US20220372667A1 - Core-sheath composite fiber for artificial hair, hair ornament including same, and method for manufacturing same - Google Patents

Core-sheath composite fiber for artificial hair, hair ornament including same, and method for manufacturing same Download PDF

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US20220372667A1
US20220372667A1 US17/879,133 US202217879133A US2022372667A1 US 20220372667 A1 US20220372667 A1 US 20220372667A1 US 202217879133 A US202217879133 A US 202217879133A US 2022372667 A1 US2022372667 A1 US 2022372667A1
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core
based resin
polyamide
sheath
resin composition
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Norikazu Yasutomo
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Kaneka Corp
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Kaneka Corp
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    • 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
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • 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
    • A41G5/00—Hair pieces, inserts, rolls, pads, or the like; Toupées
    • A41G5/004—Hair pieces
    • 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
    • D01D5/08—Melt spinning methods
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • 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
    • D01F1/04—Pigments
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • 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

  • One or more embodiments of the present invention relate to a core-sheath conjugate fiber for artificial hair capable of being used as an alternative to human hair, a hair ornament product including the same, and a production method therefor.
  • human hair is used for hair ornament products such as hairpieces, hair wigs, hair extensions, hair bands, and doll hair.
  • hair ornament products such as hairpieces, hair wigs, hair extensions, hair bands, and doll hair.
  • synthetic fibers that can be used for artificial hair include acrylic-based fibers, vinyl chloride-based fibers, vinylidene chloride-based fibers, polyester-based fibers, polyamide-based fibers, and polyolefin-based fibers.
  • a core-sheath conjugate fiber containing polyester as a core component and polyamide as a sheath component has been developed as a fiber for artificial hair having a texture close to that of human hair and excellent durability and heat resistance (Patent Document 1).
  • polyethylene terephthalate having a high degree of polymerization and polyamide having a high degree of polymerization are used, and in a melt spinning method, the fiber is rapidly cooled and solidified through liquid cooling, and thereafter passed through a fiber surface layer crystallization promoting machine to form a specific streak-like asperity structure on the fiber surface, and thus, the desired fiber for artificial hair described above is obtained by suppressing the gloss of the polyamide constituting the sheath while securing the strength of the fiber.
  • Patent Document 1 JP H03-185103A
  • a cross section of a core-sheath conjugate fiber has a non-circular shape, e.g., a flat two-lobed shape, die swell (also called “Barus effect”) that occurs when the fiber is discharged from a nozzle becomes ununiform. Accordingly, if the degree of polymerization of the resin used is high, the fiber cross section is significantly deformed from the shape of the nozzle, and consequently, the cross sectional shape of the core part also significantly changes from the shape of the nozzle.
  • both of the core and the sheath are formed using resins having high degrees of polymerization as in Patent Document 1, it is difficult to form cross sections of the core and the sheath into the same shape as the nozzle due to Barus effect, and the core component may be exposed, for example. Therefore, there is room for improvement from the viewpoint of the production yield of the fiber. Furthermore, the fiber has unintended waviness due to displacement of the center of the fiber cross section, and there is room for improvement. Moreover, depending on spinning conditions, streak-like asperities are formed on the fiber surface due to spherulites formed in the polyamide used for the sheath, and the touch and the combing property are impaired.
  • one or more embodiments of the present invention provide a core-sheath conjugate fiber for artificial hair in which exposure of the core part is suppressed and that has a touch close to that of human hair and an improved combing property, a hair ornament product including the same, and a method for producing the same.
  • one or more embodiments of the present invention relate to a hair ornament product including the core-sheath conjugate fiber for artificial hair.
  • one or more embodiments of the present invention relate to a method for producing the core-sheath conjugate fiber for artificial hair, including a step of melt spinning the polyester-based resin composition and the polyamide-based resin composition using a core-sheath conjugate nozzle, wherein the polyamide-based resin composition has a melt viscosity of 140 Pa ⁇ s or less at a set temperature of the core-sheath conjugate nozzle.
  • a core-sheath conjugate fiber for artificial hair in which exposure of the core part is suppressed and that has a touch close to that of human hair and an improved combing property, a hair ornament product including the same, and a method for producing the same.
  • a core-sheath conjugate fiber for artificial hair in which exposure of the core part is suppressed and that has a touch close to that of human hair and a good combing property.
  • FIG. 1 is a schematic view showing a fiber cross section of a core-sheath conjugate fiber for artificial hair according to one or more embodiments of the present invention.
  • FIG. 2 is a laser microscopic photograph of a fiber cross section of a fiber of Example 4.
  • FIG. 3 is a laser microscopic photograph of a fiber cross section of a fiber of Comparative Example 5.
  • the inventor of one or more embodiments of the present invention conducted an in-depth research in order to address the above, and found that, in a core-sheath conjugate fiber for artificial hair that has a flat two-lobed cross sectional shape and in which a polyester-based resin composition is used for a core part and a polyamide-based resin composition is used for a sheath part, if the core-to-sheath area ratio is set to a predetermined value and the polyamide-based resin composition used for the sheath part has a melt viscosity of 140 Pa ⁇ s or less, deformation of the fiber cross section due to Barus effect is suppressed and exposure of the core part is suppressed, and if a pigment is contained in the polyamide-based resin composition, streak-like asperities are unlikely to be formed on the fiber surface, the gloss peculiar to polyamide can be suppressed, and it is possible to obtain a core-sheath conjugate fiber for artificial hair (hereinafter also simply referred to as a “core-s
  • a core-sheath conjugate fiber for artificial hair according to one or more embodiments of the present invention is comprised of a core part and a sheath part and has a flat two-lobed cross sectional shape.
  • the core part also has a flat two-lobed cross sectional shape.
  • two lobal portions having a shape selected from the group consisting of a circular shape and an elliptical shape are connected via recessed portions.
  • the circular or elliptical shape does not absolutely have to be a continuous arc, and may also be a substantially circular shape or a substantially elliptical shape that is partially deformed, as long as no acute angle is formed. Furthermore, no consideration needs to be given to asperities with a size of 2 ⁇ m or less generated at the outer circumference of the fiber cross section and the outer circumference of the core part due to an additive or the like contained.
  • FIG. 1 is a schematic view showing a fiber cross section of a core-sheath conjugate fiber for artificial hair according to one or more embodiments of the present invention.
  • a core-sheath conjugate fiber 1 for artificial hair of this embodiment is comprised of a sheath part 10 and a core part 20 , and the fiber 1 and the core part 20 both have flat two-lobed cross sections in which two elliptical portions are connected via recessed portions.
  • a length (represented by “L”) of a major axis of the fiber cross section which is a straight line with the largest length among an axisymmetric axis and straight lines connecting any two points on the outer circumference of the fiber cross section so as to be in parallel to the axisymmetric axis
  • a length (represented by “S 1 ”) of a first minor axis of the fiber cross section which is a straight line connecting two points so as to have the largest length when connecting any two points on the outer circumference of the fiber cross section so as to be perpendicular to the major axis of the fiber cross section, satisfy the equation (1) below.
  • a length (represented by “Lc”) of a major axis of the core part cross section which is a straight line with the largest length among an axisymmetric axis and straight lines connecting any two points on the outer circumference of the core part cross section so as to be in parallel to the axisymmetric axis
  • a length (represented by “Sc 1 ”) of a first minor axis of the core part cross section which is a straight line connecting two points so as to have the largest length when connecting any two points on the outer circumference of the core part cross section so as to be perpendicular to the major axis of the core part cross section, satisfy the equation (2) below.
  • the center point of the major axis of the core part coincides with the center point of the major axis of the fiber cross section, in which case, the fiber can be kept from having unintended waviness.
  • the above-described cross sectional shapes of the fiber and the core part can be controlled by using a nozzle (pores) with a shape close to the target cross sectional shape.
  • the core-sheath conjugate fiber for artificial hair having the flat two-lobed fiber cross section has a shape in which two lobal portions having a shape selected from the group consisting of a circular shape and an elliptical shape are connected via recessed portions. Accordingly, there are smooth recessed portions and protrusions on the fiber surface, the area of flat portions in the surface decreases, and thus reflection of light is suppressed and the gloss of the fiber is likely to be close to that of human hair.
  • the fiber surface includes smooth asperities, the area of contact between fibers or between fibers and a comb passed therethrough decreases, and thus it is easy to realize a touch close to that of human hair and a good combing property.
  • the core-sheath conjugate fiber for artificial hair may have a single fiber fineness of 10 dtex or more and 150 dtex or less, 30 dtex or more and 120 dtex or less, 40 dtex or more and 100 dtex or less, or 50 dtex or more and 90 dtex or less.
  • a mass of the core-sheath conjugate fibers for artificial hair e.g., a fiber bundle of the core-sheath conjugate fibers for artificial hair
  • all fibers do not necessarily have to have the same fineness and the same cross sectional shape, and fibers having different values of fineness and different cross sectional shapes may be mixed.
  • the melt viscosity of a resin composition used for the core part or the sheath part is a value that is measured using the resin composition in the form of pellets dehumidified and dried to have a moisture content of 1000 ppm or less, under conditions of a resin composition sample amount of 20 cc, a piston speed of 200 mm/min, a capillary length of 20 mm, and a capillary diameter of 1 mm, while setting the temperature to the temperature during formation of fibers, that is, the nozzle temperature during spinning.
  • resin and the additives are melt kneaded in advance using an ordinary kneader, and the mixture is pelletized and then used for the measurement of the melt viscosity.
  • a capillary rheometer LCR7000 manufactured by Dynisco is used as the measurement apparatus.
  • the melt viscosity of the polyamide-based resin composition at the time of spinning in the production of the artificial fiber is 140 Pa ⁇ s or less, and preferably 60 Pa ⁇ s or more and 120 Pa ⁇ s or less.
  • the cross sectional shape of the core part of the core-sheath conjugate fiber changes depending on viscosities of the resin compositions used for the core part and the sheath part. In particular, when a nozzle having a flat two-lobed shape is used, a polymer is not discharged uniformly with respect to the fiber cross section due to Barus effect, and therefore, the shape of the fiber cross section changes from the shape of the nozzle.
  • the cross sectional shape of the core part also changes from the shape of the nozzle.
  • the polyamide-based resin composition that constitutes the sheath part has a viscosity of 140 Pa ⁇ s or less, Barus effect can be suppressed and a core-sheath conjugate fiber that has a cross sectional shape similar to the shape of the nozzle can be stably obtained.
  • the viscosity of the polyamide-based resin composition that constitutes the sheath part is higher than 140 Pa ⁇ s, Barus effect becomes very significant, and the fiber cross section is very significantly deformed from the shape of the nozzle. Therefore, a core-sheath conjugate fiber having the flat two-lobed shape is unlikely to be obtained, and the core component and the sheath component may separate from each other or the core part may be exposed, for example.
  • the core part and the sheath part do not have to have the same fineness and the same cross sectional shape, and fibers having different values of fineness and different cross sectional shapes may be mixed.
  • the core part is completely covered by the sheath part without being exposed to the fiber surface, in order to prevent the core part and the sheath part from separating from each other.
  • the core part is comprised of a polyester-based resin composition that contains a polyester-based resin as a main component
  • the sheath part is comprised of a polyamide-based resin composition that contains a polyamide-based resin as a main component and also contains a pigment.
  • the polyester-based resin composition when the total weight of the polyester-based resin composition containing a polyester-based resin as a main component is taken as 100% by weight, the polyester-based resin composition may contain the polyester-based resin in an amount of more than 50% by weight, 70% by weight or more, 80% by weight or more, 90% by weight or more, or 95% by weight or more.
  • polyester-based resins selected from the group consisting of polyalkylene terephthalate and a copolymerized polyester mainly containing polyalkylene terephthalate may be used as the polyester-based resin.
  • the “copolymerized polyester mainly containing polyalkylene terephthalate” refers to a copolymerized polyester containing polyalkylene terephthalate in an amount of 80 mol % or more.
  • the polyalkylene terephthalate is not particularly limited, and may be, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, or polycyclohexane dimethylene terephthalate.
  • the copolymerized polyester mainly containing polyalkylene terephthalate is not particularly limited, and may be, for example, a copolymerized polyester mainly containing polyalkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, or polycyclohexane dimethylene terephthalate, and further containing other copolymerizable components.
  • Examples of the other copolymerizable components include: polycarboxylic acids such as isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, pyromellitic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and their derivatives; dicarboxylic acids and their derivatives containing sulfonates such as 5-sodiumsulfoisophthalic acid and dihydroxyethyl 5-sodiumsulfoisophthalate; 1,2-propanediol; 1,3-propanediol; 1,4-butanediol; 1,6-hexanediol; neopentyl glycol; 1,4-cyclohexanedimethanol; diethylene glycol; polyethylene glycol; trimethylolpropane
  • the copolymerized polyester may be produced by adding a small amount of other copolymerizable components to polyalkylene terephthalate serving as a main component, and allowing them to react with each other, from the viewpoint of stability and ease of operation.
  • polyalkylene terephthalate examples include a polymer of terephthalic acid and/or its derivatives (e.g., methyl terephthalate) and alkylene glycol.
  • the copolymerized polyester may be produced by adding a small amount of monomer or oligomer component serving as other copolymerizable components, to a mixture of terephthalic acid and/or its derivatives (e.g., methyl terephthalate) and alkylene glycol, used for polymerization of polyalkylene terephthalate serving as a main component, and subjecting them to polymerization.
  • terephthalic acid and/or its derivatives e.g., methyl terephthalate
  • alkylene glycol used for polymerization of polyalkylene terephthalate serving as a main component
  • the copolymerized polyester has a structure in which the other copolymerizable components are polycondensed on the main chain and/or side chain of polyalkylene terephthalate serving as a main component, and the copolymerization method and the like are not particularly limited.
  • the copolymerized polyester mainly containing polyalkylene terephthalate include a polyester obtained through copolymerization of polyethylene terephthalate serving as a main component with one compound selected from the group consisting of an ethylene glycol ether of bisphenol A, 1,4-cyclohexanedimethanol, isophthalic acid, and dihydroxyethyl 5-sodiumsulfoisophthalate.
  • the polyalkylene terephthalate and the copolymerized polyester mainly containing polyalkylene terephthalate may be used alone or in a combination of two or more.
  • polyethylene terephthalate; polypropylene terephthalate; polybutylene terephthalate; a polyester obtained through copolymerization of polyethylene terephthalate serving as a main component with an ethylene glycol ether of bisphenol A; a polyester obtained through copolymerization of polyethylene terephthalate serving as a main component with 1,4-cyclohexanedimethanol; a polyester obtained through copolymerization of polyethylene terephthalate serving as a main component with isophthalic acid; a polyester obtained through copolymerization of polyethylene terephthalate serving as a main component with dihydroxyethyl 5-sodiumsulfoisophthalate, and the like may be used alone or in a combination of two or more.
  • the intrinsic viscosity (alternatively referred to as “IV value”) of the polyester-based resin is not particularly limited, but may be 0.3 or more and 1.2 or less, or 0.4 or more and 1.0 or less. If the intrinsic viscosity is 0.3 or more, the mechanical strength of the obtained fiber does not decrease, and there is no risk of dripping during a combustion test. On the other hand, if the intrinsic viscosity is 1.2 or less, the molecular weight is not too large, and the melt viscosity is not too high, and thus it is easy to perform melt spinning, and the fineness is likely to be uniform.
  • the polyester-based resin composition may further contain other resins in addition to the polyester-based resin.
  • the other resins include a polyamide-based resin, a vinyl chloride-based resin, a modacrylic-based resin, a polycarbonate-based resin, a polyolefin-based resin, and a polyphenylenesulfide-based resin. These resins may be used alone or in a combination of two or more.
  • the polyamide-based resin composition when the total weight of the polyamide-based resin composition containing a polyamide-based resin as a main component is taken as 100% by weight, the polyamide-based resin composition may contain the polyamide-based resin in an amount of more than 50% by weight, 70% by weight or more, 80% by weight or more, 90% by weight or more, or 95% by weight or more.
  • the polyamide-based resin used in the present disclosure means a nylon resin obtained through polymerization of one or more selected from the group consisting of lactam, aminocarboxylic acid, a mixture of dicarboxylic acid and diamine, a mixture of a dicarboxylic acid derivative and diamine, and a salt of dicarboxylic acid and diamine.
  • lactam examples include, but are not particularly limited to, for example, 2-azetidinone, 2-pyrrolidinone, ⁇ -valerolactam, ⁇ -caprolactam, enantholactam, capryllactam, undecalactam, and laurolactam.
  • lactams it is preferable to use ⁇ -caprolactam, undecalactam, and laurolactam, and more preferable to use ⁇ -caprolactam.
  • These lactams may be used alone or in a combination of two or more.
  • aminocarboxylic acid examples include, but are not particularly limited to, for example, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
  • 6-aminocaproic acid 7-aminoheptanoic acid
  • 8-aminooctanoic acid 9-aminononanoic acid
  • 10-aminodecanoic acid 11-aminoundecanoic acid
  • 12-aminododecanoic acid 12-aminododecanoic acid
  • 6-aminocaproic acid it is preferable to use 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, and more preferable to use 6-aminocaproic acid.
  • dicarboxylic acid that can be used for the mixture of dicarboxylic acid and diamine, the mixture of a dicarboxylic acid derivative and diamine, or the salt of dicarboxylic acid and diamine include, but are not particularly limited to, for example: aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brasylic acid, tetradecanedioic acid, pentadecanedioic acid, and octadecanedioic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedi
  • dicarboxylic acids it is preferable to use adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, and isophthalic acid, and more preferable to use adipic acid, terephthalic acid, and isophthalic acid.
  • dicarboxylic acids may be used alone or in a combination of two or more.
  • diamines such as 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-diaminopentane (MDP), 1, 7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononan, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecan
  • the polyamide-based resin (alternatively referred to as a “nylon resin”) is not particularly limited, but it is preferable to use, for example, Nylon 6, Nylon 66, Nylon 11, Nylon 12, Nylon 6/10, Nylon 6/12, semi-aromatic nylon containing the Nylon 6T and/or 61 unit, copolymers of these nylon resins, or the like. It is more preferable to use Nylon 6, Nylon 66, or a copolymer of Nylon 6 and Nylon 66.
  • the polyamide-based resin can be produced for example, using a polyamide-based resin polymerization method in which a raw material for the polyamide-based resin is heated in the presence or absence of a catalyst. During the polymerization, stirring may or may not be performed, but it is preferable to perform stirring in order to obtain a uniform product.
  • the polymerization temperature can be set as appropriate according to the degree of polymerization, the reaction yield, and the reaction time of a target polymer, but it is preferable to set the temperature to a low temperature in consideration of the quality of a finally obtained polyamide-based resin.
  • the reaction ratio can also be set as appropriate.
  • the pressure is not limited, but it is preferable to reduce the pressure in the system in order to efficiently let volatile components move to the outside of the system.
  • the polyamide-based resin used in one or more embodiments of the present invention may have a terminal end that is capped by an end-capping agent such as a carboxylic acid compound or an amine compound as necessary.
  • an end-capping agent such as a carboxylic acid compound or an amine compound as necessary.
  • the concentration of terminal amino groups or terminal carboxyl groups in a nylon resin obtained when a terminal end is capped by adding monocarboxylic acid and/or monoamine is lower than that when such an end-capping agent is not used.
  • the total concentration of terminal amino groups and terminal carboxyl groups does not change when a terminal end is capped by dicarboxylic acid or diamine, but the concentration ratio between terminal amino groups and terminal carboxyl groups changes.
  • carboxylic acid compound examples include, but are not particularly limited to, for example: aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and arachic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, ethylbenzoic acid, and phenylacetic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic
  • amine compound examples include, but are not particularly limited to, for example: aliphatic monoamines such as butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2 -ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, nonadecylamine, and icosylamine; alicyclic monoamines such as cyclohexylamine and methylcyclohexylamine; aromatic monoamines such as benzylamine and ⁇ -phenylethylamine; aliphatic diamines such as 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane,
  • the terminal group concentration of the polyamide-based resin is not particularly limited, but the terminal amino group concentration may be high, for example, when it is necessary to increase the dyeability for fiber uses or when designing a material suitable for alloying for resin uses.
  • the terminal amino group concentration may be low, for example, when it is required to suppress coloring or gelation under extended aging conditions.
  • the terminal carboxyl group concentration and the terminal amino group concentration may be both low when it is required to suppress reproduction of lactam during re-melting, yarn breakage during melt spinning due to production of oligomer, mold deposit during continuous injection molding, and generation of die marks during continuous extrusion of a film.
  • the terminal amino group concentration and the terminal carboxyl group concentration both may be 1.0 ⁇ 10 ⁇ 5 to 15.0 ⁇ 10 ⁇ 5 eq/g, 2.0 ⁇ 10 ⁇ 5 to 12.0 ⁇ 10 ⁇ 5 eq/g, or 3.0 ⁇ 10 ⁇ 5 to 11.0 ⁇ 10 ⁇ 5 eq/g.
  • the end-capping agent may be added using a method in which the end-capping agent is added simultaneously with raw materials such as caprolactam at the initial stage of polymerization, a method in which the end-capping agent is added during polymerization, a method in which the end-capping agent is added when a nylon resin in a molten state is caused to pass through a vertical stirring thin-film evaporator, or the like.
  • the end-capping agent may be added without any treatment, or in the form of being dissolved in a small amount of solvent.
  • the polyamide-based resin composition may contain other resins in addition to the polyamide-based resin.
  • the other resins include a vinyl chloride-based resin, a modacrylic-based resin, a polycarbonate-based resin, a polyolefin-based resin, and a polyphenylenesulfide-based resin. These resins may be used alone or in a combination of two or more.
  • the core part of the core-sheath conjugate fiber for artificial hair is comprised of a polyester-based resin composition containing, as a main component, one or more of polyester-based resins selected from the group consisting of polyalkylene terephthalate and a copolymerized polyester mainly containing polyalkylene terephthalate, and it is more preferable that the sheath part of the core-sheath conjugate fiber for artificial hair is comprised of a polyamide-based resin composition containing, as a main component, a polyamide-based resin mainly containing at least one selected from the group consisting of Nylon 6 and Nylon 66.
  • the “polyamide-based resin mainly containing at least one selected from the group consisting of Nylon 6 and Nylon 66” means a polyamide-based resin that contains Nylon 6 and/or Nylon 66 in an amount of 80 mol % or more.
  • the sheath part is comprised of a polyamide-based resin composition that contains a pigment, in which case, streak-like asperities are unlikely to be formed on the fiber surface, and it is possible to suppress the gloss peculiar to polyamide and obtain a good touch and a good combing property. Moreover, it is possible to obtain a core-sheath fiber for artificial hair having a desired color.
  • the pigment is not particularly limited, and an ordinary pigment such as carbon black or an anthraquinone-based pigment can be used, for example. It is also possible to use a pigment masterbatch.
  • the pigment masterbatch is obtained by kneading and pelletizing (which may be referred to as “compounding”) a pigment and a resin composition using a kneader such as an extruder, wherein the pigment, which is typically difficult to handle due to its fine powder form, is dispersed in advance in the resin composition, and thus it is possible to easily handle the pigment and to suppress color spots of the obtained fiber.
  • the core-sheath conjugate fiber for artificial hair which is required to have a large number of colors
  • the polyamide-based resin composition may contain a pigment in an amount of 0.005 parts by weight or more and 2 parts by weight or less, or 0.01 parts by weight or more and 1 part by weight or less, with respect to 100 parts by weight of the polyamide-based resin, although there is no particular limitation thererto.
  • the polyester-based resin composition constituting the core part may also contain a pigment, and a pigment similar to that used for the sheath part may be used for the core part.
  • the pigment may be used in an amount of 0.005 parts by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the polyester-based resin.
  • a flame retardant may also be used from the viewpoint of flame retardance.
  • the flame retardant include a bromine-containing flame retardant and a phosphorus-containing flame retardant.
  • Examples of the phosphorus-containing flame retardant include a phosphoric acid ester amide compound and an organic cyclic phosphorus-based compound.
  • Examples of the bromine-based flame retardant include, but are not particularly limited to, for example: a brominated epoxy-based flame retardant; bromine-containing phosphoric acid esters such as pentabromotoluene, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether, bis(tribromophenoxy)ethane, tetrabromophthalic anhydride, ethylene bis(tetrabromophthalimide), ethylene bis(pentabromophenyl), octabromotrimethylphenylindan, and tris(tribromoneopentyl)phosphate; brominated polystyrenes; brominated polybenzyl acrylates; a brominated phenoxy resin; brominated polycarbonate oligomers; tetrabrom
  • a brominated epoxy-based flame retardant having an epoxy group or tribromophenol at a molecular end thereof may be used as a raw material.
  • the structure of the brominated epoxy-based flame retardant after melt kneading is not particularly limited, but it is preferable that 80 mol % or more of the structure is comprised of a constituent unit represented by the chemical formula (1) below when the total number of constituent units each represented by the chemical formula (1) below and constituent units obtained by at least partially modifying the chemical formula (1) below is taken as 100 mol %.
  • the structure of the brominated epoxy-based flame retardant may change at a molecular end thereof after melt kneading.
  • a molecular end of the brominated epoxy-based flame retardant may be substituted by a hydroxyl group, a phosphate group, a phosphoric acid group, or the like other than an epoxy group or tribromophenol, or may be bound to a polyester component through an ester group.
  • the brominated epoxy-based flame retardant may have a branched structure in which the secondary hydroxyl group and the epoxy group are bound.
  • part of the bromine of the chemical formula (1) may be eliminated or added, as long as the bromine content in the molecules of the brominated epoxy-based flame retardant does not change significantly.
  • a polymeric brominated epoxy-based flame retardant as represented by the general formula (2) below may be used as the brominated epoxy-based flame retardant.
  • m is 1 to 1000.
  • examples of the polymeric brominated epoxy-based flame retardant represented by the general formula (2) below include a commercially available product such as a brominated epoxy-based flame retardant (product name “SR-T2MP”) manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.
  • the bromine-based epoxy flame retardant may be contained in an amount of 5 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the main component resin, although there is no particular limitation thereto.
  • the core part is comprised of a polyester-based resin composition containing 100 parts by weight of one or more of polyester resins selected from the group consisting of polyalkylene terephthalate and a copolymerized polyester mainly containing polyalkylene terephthalate and 5 parts by weight or more and 40 parts by weight or less of the bromine-based epoxy flame retardant
  • the sheath part is comprised of a polyaniide-based resin composition containing 100 parts by weight of a polyaniide-based resin mainly containing at least one selected from the group consisting of Nylon 6 and Nylon 66 and 5 parts by weight or more and 40 parts by weight or less of the bromine-based epoxy flame retardant.
  • a flame retardant auxiliary may also be used.
  • the flame retardant auxiliary is not particularly limited, but from the viewpoint of flame retardance, it is preferable to use an antimony-based compound or a composite metal including antimony, for example.
  • the antimony-based compound include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate, potassium antimonate, and calcium antimonate. It is more preferable to use one or more selected from the group consisting of antimony trioxide, antimony pentoxide, and sodium antimonate, from the viewpoint of improving the flame retardance and the influence on a touch.
  • the flame retardant auxiliary is contained in an amount of 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the main component resin, although there is no particular limitation thereto.
  • the polyamide-based resin composition constituting the sheath part contains the flame retardant auxiliary, appropriate asperities are formed on the surface of the fiber, and a core-sheath conjugate fiber for artificial hair having an appearance with a low gloss close to that of human hair as well as flame retardance is likely to be obtained.
  • the core-sheath conjugate fiber for artificial hair may contain various types of additives such as a heat-resistant agent, a stabilizer, a fluoresces, an antioxidant, and an antistatic agent within a range that does not inhibit the effects of one or more embodiments of the present invention.
  • additives such as a heat-resistant agent, a stabilizer, a fluoresces, an antioxidant, and an antistatic agent within a range that does not inhibit the effects of one or more embodiments of the present invention.
  • a core component is prepared by dry blending components such as the above-described polyester-based resin and the brominated epoxy-based flame retardant, and melt-kneading the obtained polyester-based resin composition using any of various ordinary kneaders.
  • a sheath component is prepared by dry blending components such as the above-described polyamide-based resin, the pigment, and the brominated epoxy-based flame retardant, and melt-kneading the obtained polyamide-based resin composition using any of various ordinary kneaders.
  • the core-sheath conjugate fiber can be produced by melt spinning the core component and the sheath component using a core-sheath conjugate spinning nozzle.
  • the kneaders include a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, and a kneader. Of these kneaders, it is preferable to use a twin-screw extruder from the viewpoint of adjusting the kneading degree and easily performing the operation.
  • a melt spinning method may be used as the method for producing the fiber of one or more embodiments of the present invention, and, for example, in the case of a polyester-based resin composition, melt spinning is performed while the temperatures of an extruder, a gear pump, a nozzle, and the like are set to 250° C. or more and 300° C. or less, and in the case of a polyamide-based resin composition, melt spinning is performed while the temperatures of an extruder, a gear pump, a nozzle, and the like are set to 260° C. or more and 320° C.
  • the polyester-based resin composition that constitutes the core part is supplied from a core-part extruder of a melt spinning machine
  • the polyamide-based resin composition that constitutes the sheath part is supplied from a sheath-part extruder of the melt spinning machine
  • a molten polymer is discharged from a core-sheath conjugate spinning nozzle (pores) having a predetermined shape, and thus extruded yarns (undrawn yarns) are obtained.
  • the melt viscosity of the polyamide-based resin composition at the set temperature of the core-sheath conjugate nozzle needs to be 140 Pa ⁇ s or less. In this case, it is possible to suppress deformation of the fiber cross section due to Barus effect, and to stably obtain a core-sheath conjugate fiber having a cross sectional shape similar to the shape of the nozzle.
  • the extruded yarns are hot drawn.
  • the drawing may be performed by either a two-step method or a direct drawing method.
  • the extruded yarns are wound once, and then drawn.
  • the direct drawing method the extruded yarns are drawn continuously without winding.
  • the hot drawing may be performed by a single-stage drawing method or a multi-stage drawing method that includes two or more stages.
  • the heating means for the hot drawing may be a heating roller, a heat plate, a steam jet apparatus, a hot water bath, or the like, which can be used in combination as desired.
  • an oil solution such as a fiber treating agent and a softener
  • the fiber treating agent include a silicone-based fiber treating agent and a non-silicone-based fiber treating agent for improving the touch and the combing property.
  • the core-sheath conjugate fiber for artificial hair may be subjected to gear crimping.
  • gear crimping typically, a fiber heated to the softening temperature or more is caused to pass through a portion between two meshing gears, so that the shape of the gears is transferred to the fiber, and the fiber is thus curved.
  • a fiber curled in different shapes by heat-treating the core-sheath conjugate fiber for artificial hair at different temperatures during the fiber treatment processes.
  • the core-sheath conjugate fiber for artificial hair can be used for hair ornament products without particular limitation.
  • the hair ornament product may be constituted only by the core-sheath conjugate fiber for artificial hair of one or more embodiments of the present invention.
  • the hair ornament product may be comprised of the core-sheath conjugate fiber for artificial hair of one or more embodiments of the present invention combined with other fibers for artificial hair and natural fibers such as human hair and animal hair.
  • the measuring methods and the evaluation methods used in the examples and comparative examples are as follows.
  • the melt viscosity of a resin composition in the form of pellets that were used for the core part or the sheath part and dried to have a moisture content of 1000 ppm or less was measured under conditions of a sample amount of 20 cc, a piston speed of 200 mm/min, a capillary length of 20 mm, and a capillary diameter of 1 mm, while setting the temperature to the temperature during formation of fibers, i.e., the nozzle temperature during spinning.
  • the measurement was performed using an autovibro type fineness measuring apparatus “Denier Computer type DC-11” (manufactured by Search), and an average of measured values of 30 samples was calculated and taken as the single fiber fineness.
  • Fibers were bundled at room temperature (23° C.) and fixed with a shrinkage tube such that the fiber bundle was not displaced, after which the bundle was cut using a cutter, and whether or not the core part was exposed was evaluated through visual observation or evaluated by observing cross sections of the cut fibers using a laser microscope (“VK-9500” manufactured by Keyence Corporation).
  • Fibers were bundled at room temperature (23° C.) and fixed with a shrinkage tube such that the fiber bundle was not displaced, after which the fiber bundle was cut in round slices using a cutter, and thus a fiber bundle for cross section observation was prepared.
  • An image of this fiber bundle was captured using a laser microscope (“VK-9500” manufactured by Keyence Corporation) at a magnification of 500 times, and thus a photograph of a fiber cross section was obtained.
  • L/S 1 and Lc/Sc 1 were obtained based on the photograph of the fiber cross section.
  • Fibers whose curls were completely stretched were cut to have a length of 63.5 cm, and 5.0 g of thus obtained fibers with a fiber length of 63.5 cm was bundled. Subsequently, the fiber bundle was bound with a string at the middle thereof, folded in half, and fixed at the string portion, and thus a fiber bundle for hair iron treatment was prepared. Next, the fiber bundle was heated and crimped five times from the root at which the fiber bundle was fixed to the ends, using a hair iron (“Izunami ITC450 flat iron” manufactured by Izunami. Inc, U.S.) heated to 180° C., and thus a fiber bundle for combing property evaluation was prepared.
  • a hair iron (“Izunami ITC450 flat iron” manufactured by Izunami. Inc, U.S.) heated to 180° C.
  • a comb for combing hair (“Matador Professional 386.8 1/2F” made in Germany) was passed through the fiber bundle for combing property evaluation 100 times from the root at which the fiber bundle was fixed to the ends, the combing property was evaluated according to the following criteria based on the number of fibers deformed or split, and if the evaluation result was level B or higher, the combing property was taken as acceptable.
  • a brominated epoxy-based flame retardant product name “SR-T2MP” manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.
  • 2 parts by weight of sodium antimonate product name “SA-A′ manufactured by NIHON SEIKO CO., LTD.
  • a black pigment masterbatch product name TESM22367BLACK (20)” manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., pigment: 20% by weight, base resin: polyester-based resin
  • 0.8 parts by weight of a yellow pigment masterbatch product name “PESM1001YELLOW (20)” manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., pigment: 20% by weight, base resin: polyester-based resin
  • a red pigment masterbatch product name
  • PET Polyethylene terephthalate pellets
  • PESM1001YELLOW (20) manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.
  • 0.6 parts by weight of a red pigment masterbatch product name “PESM3005RED (20)” manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.
  • Nylon 66 product name “AMILAN CM3001” manufactured by Toray Industries, Inc., hereinafter also referred to as “PA66”
  • the polyester-based resin composition and the polyamide-based resin composition in the form of pellets were supplied to extruders, extruded from a core-sheath conjugate spinning nozzle (pores) at a set temperature of 280° C. having a nozzle shape shown in Table 1 below, and wound up at a speed of 40 to 200 m/min, and thus undrawn yarns of core-sheath conjugate fibers each including a core part comprised of the polyester-based resin composition and a sheath part comprised of the polyamide-based resin composition and having a core-to-sheath area ratio of 5:5 were obtained.
  • the obtained undrawn yarns were drawn to 3 times while being wound up at a speed of 45 m/min using a heat roll at 85° C., and subsequently heat-treated by being wound up at a speed of 45 m/min using a heat roll heated to 200° C.
  • a polyether-based oil solution product name “KWC-Q” manufactured by Marubishi Oil Chemical Corporation
  • the yarns were dried, and thus a core-sheath conjugate fiber having a single fiber fineness shown in Table 1 below was obtained.
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 1, except that the resin used for the core part was changed to polyethylene terephthalate pellets (EastPET product name “A-12” manufactured by East West Chemical Private
  • the resin used for the sheath part was changed to Nylon 6 (product name “A1030BRL” manufactured by UNITIKA LTD., hereinafter also referred to as “PM”), the barrel setting temperature during pelletization was changed to 260° C., the nozzle setting temperature was changed to 270° C., and the core-to-sheath area ratio was changed to 8:2.
  • PM Nylon 6
  • the barrel setting temperature during pelletization was changed to 260° C.
  • the nozzle setting temperature was changed to 270° C.
  • the core-to-sheath area ratio was changed to 8:2.
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 1, except that the resin used for the core part was changed to polybutylene terephthalate pellets (product name “NOVADURAN 5020” manufactured by Mitsubishi Chemical Corporation, hereinafter also referred to as “PBT”), the barrel setting temperature during pelletization was changed to 260° C., the resin used for the sheath part was changed to Nylon 6 (product name “A1030BRL” manufactured by UNITIKA LTD.), the barrel setting temperature during pelletization was changed to 260° C., and the nozzle setting temperature was changed to 260° C.
  • PBT polybutylene terephthalate pellets
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 2, except that the core-to-sheath area ratio was changed to 5:5 and the sheath part was comprised of a polyamide-based resin composition obtained by adding 20 parts by weight of a brominated epoxy-based flame retardant (product name “SR-T2MP” manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), 2 parts by weight of sodium antimonate (product name “SA-A” manufactured by NIHON SEIKO CO., LTD.), 2.1 parts by weight of a black pigment masterbatch (product name “PESM22367BLACK (20)” manufactured by Dainichiseika Color & Chemicals Mfg.
  • SR-T2MP brominated epoxy-based flame retardant
  • SA-A sodium antimonate
  • PESM22367BLACK (20) manufactured by Dainichiseika Color & Chemicals Mfg.
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 4, except that the resin used for the core part was changed to polyethylene terephthalate pellets (product name “DFG1” manufactured by Bell Polyester Products, Inc.), and the extruded yarn was cooled for 1 second using a water bath at 20° C. right after the resins were extruded from the spinning nozzle.
  • resin used for the core part was changed to polyethylene terephthalate pellets (product name “DFG1” manufactured by Bell Polyester Products, Inc.), and the extruded yarn was cooled for 1 second using a water bath at 20° C. right after the resins were extruded from the spinning nozzle.
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 4, except that the resin used for the sheath part was changed to Nylon 66 (product name
  • the barrel setting temperature during pelletization was changed to 280° C.
  • the nozzle setting temperature was changed to 280° C.
  • the core-to-sheath area ratio was changed to 2:8.
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 2, except that the resin used for the sheath part was changed to Nylon 6 (product name “A1030BRT” manufactured by UNITIKA LTD.).
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 2, except that the core-to-sheath area ratio was changed to 9:1.
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 2, except that the sheath part was comprised of a polyamide-based resin composition obtained by supplying Nylon 6 (product name “A1030BRL” manufactured by UNITIKA
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 6, except that the resin used for the core part was changed to polyethylene terephthalate pellets (product name “DFG1” manufactured by Bell Polyester Products, Inc.), the resin used for the sheath part was changed to Nylon 66 (product name “Zyte142A” manufactured by DuPont), and the core-to-sheath area ratio was changed to 8:2.
  • polyethylene terephthalate pellets product name “DFG1” manufactured by Bell Polyester Products, Inc.
  • Nylon 66 product name “Zyte142A” manufactured by DuPont
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 4, except that the cross sectional shape was changed as shown in Table 1.
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 6, except that the core-to-sheath area ratio was changed to 5:5 and the sheath part was comprised of a polyamide-based resin composition obtained by adding 20 parts by weight of a brominated epoxy-based flame retardant (product name “SR-T2MP” manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) and 2 parts by weight of sodium antimonate (product name “SA-A” manufactured by NIHON SEIKO CO., LTD.) with respect to 100 parts by weight of Nylon 66 (product name “AMILAN CM3001” manufactured by Toray Industries, Inc.), dry blending the mixture, then supplying the mixture to a twin-screw extruder, melt-kneading the mixture at a barrel setting temperature of 280° C., and pelletizing the mixture.
  • SR-T2MP brominated epoxy-based flame retardant
  • SA-A sodium antimonate
  • a core-sheath conjugate fiber was obtained in a similar way to that of Example 4, except that the core-to-sheath area ratio was changed to 1:9.
  • FIG. 3 photograph Exposure of No No No No No No Yes Yes No Yes No No No core part Touch
  • FIG. 2 is a laser microscopic photograph of a fiber cross section of the fiber of Example 4.
  • the fiber and the core part both have flat two-lobed cross sectional shapes.
  • FIG. 3 is a laser microscopic photograph of a fiber cross section of the fiber of Comparative Example 5.
  • the fiber and the core part both have substantially circular cross sectional shapes.
  • the fiber surface did not include asperities, and therefore, the appearance of the fiber was unnatural, and the touch and the combing property were both bad.
  • the fiber of Comparative Example 7 lacked firmness because the ratio of the core component was too low, and the fiber could not have a touch close to that of human hair.

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US20200024774A1 (en) * 2017-03-30 2020-01-23 Kaneka Corporation Core-sheath composite fiber for artificial hair and headdress product comprising same

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JP2008106410A (ja) * 2006-03-01 2008-05-08 Toray Ind Inc 捲縮糸およびそれらを用いてなる繊維構造体
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US20200024774A1 (en) * 2017-03-30 2020-01-23 Kaneka Corporation Core-sheath composite fiber for artificial hair and headdress product comprising same
WO2019172147A1 (ja) * 2018-03-06 2019-09-12 デンカ株式会社 人工毛髪用繊維束
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