WO2019235055A1 - 人工毛髪用繊維及び頭髪装飾製品 - Google Patents
人工毛髪用繊維及び頭髪装飾製品 Download PDFInfo
- Publication number
- WO2019235055A1 WO2019235055A1 PCT/JP2019/015429 JP2019015429W WO2019235055A1 WO 2019235055 A1 WO2019235055 A1 WO 2019235055A1 JP 2019015429 W JP2019015429 W JP 2019015429W WO 2019235055 A1 WO2019235055 A1 WO 2019235055A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fiber
- vinyl
- artificial hair
- mass
- vinyl chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
- A41G3/00—Wigs
- A41G3/0083—Filaments for making wigs
-
- 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
- A41G5/00—Hair pieces, inserts, rolls, pads, or the like; Toupées
- A41G5/004—Hair pieces
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/014—Stabilisers against oxidation, heat, light or ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0075—Antistatics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Definitions
- the present invention relates to a fiber for artificial hair having good combability and a hair decoration product using the same.
- vinyl chloride resin fibers obtained by spinning vinyl chloride resin are excellent in flexibility, they are often used as artificial hair fibers constituting hair ornament products.
- the vinyl chloride resin fiber is not suitable for a style that requires a volume because the specific gravity of the vinyl chloride resin as a raw material is large.
- the composition ratio of the vinyl copolymer was set within a specific range.
- the proportion of vinyl cyanide bond units in the vinyl copolymer increases, the yarn tends to break during stretching, so the maximum draw ratio must be reduced. There was a problem that the yarn was easily broken.
- the present invention provides a fiber for artificial hair and a hair decoration product having good combability.
- a fiber for artificial hair comprising a resin composition containing a vinyl chloride resin, a vinyl copolymer, and a vinyl chloride acrylic graft copolymer.
- the artificial hair fiber according to (1) wherein the vinyl chloride acrylic graft copolymer is 1 to 20 parts by mass with respect to 100 parts by mass in total of the vinyl chloride resin and the vinyl copolymer.
- a fiber for artificial hair containing parts (3) The artificial hair fiber according to (1) or (2), wherein 50 to 95 mass of the vinyl chloride resin is contained in a total of 100 mass parts of the vinyl chloride resin and the vinyl copolymer. And a fiber for artificial hair containing 5 to 50 parts by mass of the vinyl copolymer.
- a fiber for artificial hair having 0 to 40% by mass of monomer units and 0 to 85% by mass of methacrylic acid ester monomer units.
- a fiber for artificial hair. (9) The artificial hair fiber according to any one of (1) to (8), wherein the antistatic agent is used with respect to 100 parts by mass in total of the vinyl chloride resin and the vinyl copolymer.
- a hair ornament product comprising the artificial hair fiber according to any one of (1) to (9).
- a fiber for artificial hair having a good combing property and a hair decoration product using the same are obtained.
- the present invention is a fiber for artificial hair comprising a resin composition containing a vinyl chloride resin, a vinyl copolymer, and a vinyl chloride acrylic graft copolymer.
- the vinyl chloride resin used in the present invention is a conventionally known vinyl chloride homopolymer resin, or a conventionally known copolymer resin of vinyl chloride and various monomers, and is not particularly limited.
- the copolymer resins include vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl propionate copolymer resins and other vinyl chloride and vinyl ester copolymer resins, vinyl chloride-butyl acrylate copolymer resins, vinyl chloride-acrylic acid 2 Copolymer resins of vinyl chloride and acrylates such as ethylhexyl copolymer resin, vinyl chloride-ethylene copolymer resins, vinyl chloride-propylene copolymer resins such as vinyl chloride-olefin copolymer resins, vinyl chloride-acrylonitrile copolymer resins, etc.
- Preferred vinyl chloride resins include homopolymer resins that are homopolymers of vinyl chloride, vinyl chloride-ethylene copolymer resins, vinyl chloride-vinyl acetate copolymer resins, and the like.
- the content of the comonomer is not particularly limited, and can be determined according to the moldability of the fiber, the properties of the fiber, and the like.
- the viscosity average polymerization degree of the vinyl chloride resin used in the present invention is preferably in the range of 450 to 1700 in order to obtain sufficient strength and heat resistance as a fiber.
- the viscosity average degree of polymerization is preferably adjusted to 650 to 1450.
- the viscosity average degree of polymerization is preferably adjusted to 1000 to 1700.
- the viscosity average degree of polymerization is calculated according to JIS-K6721 by dissolving 200 mg of resin in 50 ml of nitrobenzene, measuring the specific viscosity of this polymer solution in a constant temperature bath at 30 ° C. using an Ubbelohde viscometer.
- the vinyl chloride resin used in the present invention can be produced by emulsion polymerization, bulk polymerization or suspension polymerization.
- a polymer produced by suspension polymerization is preferable, and can be obtained by a known method described in Patent Document 3 and the like.
- vinyl copolymer examples include aromatic vinyls such as styrene, ⁇ -methylstyrene, vinyltoluene, ethylstyrene, t-butylstyrene, chlorostyrene, dichlorostyrene, acrylonitrile, methacrylonitrile, 2 types from vinyl cyanides such as chloroacrylonitrile, acrylic esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, vinyl carboxylic acids such as acrylic acids and methacrylic acids, etc. Those selected and copolymerized may be mentioned.
- aromatic vinyls such as styrene, ⁇ -methylstyrene, vinyltoluene, ethylstyrene, t-butylstyrene, chlorostyrene, dichlorostyrene, acrylon
- the vinyl copolymer preferably contains 10 to 85% by mass of aromatic vinyl monomer units, 0 to 40% by mass of vinyl cyanide monomer units, and 0 to 85% by mass of methacrylic acid ester monomer units. Have. Within such a range, the compatibility with the vinyl chloride resin is improved, and the spinnability is improved, so that more stable productivity can be obtained.
- the vinyl-based copolymer preferably has 60 to 85% by mass of aromatic vinyl monomer units and 40 to 15% by mass of vinyl cyanide monomer units. Within such a range, the compatibility with the vinyl chloride resin is improved, and the spinnability is improved, so that more stable productivity can be obtained.
- aromatic vinyl monomer unit of the vinyl copolymer examples include styrenes such as styrene, ⁇ -methylstyrene, vinyltoluene, ethylstyrene, t-butylstyrene, chlorostyrene, dichlorostyrene, and substituted products thereof.
- styrene is particularly preferred. Since the styrene can easily adjust the resin pressure during spinning and can reduce the screw load, it can ensure long run performance for a long time.
- Examples of the vinyl cyanide monomer unit of the vinyl copolymer include acrylonitrile, methacrylonitrile, chloroacrylonitrile and the like, among which acrylonitrile is particularly preferable. Since the acrylonitrile can easily adjust the resin pressure during spinning and can reduce the screw load, it can ensure long run performance for a long time.
- Examples of the methacrylic acid ester monomer unit of the vinyl copolymer include methyl methacrylate and ethyl methacrylate. Among these, methyl methacrylate is particularly preferable. Since the methyl methacrylate has a solubility parameter close to that of the vinyl chloride resin, the transparency of the fiber can be improved.
- the blending ratio of the vinyl chloride resin and the vinyl copolymer is such that the vinyl chloride resin and the vinyl copolymer in a total of 100 parts by mass are vinyl based on 50 to 95 parts by mass of the vinyl chloride resin.
- the amount of the copolymer is preferably 5 to 50 parts by mass, and more preferably 15 to 40 parts by mass of the vinyl copolymer with respect to 60 to 85 parts by mass of the vinyl chloride resin. In such a range, the resulting artificial hair fiber has a large volume and the spinnability of the resin composition is particularly good.
- the vinyl chloride acrylic graft copolymer used in the present invention comprises a backbone polymer derived from a (meth) acrylic copolymer, and a graft chain derived from a vinyl chloride monomer grafted on the backbone polymer or a vinyl chloride mixed monomer. Including.
- the vinyl chloride acrylic graft copolymer can be produced by, for example, a conventionally known method described in Patent Document 4.
- the compatibility of the vinyl chloride resin and the vinyl copolymer is increased. Therefore, it becomes possible to extend
- the vinyl chloride acrylic graft copolymer has a particle form, and the basic polymer (derived from the (meth) acrylic copolymer) constitutes the core, and the graft chain (vinyl chloride) Monomer or vinyl chloride mixed monomer) having a core-shell structure constituting the shell, the resin particles are stable, and when mixed with a resin mixture of vinyl chloride resin and vinyl copolymer, spinnability It is preferable in terms of improvement.
- the average degree of polymerization of the vinyl chloride acrylic graft copolymer is preferably 400 to 1800, more preferably 600 to 1000, and still more preferably 600 to 800.
- the spinnability is particularly good when the average degree of polymerization of the vinyl chloride acrylic graft copolymer is within the above range.
- the average degree of polymerization refers to a resin obtained by dissolving a vinyl chloride acrylic graft copolymer in tetrahydrofuran (THF), removing insoluble components by filtration, and then removing the THF in the filtrate by drying.
- THF tetrahydrofuran
- the acrylic copolymer content in the vinyl chloride acrylic graft copolymer is preferably 8 to 55% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 45% by mass. %. This is because the spinnability and combability are particularly good when the thickness is within such a range.
- the compounding amount of the vinyl chloride acrylic graft copolymer used in the present invention is preferably 1 to 20 parts by mass, more preferably 100 parts by mass with respect to a total of 100 parts by mass of the vinyl chloride resin and the vinyl copolymer. 2 to 15 parts by mass. This is because the spinnability and combability are particularly good when the thickness is within such a range.
- an antistatic agent, a heat stabilizer and a lubricant can be appropriately mixed at a predetermined ratio.
- the antistatic agent used in the present invention may be cationic, anionic or amphoteric.
- the blending amount of the antistatic agent is preferably in the range of 0.01 to 1 part by mass with respect to 100 parts by mass in total of the vinyl chloride resin and the vinyl copolymer. By adjusting the blending amount of the antistatic agent within this range, generation of static electricity is suppressed, and thread breakage is less likely to occur in the manufacturing process of the artificial hair fiber.
- heat stabilizers can be used as the heat stabilizer used in the present invention.
- the thermal stabilizer is used to improve thermal decomposition during molding, long run property, and color tone of the filament, and is particularly preferably a Ca-Zn based thermal stabilizer that has an excellent balance of molding processability and yarn characteristics.
- the combined use of an agent and a hydrotalcite heat stabilizer is preferred.
- the blending amount of these heat stabilizers is preferably 0.1 to 5.0 parts by mass with respect to a total of 100 parts by mass of the vinyl chloride resin and the vinyl copolymer.
- the hydrotalcite-based heat stabilizer is specifically a hydrotalcite compound, more specifically, a complex salt compound composed of magnesium and / or alkali metal and aluminum or zinc, magnesium and aluminum, There is something that has been dehydrated.
- the hydrotalcite compound may be a natural product or a synthetic product, and the synthesis method of the synthetic product may be a conventionally known method.
- examples of the Ca—Zn heat stabilizer include zinc stearate, calcium stearate, zinc 12-hydroxystearate, and calcium 12-hydroxystearate.
- examples of the hydrotalcite-based heat stabilizer include Alkamizer manufactured by Kyowa Chemical Industry Co., Ltd.
- Tin stabilizers include dimethyltin mercapto, dimethyltin mercaptoide, dibutyltin mercapto, dioctyltin mercapto, dioctyltin mercaptopolymer, mercaptotin thermal stabilizers such as dioctyltin mercaptoacetate, dimethyltin maleate, dibutyltin maleate , Maleate tin thermal stabilizers such as dioctyl tin maleate and dioctyl tin maleate polymer, and laurate tin thermal stabilizers such as dimethyltin laurate, dibutyltin laurate and dioctyltin laurate.
- Examples of the epoxy heat stabilizer include epoxidized oils such as epoxidized soybean oil and epoxidized linseed oil.
- Examples of the ⁇ -diketone heat stabilizer include stearoylbenzoylmethane (SBM) and dibenzoylmethane (DBM).
- SBM stearoylbenzoylmethane
- DBM dibenzoylmethane
- the blending amount of these heat stabilizers is preferably 0.2 to 10.0 parts by mass with respect to a total of 100 parts by mass of the vinyl chloride resin and the vinyl copolymer.
- a conventionally well-known thing can be used for the lubricant used for this invention.
- at least one selected from the group consisting of metal soap lubricants, hydrocarbon lubricants, higher fatty acid lubricants, ester lubricants and higher alcohol lubricants is preferred.
- the lubricant can reduce the friction with the metal surface of the processing machine and the friction between the resins, improve the fluidity, and improve the workability.
- the blending amount of the lubricant is preferably 0.2 to 5.0 parts by mass with respect to 100 parts by mass in total of the vinyl chloride resin and the vinyl copolymer. By adjusting the blending amount of the lubricant within this range, the fluidity of the resin composition is improved, so that the resin composition can be stably molded.
- metal soap lubricant examples include metal soaps such as stearates such as Na, Mg, Al, Ca and Ba, laurates, palmitates and oleates.
- hydrocarbon lubricant examples include polyethylene wax and polypropylene wax.
- higher fatty acid lubricant examples include saturated fatty acids such as stearic acid, palmitic acid, myristic acid, lauric acid and capric acid, unsaturated fatty acids such as oleic acid, and mixtures thereof.
- ester lubricants include ester lubricants composed of alcohol and fatty acid, pentaerythritol lubricants such as monoester, diester, triester, tetraester, and mixtures of pentaerythritol or dipentaerythritol and higher fatty acids, and montanic acid.
- ester lubricants include montanic acid wax-based lubricants of esters of stearyl alcohol, palmityl alcohol, myristyl alcohol, lauryl alcohol, oleyl alcohol, and other higher alcohols.
- higher alcohol lubricants include stearyl alcohol, palmityl alcohol, myristyl alcohol, lauryl alcohol, oleyl alcohol, and the like.
- known compounding agents can be added to the resin composition of the present invention within a range that does not impair the effects of the present invention.
- the compounding agents include processing aids, plasticizers, reinforcing agents, ultraviolet absorbers, antioxidants, fillers, flame retardants, pigments, initial color improvers, conductivity imparting agents, and fragrances.
- Resin Composition and Method for Producing Artificial Hair Fiber To obtain a resin composition, an antistatic agent is appropriately added to the vinyl chloride resin, the vinyl copolymer, and the vinyl chloride acrylic graft copolymer, A heat stabilizer and a lubricant are mixed at a predetermined ratio, and a powder compound is obtained by stirring and mixing using a conventionally known Henschel mixer, super mixer, ribbon blender, etc., and then melt-kneaded with an extruder to make a pellet compound. To.
- the powder compound can be produced by either hot blend or cold blend, and normal conditions can be used as production conditions.
- hot blending is used to reduce the volatile content in the resin composition.
- the pellet compound can be produced in the same manner as ordinary vinyl chloride-based pellet compounds. For example, pellet compounding using a kneader such as a single screw extruder, a different direction twin screw extruder, a conical twin screw extruder, a same direction twin screw extruder, a kneader, a planetary gear extruder, or a roll kneader. It can be.
- the conditions for producing the pellet compound are not particularly limited, but it is preferable to set the resin temperature to 190 ° C.
- a mesh can be installed in the vicinity of the tip of the screw in order to remove the metal pieces of the screw and the fibers attached to the protective gloves that can be mixed in a small amount in the pellet compound.
- the cold cut method can be used for the production of pellets. It is possible to employ means for removing “cutting powder” (fine powder generated during pellet production) and the like that may be mixed during cold cutting. In addition, if the cutter is used for a long time, the cutter spills and chips are likely to be generated.
- a cylinder temperature of 150 to 190 ° C. and a nozzle temperature of 165 to 195 ° C. are used by using a nozzle in which the secondary moment of the weak axis of the nozzle hole section is in a predetermined range. In the range, the resin is extruded and melt-spun under conditions with good spinnability.
- Unstretched yarn (fiber of resin composition) melt-spun from the nozzle is introduced into a heated cylinder (heated cylinder temperature of about 250 ° C.), instantaneously heat-treated, and placed at a position of about 4.5 m directly under the nozzle. It is wound up by a take-up machine. The strand remains an undrawn yarn. At the time of winding, the take-up speed is adjusted so that the fineness of the undrawn yarn is 194 to 206 dtex.
- a conventionally well-known extruder can be used.
- a single-screw extruder, a different-direction twin-screw extruder, a conical twin-screw extruder, etc. can be used.
- the undrawn yarn is drawn 2 to 4 times with a drawing machine (90 to 120 ° C. in an air atmosphere) and then 0.5 to 0.9 times using a heat treatment machine (110 to 140 ° C. under an air atmosphere). Heat treatment is performed to prepare artificial hair fibers so that the fineness is 64 to 69 dtex.
- the artificial hair fiber of the present invention obtained as described above can improve volume and heat resistance.
- Hair decoration products Artificial hair fibers may be used alone in hair decoration products, or may be used by mixing human hair or other artificial hair.
- the hair decoration products are wigs, hair pieces, blades, extension hairs, doll hairs, etc., and the use of artificial hair fibers is not particularly limited.
- hair ornament products it can also be used for false eyelashes, false eyelashes, false eyebrows and the like.
- Tables 1 and 2 show the results. ⁇ Examples 1 to 23, Comparative Example 1> Tables 1 and 2 summarize the formulations and the evaluation results of Examples 1 to 23 and Comparative Example 1.
- Vinyl chloride acrylic graft copolymer (average polymerization degree 800, acrylic copolymer content 16%, Sekisui Chemical Co., Ltd., AG-162E) -Other than the above, manufactured in-house (produced by combining an average degree of polymerization of 300, 400, 800, 1800, 2000 and an acrylic copolymer content of 3, 8, 16, 40, 55, 70)
- the combability is the occurrence of yarn breakage when a fiber bundle sample in which fibers for artificial hair are bundled in a length of 300 mm and a mass of 20.0 g is used and the combing is repeated 50 times.
- the evaluation was as follows. S: No thread break A: 2 to 3 thread breaks B: 4 to 5 thread breaks X: 6 or more thread breaks
- volume is a 56 cc container (100 mm x 14 mm x 40 mm) filled with 100 mm cut fibers until the container is full, the filled fibers are taken out and weighed, and the following formula is used: The specific volume was calculated, and the second decimal place was rounded off and evaluated as follows.
- Container volume (cc) / fiber weight (g) specific volume (cc / g) S: Specific volume is 2.5 (cc / g) or more A: Specific volume is 2.0 to 2.4 (cc / g) B: Specific volume is 1.7 to 1.9 (cc / g) C: Specific volume is 1.4 to 1.6 (cc / g) X: Specific volume is 1.3 (cc / g) or less
- the comparative example 1 which does not contain a vinyl chloride acrylic graft copolymer has poor combability.
- Wigs, hairpieces, blades, extension hairs, and doll hairs were prepared by the conventionally known methods using the artificial hair fibers of the examples. These obtained hair ornament products had good combability.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
(1)塩化ビニル系樹脂と、ビニル系共重合体と、塩化ビニル系アクリルグラフト共重合体を含有する樹脂組成物からなる人工毛髪用繊維。
(2)(1)に記載の人工毛髪用繊維であって、前記塩化ビニル系樹脂と前記ビニル系共重合体の合計100質量部に対し、前記塩化ビニル系アクリルグラフト共重合体1~20質量部を含有する、人工毛髪用繊維。
(3)(1)又は(2)に記載の人工毛髪用繊維であって、前記塩化ビニル系樹脂と前記ビニル系共重合体の合計100質量部中に、前記塩化ビニル系樹脂50~95質量部と、前記ビニル系共重合体5~50質量部を含有する、人工毛髪用繊維。
(4)(1)~(3)の何れか1つに記載の人工毛髪用繊維であって、前記塩化ビニル系アクリルグラフト共重合体は、平均重合度400~1800である、人工毛髪用繊維。
(5)(1)~(4)の何れか1つに記載の人工毛髪用繊維であって、前記塩化ビニル系アクリルグラフト共重合体は、アクリル系共重合体含量8~55質量%である、人工毛髪用繊維。
(6)(1)~(5)の何れか1つに記載の人工毛髪用繊維であって、前記ビニル系共重合体が、芳香族ビニル単量体単位10~85質量%、シアン化ビニル単量体単位0~40質量%、メタクリル酸エステル単量体単位0~85質量%を有する、人工毛髪用繊維。
(7)(6)に記載の人工毛髪用繊維であって、前記芳香族ビニル単量体単位が60~85質量%であり、シアン化ビニル単量体単位が40~15質量%である、人工毛髪用繊維。
(8)(6)又は(7)に記載の人工毛髪用繊維であって、前記芳香族ビニル単量体単位がスチレンに由来するものであり、前記シアン化ビニル単量体単位がアクリロニトリルに由来するものである、人工毛髪用繊維。
(9)(1)~(8)の何れか1つに記載の人工毛髪用繊維であって、前記塩化ビニル系樹脂と前記ビニル系共重合体の合計100質量部に対して、帯電防止剤0.01~1質量部、ハイドロタルサイト系複合熱安定剤0.1~5.0質量部、エポキシ化油0.2~10.0質量部、及び、エステル系滑剤0.2~5.0質量部含有する、人工毛髪用繊維。
(10)(1)~(9)の何れか1つに記載の人工毛髪用繊維からなる頭髪装飾製品。
(11)(10)に記載の頭髪装飾製品であって、ウィッグ、ヘアーピース、ブレード、エクステンションヘアー、ドールヘアーから選ばれる少なくとも一種である、頭髪装飾製品。
なお、本発明は、以下に説明する実施形態に限定されるものではない。
本発明は、塩化ビニル系樹脂と、ビニル系共重合体と、塩化ビニル系アクリルグラフト共重合体を含有する樹脂組成物からなる人工毛髪用繊維である。
本発明に使用する塩化ビニル系樹脂は、従来公知の塩化ビニルのホモポリマー樹脂、又は従来公知の塩化ビニルと各種モノマーとのコポリマー樹脂であり、特に限定されるものではない。該コポリマー樹脂としては、塩化ビニル-酢酸ビニルコポリマー樹脂、塩化ビニル-プロピオン酸ビニルコポリマー樹脂などの塩化ビニルとビニルエステル類とのコポリマー樹脂、塩化ビニル-アクリル酸ブチルコポリマー樹脂、塩化ビニル-アクリル酸2エチルヘキシルコポリマー樹脂などの塩化ビニルとアクリル酸エステル類とのコポリマー樹脂、塩化ビニル-エチレンコポリマー樹脂、塩化ビニル-プロピレンコポリマー樹脂などの塩化ビニルとオレフィン類とのコポリマー樹脂、塩化ビニル-アクリロニトリルコポリマー樹脂などが代表的に例示される。好ましい塩化ビニル系樹脂は、塩化ビニルの単独重合物であるホモポリマー樹脂、塩化ビニル-エチレンコポリマー樹脂、塩化ビニル-酢酸ビニルコポリマー樹脂などがあげられる。該コポリマー樹脂において、コモノマーの含有量は特に限定されず、繊維への成型加工性、繊維の特性などに応じて決めることができる。
本発明に使用されるビニル系共重合体としては、スチレン、α-メチルスチレン、ビニルトルエン、エチルスチレン、t-ブチルスチレン、クロロスチレン、ジクロロスチレン等の芳香族ビニル類、アクリロニトリル、メタクリロニトリル、クロロアクリロニトリル等のシアン化ビニル類、メチルアクリレート、エチルアクリレート、ブチルアクリレート等のアクリル酸エステル類、メチルメタクリレート、エチルメタクリレート等のメタクリル酸エステル類、アクリル酸類、メタクリル酸類等のビニルカルボン酸等から2種以上選択し共重合したものが挙げられる。
本発明に使用する塩化ビニル系アクリルグラフト共重合体は、(メタ)アクリル系共重合体に由来する基幹ポリマーと、当該基幹ポリマーにグラフトされた塩化ビニルモノマーまたは塩化ビニル混合モノマーに由来するグラフト鎖とを含む。
高級アルコール系滑剤としては、ステアリルアルコール、パルミチルアルコール、ミリスチルアルコール、ラウリルアルコール、オレイルアルコールなどが例示される。
樹脂組成物を得るには、前記塩化ビニル系樹脂と、前記ビニル系共重合体と、塩化ビニル系アクリルグラフト共重合体に、適宜、帯電防止剤、熱安定剤及び滑剤等を所定の割合で混合し、従来公知のヘンシェルミキサー、スーパーミキサー、リボンブレンダーなどを使用して攪拌混合してパウダーコンパウンドを得た後、押出機で溶融混練してペレットコンパウンドにする。
人工毛髪繊維は、単独で頭髪装飾製品に用いてもよいが、人毛や他の人工毛髪を混合して用いてもよい。頭髪装飾製品は、ウィッグ(かつら)、ヘアーピース、ブレード、エクステンンョンヘアー、ドールヘアー等であり、人工毛髪繊維の用途は特に限定されない。また、頭髪装飾製品以外にも付け髭、付け睫毛、付け眉毛等に用いることもできる。
<実施例1>
<実施例1~23、比較例1>
実施例1~23、比較例1の配合等と評価結果を表1~表2にまとめる。
<塩化ビニル系樹脂>
・塩化ビニル系樹脂(大洋塩ビ株式会社製、TH-1000)
・スチレン単量体単位68質量%、アクリロニトリル単量体単位32質量%(自社製、GR-AT-6S)
・スチレン単量体単位80質量%、アクリロニトリル単量体単位20質量%(自社製)
・スチレン単量体単位55質量%、アクリロニトリル単量体単位45質量%(自社製)
・メタクリル酸メチル単量体単位80質量%、アクリロニトリル単量体単位20質量%(自社製)
・スチレン単量体単位20質量%、メタクリル酸メチル単量体単位75質量%、アクリロニトリル単量体単位5質量%(自社製)
・塩化ビニル系アクリルグラフト共重合体(平均重合度800、アクリル系共重合体含量16%、積水化学工業株式会社製、AG-162E)
・上記以外は、自社製(平均重合度300、400、800、1800、2000と、アクリル系共重合体含量3、8、16、40、55、70を組み合わせたものを作製)
紡糸性は、溶融紡糸し、未延伸糸ができる間で、糸切れの発生状況を観察し、次のとおり評価した。
S:糸切れが1回/1時間
A:糸切れが2~3回/1時間
B:糸切れが4~5回/1時間
X:糸切れが6回以上/1時間
櫛掛け性は、人工毛髪用繊維を長さ300mm、質量20.0gに束ねた繊維束サンプルを使用し、櫛掛けを50回繰り返した際の糸切れの発生状況を、次のとおり評価した。
S:糸切れ無し
A:糸切れが2~3箇所
B:糸切れが4~5箇所
X:糸切れが6箇所以上
ボリュームは、56ccの容器(100mm×14mm×40mm)に、100mmに切断した繊維を容器が一杯になるまで充填させた後、充填させた繊維を取り出し計量し、下記の式にて比容積を算出し、小数第2位を四捨五入して、次のとおり評価した。
容器の容積(cc)÷繊維重量(g)=比容積(cc/g)
S:比容積が2.5(cc/g)以上
A:比容積が2.0~2.4(cc/g)
B:比容積が1.7~1.9(cc/g)
C:比容積が1.4~1.6(cc/g)
X:比容積が1.3(cc/g)以下
Claims (11)
- 塩化ビニル系樹脂と、ビニル系共重合体と、塩化ビニル系アクリルグラフト共重合体を含有する樹脂組成物からなる人工毛髪用繊維。
- 請求項1に記載の人工毛髪用繊維であって、
前記塩化ビニル系樹脂と前記ビニル系共重合体の合計100質量部に対し、前記塩化ビニル系アクリルグラフト共重合体1~20質量部を含有する、人工毛髪用繊維。 - 請求項1又は請求項2に記載の人工毛髪用繊維であって、
前記塩化ビニル系樹脂と前記ビニル系共重合体の合計100質量部中に、前記塩化ビニル系樹脂50~95質量部と、前記ビニル系共重合体5~50質量部を含有する、人工毛髪用繊維。 - 請求項1~請求項3の何れか1つに記載の人工毛髪用繊維であって、
前記塩化ビニル系アクリルグラフト共重合体は、平均重合度400~1800である、人工毛髪用繊維。 - 請求項1~請求項4の何れか1つに記載の人工毛髪用繊維であって、
前記塩化ビニル系アクリルグラフト共重合体は、アクリル系共重合体含量8~55質量%である、人工毛髪用繊維。 - 請求項1~請求項5の何れか1つに記載の人工毛髪用繊維であって、
前記ビニル系共重合体が、芳香族ビニル単量体単位10~85質量%、シアン化ビニル単量体単位0~40質量%、メタクリル酸エステル単量体単位0~85質量%を有する、人工毛髪用繊維。 - 請求項6に記載の人工毛髪用繊維であって、
前記芳香族ビニル単量体単位が60~85質量%であり、シアン化ビニル単量体単位が40~15質量%である、人工毛髪用繊維。 - 請求項6又は請求項7に記載の人工毛髪用繊維であって、
前記芳香族ビニル単量体単位がスチレンに由来するものであり、前記シアン化ビニル単量体単位がアクリロニトリルに由来するものである、人工毛髪用繊維。 - 請求項1~請求項8の何れか1つに記載の人工毛髪用繊維であって、
前記塩化ビニル系樹脂と前記ビニル系共重合体の合計100質量部に対して、帯電防止剤0.01~1質量部、ハイドロタルサイト系複合熱安定剤0.1~5.0質量部、エポキシ化油0.2~10.0質量部、及び、エステル系滑剤0.2~5.0質量部含有する、人工毛髪用繊維。 - 請求項1~請求項9の何れか1つに記載の人工毛髪用繊維からなる頭髪装飾製品。
- 請求項10に記載の頭髪装飾製品であって、
ウィッグ、ヘアーピース、ブレード、エクステンションヘアー、ドールヘアーから選ばれる少なくとも一種である、頭髪装飾製品。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17/046,155 US11807747B2 (en) | 2018-06-07 | 2019-04-09 | Fiber for artificial hair and hair decorating product |
| KR1020207035493A KR20210016546A (ko) | 2018-06-07 | 2019-04-09 | 인공 모발용 섬유 및 두발 장식 제품 |
| CN201980033358.5A CN112135540B (zh) | 2018-06-07 | 2019-04-09 | 人工毛发用纤维以及头发装饰制品 |
| JP2020523542A JP7198278B2 (ja) | 2018-06-07 | 2019-04-09 | 人工毛髪用繊維及び頭髪装飾製品 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-109386 | 2018-06-07 | ||
| JP2018109386 | 2018-06-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2019235055A1 true WO2019235055A1 (ja) | 2019-12-12 |
Family
ID=68770008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2019/015429 Ceased WO2019235055A1 (ja) | 2018-06-07 | 2019-04-09 | 人工毛髪用繊維及び頭髪装飾製品 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US11807747B2 (ja) |
| JP (1) | JP7198278B2 (ja) |
| KR (1) | KR20210016546A (ja) |
| CN (1) | CN112135540B (ja) |
| WO (1) | WO2019235055A1 (ja) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023145171A1 (ja) * | 2022-01-25 | 2023-08-03 | デンカ株式会社 | 人工毛髪用繊維及び頭髪装飾製品 |
| WO2024090375A1 (ja) * | 2022-10-26 | 2024-05-02 | 株式会社カネカ | 塩化ビニル系繊維、及びその製造方法 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2022196437A1 (ja) * | 2021-03-15 | 2022-09-22 | ||
| US20240426028A1 (en) * | 2021-08-20 | 2024-12-26 | Denka Company Limited | Fibers for artificial hair, fiber bundle for artificial hair, and hair decoration product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10102317A (ja) * | 1996-09-26 | 1998-04-21 | Kanegafuchi Chem Ind Co Ltd | ポリ塩化ビニル系繊維及びその製造法 |
| WO2006038447A1 (ja) * | 2004-10-01 | 2006-04-13 | Denki Kagaku Kogyo Kabushiki Kaisha | 塩化ビニル系樹脂組成物、塩化ビニル系繊維及びその製造方法、並びに、人工毛髪用繊維 |
| WO2012046748A1 (ja) * | 2010-10-06 | 2012-04-12 | 株式会社カネカ | 人工毛髪用繊維及びそれからなる頭髪装飾品 |
| JP2013002014A (ja) * | 2011-06-15 | 2013-01-07 | Denki Kagaku Kogyo Kk | 人工毛髪用繊維とその製造方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001131824A (ja) | 1999-10-28 | 2001-05-15 | Kanegafuchi Chem Ind Co Ltd | ポリ塩化ビニル系樹脂組成物よりなる繊維 |
| KR100473043B1 (ko) * | 2002-01-09 | 2005-03-08 | (주)우노파이버 | 염화비닐계 가발용 섬유 및 제조방법 |
| JP2012208136A (ja) | 2009-08-12 | 2012-10-25 | Denki Kagaku Kogyo Kk | 光学成形体用樹脂組成物及びその光学成形体 |
| JP6755808B2 (ja) | 2016-01-22 | 2020-09-16 | 積水化学工業株式会社 | 防水シート用ポリ塩化ビニル系樹脂組成物およびポリ塩化ビニル系樹脂防水シート |
-
2019
- 2019-04-09 JP JP2020523542A patent/JP7198278B2/ja active Active
- 2019-04-09 KR KR1020207035493A patent/KR20210016546A/ko not_active Ceased
- 2019-04-09 US US17/046,155 patent/US11807747B2/en active Active
- 2019-04-09 WO PCT/JP2019/015429 patent/WO2019235055A1/ja not_active Ceased
- 2019-04-09 CN CN201980033358.5A patent/CN112135540B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10102317A (ja) * | 1996-09-26 | 1998-04-21 | Kanegafuchi Chem Ind Co Ltd | ポリ塩化ビニル系繊維及びその製造法 |
| WO2006038447A1 (ja) * | 2004-10-01 | 2006-04-13 | Denki Kagaku Kogyo Kabushiki Kaisha | 塩化ビニル系樹脂組成物、塩化ビニル系繊維及びその製造方法、並びに、人工毛髪用繊維 |
| WO2012046748A1 (ja) * | 2010-10-06 | 2012-04-12 | 株式会社カネカ | 人工毛髪用繊維及びそれからなる頭髪装飾品 |
| JP2013002014A (ja) * | 2011-06-15 | 2013-01-07 | Denki Kagaku Kogyo Kk | 人工毛髪用繊維とその製造方法 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023145171A1 (ja) * | 2022-01-25 | 2023-08-03 | デンカ株式会社 | 人工毛髪用繊維及び頭髪装飾製品 |
| WO2024090375A1 (ja) * | 2022-10-26 | 2024-05-02 | 株式会社カネカ | 塩化ビニル系繊維、及びその製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2019235055A1 (ja) | 2021-08-05 |
| CN112135540A (zh) | 2020-12-25 |
| KR20210016546A (ko) | 2021-02-16 |
| US20210171754A1 (en) | 2021-06-10 |
| US11807747B2 (en) | 2023-11-07 |
| JP7198278B2 (ja) | 2022-12-28 |
| CN112135540B (zh) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7198278B2 (ja) | 人工毛髪用繊維及び頭髪装飾製品 | |
| JP5491213B2 (ja) | 人工毛髪用繊維及び頭飾品 | |
| WO2019181868A1 (ja) | 人工毛髪用繊維及び頭髪装飾製品 | |
| JP6823654B2 (ja) | ポリ塩化ビニル系人工毛髪繊維の製造方法 | |
| JP2004156149A (ja) | ポリ塩化ビニル系繊維 | |
| JP2024069549A (ja) | 人工毛髪用繊維および頭飾品 | |
| WO2023145171A1 (ja) | 人工毛髪用繊維及び頭髪装飾製品 | |
| JP7072567B2 (ja) | 人工毛髪用繊維 | |
| JP7697015B2 (ja) | 人工毛髪用繊維、人工毛髪用繊維束及び頭髪装飾製品 | |
| JP3613960B2 (ja) | 塩化ビニル繊維の製造方法 | |
| JP5019813B2 (ja) | 人工毛髪用繊維、及び、その製造方法 | |
| JP2002266160A (ja) | 塩化ビニル系樹脂繊維 | |
| CN116390668A (zh) | 人工毛发用纤维 | |
| JP2006097182A (ja) | ポリ塩化ビニル系繊維 | |
| JP2003293217A (ja) | ポリ塩化ビニル系繊維 | |
| JP2001115332A (ja) | ポリ塩化ビニル系繊維 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19814532 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2020523542 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 19814532 Country of ref document: EP Kind code of ref document: A1 |
|
| WWR | Wipo information: refused in national office |
Ref document number: 1020207035493 Country of ref document: KR |