural units derived from halogen-containing monomers, and sulfonic acid group-containing monomers. It may contain 0.5 to 5% by mass of structural units derived from polymers.
• halogen-containing monomer examples include halogen-containing vinyl monomers such as vinyl chloride and vinyl bromide, and halogen-containing vinylidene monomers such as vinylidene chloride and vinylidene bromide.
• the halogen-containing monomers may be used alone or in combination of two or more.
• the halogen-containing monomer preferably contains one or more selected from the group consisting of vinyl chloride and vinylidene chloride, and from the viewpoint of feel, preferably contains vinyl chloride.
• the sulfonic acid group-containing monomer is not particularly limited, but includes, for example, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and sodium salts thereof. Metal salts such as, amine salts, etc. can be used.
• the sulfonic acid group-containing monomers may be used alone or in combination of two or more.
• the single fiber fineness of the polyacrylonitrile synthetic fiber (A) is not particularly limited, and is preferably, for example, 1 dtex or more and 100 dtex or less, and from the viewpoint of suitably using it as artificial hair, the single fiber fineness is 10 dtex or more and 90 dtex or less. It is more preferably 20 dtex or more and 80 dtex or less, even more preferably 30 dtex or more and 70 dtex or less, and particularly preferably 35 dtex or more and 65 dtex or less.
• the method for producing the polyacrylonitrile synthetic fiber (A) is not particularly limited, and, for example, it can be produced by a wet spinning method.
• the wet spinning method is a method in which a spinning solution made of the above-mentioned copolymer is extruded from a spinning nozzle into a coagulation bath, and solidified therein to form a thread.
• the wet spinning method may include any one of a water washing process, a drying process, a stretching process, and a thermal relaxation process in addition to the above-mentioned coagulation process.
• the polyacrylonitrile synthetic fiber (A) may be produced by the method described above, or commercially available polyacrylonitrile synthetic fiber may be obtained.
• commercially available polyacrylonitrile synthetic fibers (A) include “AFRELLE” and “SYC” manufactured by Kaneka.
• Quaternary ammonium salt (B) The quaternary ammonium salt (B) (hereinafter sometimes simply referred to as “component (B)”) is represented by the following formula (1).
• R 1 is an alkyl group having 8 to 18 carbon atoms
• R 2 to R 4 are each independently a methyl group, an alkyl group having 8 to 18 carbon atoms, or 3-(trihydroxycysilyl).
• n is 1 or 2
• X n- is a bromide ion, chloride ion, fluoride ion, hydroxide ion, carbonate ion , any inorganic acid ion selected from the group consisting of sulfate ion, nitrate ion, phosphate ion, and borate ion, or a monoalkyl phosphate ion having an alkyl group having 1 to 3 carbon atoms, or a carbon number It is a dialkyl phosphate ion having 1 to 3 alkyl groups.
• R 1 is an alkyl group having 8 to 18 carbon atoms
• R 2 to R 4 are is also a methyl group
• R 1 and R 2 are both alkyl groups having 8 to 18 carbon atoms
• R 3 and R 4 are both methyl groups
• R 1 is an alkyl group having 8 to 18 carbon atoms.
• R 2 is a 3-(trihydroxycysilyl)propyl group
• R 3 and R 4 are both methyl groups
• R 1 is an alkyl group having 8 to 18 carbon atoms.
• R 2 is a 3-(trimethoxysilyl)propyl group
• R 3 and R 4 are both methyl groups
• n is preferably 1
• n- is a chloride ion or a dialkyl phosphate ion having an alkyl group having 1 to 3 carbon atoms.
• alkyl group having 8 to 18 carbon atoms in R 1 and R 2 include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, and tetradecyl group. , a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, and an alkyl group having a structural isomerism with these alkyl groups. Among these, octyl group, decyl group, dodecyl group, and hexadecyl group are preferred.
• the amount of the quaternary ammonium salt (B) to be deposited is set to 0.0% based on the total mass of the antibacterial polyacrylonitrile synthetic fibers.
• the content is preferably 0.05% by mass or more and 0.3% by mass or less, and preferably 0.1% by mass or more and 0.25% by mass or less.
• Nonionic surfactant (C) The nonionic surfactant (C) (hereinafter sometimes simply referred to as “component (C)”) includes sorbitan fatty acid ester (C1) and polyoxyethylene triglyceride (C2).
• Sorbitan fatty acid ester (C1) is an ester of sorbitan and fatty acid.
• the sorbitan fatty acid ester (C1) is not particularly limited, and examples include sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiolate, and sorbitan. Examples include triolate, sorbitan tristearate, and the like. Among these, sorbitan monostearate is preferred.
• Polyoxyethylene triglyceride (C2) Polyoxyethylene triglyceride (C2) is an ester of a fatty acid and a polymer obtained by addition polymerizing ethylene oxide to triglyceride.
• the polyoxyethylene triglyceride (C2) is not particularly limited, and examples thereof include polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene triisostearic acid, and the like. Among these, polyoxyethylene castor oil is preferred.
• the amount of the nonionic surfactant (C) attached is set to 0 based on the total mass of the antibacterial polyacrylonitrile synthetic fiber, from the viewpoint that the antibacterial polyacrylonitrile synthetic fiber has excellent antibacterial properties and has excellent texture. It is preferably 0.15% by mass or more and 0.9% by mass or less, and preferably 0.2% by mass or more and 0.6% by mass or less.
• the content of the sorbitan fatty acid ester (C1) is not particularly limited, and is preferably 20% by mass or more and 90% by mass or less, and 35% by mass or more based on the total mass of the nonionic surfactant (C). More preferably, it is 65% by mass or less.
• the content of polyoxyethylene triglyceride (C2) is not particularly limited, and is preferably 90% by mass or more and 20% by mass or less, and 65% by mass or more based on the total mass of the nonionic surfactant (C). More preferably, it is 35% by mass or less.
• the antibacterial polyacrylonitrile synthetic fiber may contain components other than the polyacrylonitrile synthetic fiber (A), the quaternary ammonium salt (B), and the nonionic surfactant (C), as long as the effects of the present invention are not impaired. (hereinafter also referred to as "other components").
• other components include gloss modifiers, organic pigments, inorganic pigments, coloring agents such as dyes, light stabilizers, heat stabilizers, fiber binding agents, deodorants, fragrances, insect repellents, crosslinking agents, etc. can be mentioned.
• the first embodiment of the method for producing the antibacterial polyacrylonitrile synthetic fiber described above involves obtaining a coagulated yarn by wet spinning a spinning solution containing an acrylonitrile polymer, and preparing a treated yarn before drying. is brought into contact with an oil containing the quaternary ammonium salt (B) and the nonionic surfactant (C). According to the manufacturing method of this embodiment, as described above, it is possible to manufacture an antibacterial polyacrylonitrile synthetic fiber suitable for use in artificial hair, which has excellent antibacterial properties and excellent texture.
• the treated yarn before being dried is treated with the quaternary ammonium salt ( B), the step of contacting with an oil agent containing the nonionic surfactant (C) (hereinafter also referred to as “contact step”), and an optional step will be explained.
• the acrylonitrile polymer is a raw material for producing yarn of polyacrylonitrile synthetic fiber (A).
• the acrylonitrile polymer is the same as the embodiment of the acrylonitrile polymer described in the item "(Polyacrylonitrile synthetic fiber (A))" above.
• the spinning solution contains the acrylonitrile polymer and an organic solvent.
• the organic solvent is not particularly limited, and it is preferable to use a good solvent for an acrylonitrile polymer.
• good solvents for acrylonitrile polymers include dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and acetone.
• DMSO dimethyl sulfoxide
• DMAc N,N-dimethylacetamide
• DMF N,N-dimethylformamide
• acetone may be used from the viewpoint of versatility.
• dimethyl sulfoxide may be used.
• the spinning solution may contain a small amount of water, for example, 1.5% by mass or more and 4.8% by mass or less of water. Thereby, formation of voids can be suppressed.
• the spinning solution may contain other additives for improving fiber properties, if necessary, within a range that does not impede the effects of the present invention.
• other additives include gloss modifiers, organic pigments, inorganic pigments, coloring agents such as dyes, and stabilizers for improving light resistance and heat resistance.
• the coagulation step is a step of discharging the above-mentioned spinning solution through a spinning nozzle into a coagulation solution (coagulation bath) and coagulating it to form a thread (hereinafter, such a thread is also referred to as a "coagulated thread"). It is.
• the operation of the coagulation step is not particularly limited, and for example, a wet spinning method may be used in which the spinning solution in the stock solution tank is directly discharged into the coagulation solution according to a conventional method. Alternatively, a dry-wet spinning method may be used in which the material is once discharged into the air from a spinning nozzle and then introduced into a coagulating liquid.
• the temperature of the spinning solution is not particularly limited as long as the spinning solution can be stably maintained in the stock solution tank without changing over time, and is usually preferably 40° C. or higher and 70° C. or lower, for example.
• the composition of the coagulating liquid is not particularly limited, and for example, it is preferable to use an aqueous solution of a good solvent such as acetone.
• the concentration of the good solvent is not particularly limited, and is preferably, for example, 10% by mass or more and 70% by mass or less. If it is less than 10% by mass, coagulation becomes rapid and the coagulation structure becomes coarse, and voids tend to be formed inside the fibers.
• the temperature of the coagulation liquid is not particularly limited, and is preferably, for example, 5°C or more and 40°C or less.
• the spinning nozzle can be used as appropriate depending on the desired fiber cross section.
• the cross section of the fiber is not particularly limited, and may be any cross section such as circular, elliptical, irregular shape, etc.
• the amount of the spinning solution discharged from the spinning nozzle is not particularly limited, and is preferably 0.1 g/min or more as a single hole discharge amount, for example.
• the spinning speed of the spinning solution from the spinning nozzle is not particularly limited, and from the viewpoint of industrial productivity, it is preferably 2 m/min or more and 17 m/min or less.
• the coagulated yarn (fiber) that has passed through the coagulation liquid is wound up by a take-up roller via a feed roller, for example, according to a conventional method, thereby obtaining an undrawn yarn.
• the film may be continuously advanced to other steps without being wound up.
• Wet spinning may include steps other than the coagulation step (hereinafter also referred to as "other steps") as long as the effects of the present invention are not impaired.
• Other steps include a water washing step, a drying step, a stretching step, a heat relaxation treatment step, and the like.
• the stretching process include a wet stretching process performed before the water washing process, or after the water washing process and before the drying process, and a dry stretching process performed after the drying process.
• each step is not particularly limited, and for example, after the coagulation step, a wet stretching step, a water washing step, a drying step, a dry stretching step, and a thermal relaxation treatment step are performed in order, or after the coagulation step, in order, Examples include a method of performing a water washing process, a wet stretching process, a drying process, a dry stretching process, and a heat relaxation treatment process.
• the wet drawing process is a process of drawing the coagulated yarn in a drawing bath (hereinafter also referred to as "primary drawing").
• a drawing bath it is preferable to use an aqueous solution having a lower concentration of a good solvent such as acetone than the coagulation bath.
• the temperature of the stretching bath is preferably 30°C or higher, more preferably 40°C or higher.
• the stretching ratio is not particularly limited, and from the viewpoint of increasing fiber strength and productivity, it is preferably 1.5 times or more and 8 times or less.
• a wet stretching process may be performed after the water washing process described below, or the primary stretching and water washing may be performed simultaneously.
• the water washing step is a step of removing a good solvent such as acetone attached to the yarn after the coagulation step or the wet stretching step.
• a good solvent such as acetone attached to the yarn after the coagulation step or the wet stretching step.
• hot water 70° C. or higher.
• the drying process is a process of densifying the yarn by drying the yarn.
• the drying temperature is not particularly limited, and is preferably, for example, 110°C or higher and 190°C or lower.
• the dry stretching process is a process of stretching the yarn under heating conditions (hereinafter also referred to as "secondary stretching").
• the stretching temperature is not particularly limited, and is preferably, for example, 110°C or higher and 190°C or lower.
• the stretching ratio is not particularly limited, and is preferably, for example, 1 to 4 times, more preferably 1.5 to 3.5 times, and even more preferably 1.5 to 3 times.
• the total stretching ratio including wet stretching before drying is preferably 2 times or more and 10 times or less, more preferably 2 times or more and 8 times or less, even more preferably 2 times or more and 6 times or less, and 2 times or more and 4 times or less. is particularly preferred.
• the thermal relaxation treatment step is a step of relaxing the yarn after dry stretching in a high temperature atmosphere.
• the relaxation rate is not particularly limited, and is preferably, for example, 5% or more, and more preferably 8% or more and 20% or less.
• the thermal relaxation treatment can be performed, for example, in a dry heat atmosphere of 140° C. or more and 200° C. or less or in a superheated steam atmosphere.
• the yarn to be treated before being dried is a yarn that has not been dried and therefore has not been densified, and is a yarn that is brought into contact with an oil agent to be described later.
• the yarn to be treated includes, in addition to the coagulated yarn obtained by the wet spinning, yarns that have been subjected to treatments other than the drying process, dry stretching process, and thermal relaxation treatment process described above.
• the yarns to be treated include coagulated yarns obtained by wet spinning, yarns after wet stretching, and yarns after washing with water. Among these, yarns that have been washed with water are preferred from the viewpoint of preventing organic solvents from being mixed into the oil agent.
• the oil agent contains the above-mentioned quaternary ammonium salt (B) and the above-mentioned nonionic surfactant (C).
• the oil agent is preferably used as a mixed liquid in which the quaternary ammonium salt (B) and the nonionic surfactant (C) are dispersed or dissolved in water.
• the oil agent may contain components other than the quaternary ammonium salt (B), the nonionic surfactant (C), and water (hereinafter also referred to as "other components") as long as the effects of the present invention are not impaired. It's okay.
• ingredients include, for example, modified silicone; antistatic agent; gloss modifier; coloring agents such as organic pigments, inorganic pigments, and dyes; light stabilizer; heat stabilizer; fiber convergence agent; deodorant; fragrance ; insect repellent; antibacterial agent; crosslinking agent, etc.
• the method of bringing the yarn to be treated into contact with the oil agent is not particularly limited, and examples thereof include dipping, spraying, showering, and coating. Among these, the method of immersion is preferred from the viewpoint of uniformly contacting each component contained in the oil agent.
• the contact temperature is not particularly limited, and can be adjusted as appropriate between 40°C and 90°C depending on the condition of the yarn to be treated and the desired amount of adhesion.
• the contact time is also not particularly limited, and can be appropriately adjusted from 1 second to 10 minutes depending on the condition of the yarn to be treated and the desired amount of adhesion.
• the dried polyacrylonitrile synthetic fiber (A) is mixed with the quaternary ammonium salt (B) and the nonionic surfactant.
• the method includes contacting with an oil agent containing (C) and drying the filament after the contact treatment. According to the manufacturing method of this embodiment, as described above, it is possible to manufacture an antibacterial polyacrylonitrile synthetic fiber suitable for use in artificial hair, which has excellent antibacterial properties and excellent texture.
• the step of bringing the dried polyacrylonitrile synthetic fiber (A) into contact with an oil agent containing the quaternary ammonium salt (B) and the nonionic surfactant (C) (hereinafter also referred to as “contact step")
• drying step a step of drying the filament after the contact treatment
• an optional step will be explained.
• the polyacrylonitrile synthetic fiber (A) is the same as the embodiment described in the above-mentioned "(Polyacrylonitrile synthetic fiber (A))" section.
• the dried polyacrylonitrile synthetic fiber (A) can be obtained by drying the polyacrylonitrile synthetic fiber (A), for example, at room temperature or higher and 190° C. or lower.
• the oil agent containing the above-mentioned quaternary ammonium salt (B) and the above-mentioned nonionic surfactant (C) is the same as the embodiment described in the above-mentioned "(Oil agent)" section.
• the method of contacting the dried polyacrylonitrile synthetic fiber (A) with the oil agent is the same as the embodiment described in the above-mentioned "(Contact method)" section.
• the contact time is preferably set longer than the contact time in ⁇ Production method 1 of antibacterial polyacrylonitrile synthetic fiber>> described above.
• the drying step is a step of drying the filamentous polyacrylonitrile synthetic fiber (A) after the contact treatment to densify the filament.
• the drying temperature is not particularly limited, and is preferably, for example, 110°C or higher and 190°C or lower.
• This manufacturing method 2 may include steps other than the contact step and the drying step (hereinafter also referred to as "other steps") as long as the effects of the present invention are not impaired.
• Other steps include a stretching step, a thermal relaxation treatment step, and the like.
• the stretching process and the thermal relaxation treatment process are the same as the embodiments described in the above-mentioned "(Stretching process)” and “(Thermal relaxation treatment process)” items.
• the headdress product includes the antibacterial polyacrylonitrile synthetic fiber described above.
• Headdress products are not particularly limited, and include, for example, hair wigs, wigs, weaving, hair extensions, braided hair, hair accessories, doll hair, and the like.
• Antibacterial polyacrylonitrile synthetic 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 form 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.
• B1 Hexadecyltrimethylammonium chloride
• B2 Dodecyltrimethylammonium chloride
• B3 Dodecyltrimethylammonium dimethyl phosphate
• B4 Dioctyldimethylammonium chloride
• B5 Didecyldimethylammonium chloride
• B6 Dimethyl (ocdadecyl) [3-(trihydroxysilyl)propyl]
• B7 dimethyl(dodecyl)[3-(trimethoxysilyl)propyl]ammonium chloride
• C1 Sorbitan monostearate
• C2 Polyoxyethylene castor oil
• the yarn was washed with warm water at 90°C, and immersed in an oil bath (60°C) containing each of the oils listed in Table 1 for 1 to 3 seconds to impregnate the yarn with the oil. , dried at 140°C, stretched 3 times, subjected to 27% relaxation treatment at 155°C, and had a single fiber fineness of about 46 dtex.
• the amount of the quaternary ammonium salt (B) and the nonionic surfactant (C) attached "%owf” is the amount of the quaternary ammonium salt (B) based on the total mass of the antibacterial polyacrylonitrile synthetic fiber. Or it means the mass % of the nonionic surfactant (C).
• the amounts of the quaternary ammonium salt (B) and the nonionic surfactant (C) deposited are as follows: After producing the antibacterial polyacrylonitrile synthetic fiber, the amount of the quaternary ammonium salt (B) and The nonionic surfactant (C) was extracted and calculated from the extracted amount of each component obtained.
• the antibacterial activity value of the antibacterial polyacrylonitrile synthetic fiber was measured according to JIS L 1902:2015 (antibacterial test/quantitative test of textile products (bacterial liquid absorption method)). Staphylococcus aureus was used in the test. In order to prevent the sample from deteriorating in shape, the test was conducted without high-pressure steam sterilization of the sample. According to the "SEK Mark Textile Product Certification Standards," an antibacterial activity value of 2.2 or more indicates that the product has an antibacterial and deodorizing effect.
• AFRELLE polyacrylonitrile synthetic fiber, manufactured by Kaneka, 46 dtex.
• the tactile sensations were comprehensively evaluated using the following three-level criteria.

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• 2023
  • 2023-03-29 JP JP2024512727A patent/JPWO2023190761A1/ja active Pending
  • 2023-03-29 KR KR1020247026129A patent/KR20240128093A/ko active Pending
  • 2023-03-29 WO PCT/JP2023/012984 patent/WO2023190761A1/ja not_active Ceased
• 2024
  • 2024-07-19 US US18/778,255 patent/US20240368830A1/en active Pending

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