WO2022145115A1 - 人工毛髪用芯鞘複合繊維、それを含む頭飾製品及びその製造方法 - Google Patents
人工毛髪用芯鞘複合繊維、それを含む頭飾製品及びその製造方法 Download PDFInfo
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- WO2022145115A1 WO2022145115A1 PCT/JP2021/038787 JP2021038787W WO2022145115A1 WO 2022145115 A1 WO2022145115 A1 WO 2022145115A1 JP 2021038787 W JP2021038787 W JP 2021038787W WO 2022145115 A1 WO2022145115 A1 WO 2022145115A1
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- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
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- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
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- 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
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
-
- 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
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/04—Heat-responsive characteristics
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2503/00—Domestic or personal
- D10B2503/08—Wigs
Definitions
- the present invention relates to a core-sheath composite fiber for artificial hair that can be used as a substitute for human hair, a headdress product containing the same, and a method for producing the same.
- Human hair has traditionally been used in headdress products such as wigs, hair wigs, hair attachments, hair bands, and doll hair.
- headdress products such as wigs, hair wigs, hair attachments, hair bands, and doll hair.
- artificial hair fibers include acrylic fibers, vinyl chloride fibers, vinylidene chloride fibers, polyester fibers, polyamide fibers, and polyolefin fibers.
- a core-sheath composite fiber containing polyester as a core component and polyamide as a sheath component has been proposed.
- Patent Document 1 a polyethylene terephthalate having a high degree of polymerization and a polyamide having a high degree of polymerization are used.
- a specific concavo-convex structure in the shape while ensuring the strength of the core-sheath composite fiber, the gloss of the polyamide of the sheath is suppressed, the texture is close to that of human hair, and the fiber for artificial hair has excellent durability. Is stated to be obtained.
- the present invention provides an artificial hair fiber having a tactile sensation close to that of human hair and having good durability, curl settability and flame retardancy.
- the present invention is, in one or more embodiments, a core-sheath composite fiber for artificial hair including a core portion and a sheath portion, wherein the core portion is composed of a polyester-based resin composition containing a polyester-based resin, and the sheath portion.
- the core portion is composed of a polyester-based resin composition containing a polyester-based resin
- the sheath portion is composed of a polyamide-based resin composition containing a polyamide-based resin
- the polyester-based resin composition and the polyamide-based resin composition contain a bromine-based flame retardant, and the core-sheath ratio in the core-sheath composite fiber for artificial hair.
- the present invention relates to an artificial hair fiber characterized in that the ratio of the area of the hollow portion is 5% or more and 30% or less, and the hollow portion is polyhedral.
- the present invention also relates to a headdress product comprising the above-mentioned core-sheath composite fiber for artificial hair in one or more embodiments.
- the present invention is also the method for producing the core-sheath composite fiber for artificial hair according to one or more embodiments, wherein the polyester-based resin composition and the polyamide-based resin composition are used for the core-sheath composite spinning nozzle.
- Artificial hair comprising a step of melt spinning, forming a polyhedron hollow portion in a fiber cross section, and reducing the ratio of the area of the hollow portion to the total area of the fiber cross section to 5% or more and 30% or less.
- the present invention relates to a method for producing a core-sheath composite fiber.
- a core-sheath composite fiber for artificial hair having a tactile sensation close to that of human hair and having good durability, curl settability and flame retardancy, and a headdress product containing the same.
- a core-sheath composite fiber for artificial hair which has a tactile sensation close to that of human hair and has good durability, curl settability and flame retardancy.
- FIG. 1 is a schematic view showing a fiber cross section of a core-sheath composite fiber for artificial hair according to one or more embodiments of the present invention.
- FIG. 2A is a schematic view showing a fiber cross section of a flat bilobed core-sheath composite fiber having a quadrangular hollow portion.
- FIG. 2B is a schematic view showing a fiber cross section of a flat bilobed core-sheath composite fiber having a hexagonal hollow portion.
- FIG. 3A is a schematic explanatory view of the bulkiness measuring machine.
- FIG. 3B is a schematic explanatory view of the bulkiness measuring machine.
- FIG. 3C is a schematic explanatory view of the bulkiness measuring machine.
- FIG. 4 is a laser micrograph of a fiber cross section of the fiber of Example 1.
- FIG. 5 is a laser micrograph of a fiber cross section of the fiber of Comparative Example 3.
- the present inventors have made a polyester resin composition containing a polyester resin as a main component in the core portion and a polyamide resin as a main component in the sheath portion.
- a polyester resin composition containing the bromine-based flame retardant the polyester-based resin composition and the polyamide-based resin composition are impregnated with a bromine-based flame retardant, and the core-sheath ratio is the core portion in terms of area ratio.
- the core-sheath composite fiber for artificial hair has a tactile sensation close to that of human hair and has good durability, curl settability, and flame retardancy (hereinafter, also referred to simply as "core-sheath composite fiber"). It is found that (described)) can be obtained, and the present invention has been reached.
- the core-sheath composite fiber for artificial hair according to one or more embodiments of the present invention includes a core portion and a sheath portion, and has a flat multi-leaf shape.
- the core portion also has a flat multi-leaf shape.
- the fiber cross section and the core cross section have the same flat multi-leaf cross-sectional shape in which the fiber cross-sectional long axis direction and the core cross-sectional long axis direction substantially coincide with each other.
- the long axis directions of the fiber cross section and the core cross section are substantially the same
- the angle formed by the fiber cross section long axis and the core long axis is less than 15 degrees. means.
- the outer peripheral shape of the fiber cross section and the outer peripheral shape of the core cross section are similar in the fiber cross section, so that the thickness of the sheath is similar. Is uniform, and it is possible to prevent the core portion from being exposed to the surface while maintaining a good tactile sensation and appearance as artificial hair.
- a flat polyleaf shape is a combination of two or more leaf shapes selected from the group consisting of a round shape and an elliptical shape through a recess.
- the circular and / or elliptical forms partially overlap at the junction.
- the circular or elliptical shape does not necessarily have to draw a continuous arc, and includes a substantially circular or substantially elliptical shape that is partially deformed if it is not an acute angle. Further, it is not necessary to consider the unevenness of 2 ⁇ m or less generated on the cross section of the fiber and the outer periphery of the core portion due to the inclusion of additives and the like.
- the fiber cross section has a hollow portion and the center position of the hollow portion coincides with the center position of the fiber.
- the core portion is present inside the sheath portion and the hollow portion is present inside the core portion. It may be a concentric structure in which the center position of the core portion coincides with the center position of the fiber, or an eccentric structure in which the center position of the core portion does not coincide with the center position of the fiber and is eccentric. From the viewpoint of spinning stability and curl settability, it is preferable to have a concentric structure in which the center positions of the core portion and the hollow portion coincide with the center positions of the fibers.
- FIG. 1 is a schematic view showing a fiber cross section of the core-sheath composite fiber for artificial hair according to one or more embodiments of the present invention.
- the core-sheath composite fiber 1 for artificial hair of the embodiment includes a sheath portion 10 and a core portion 20, and has a hollow portion 30.
- both the fiber 1 and the core portion 20 have a flat bilobed cross-sectional shape (outer peripheral shape) in which two ellipses are connected via recesses, and a polyhedron is formed in the central portion of the fiber cross section 1.
- the hollow portion 30 is formed, and the hollow portion 30 has a first side 31a perpendicular to the long axis 11 of the fiber cross section 1 and a second side 31b perpendicular to the long axis 11 of the fiber cross section 1.
- the length of the first short axis 12 in the fiber cross section, which is a straight line connecting the two satisfies the following formula (1).
- Length of fiber cross-section major axis / Length of fiber cross-section first minor axis 1.1 or more and 2.0 or less (1)
- the length of the core section long axis 21 which is the longest straight line among the straight lines connecting arbitrary two points on the outer periphery of the core section so as to be parallel to the line symmetry axis and the line symmetry axis.
- the first short line of the core section is a straight line connecting the two points that have the maximum length.
- the center point of the long axis of the core portion coincides with the center point of the long axis of the fiber cross section, whereby unintended crimping occurs. Can be suppressed.
- the core-sheath composite fiber for artificial hair has a flat multileaf fiber cross section, so that two or more leaf shapes consisting of a circular shape and an elliptical shape are connected via a recess. Since the surface of the fibers has smooth irregularities, the contact area between the fibers and the contact area with the comb when passing through the comb becomes small, and it is easy to realize a tactile sensation close to that of human hair and good combability.
- the hollow portion is a polyhedron having a first side substantially perpendicular to the long axis of the fiber cross section and a second side substantially perpendicular to the long axis of the fiber cross section.
- the angle between the first side where the angle of the fiber cross section with respect to the long axis is 70 degrees or more and 110 degrees or less and the angle of the fiber cross section with respect to the long axis is 70 degrees or more and 110 degrees or less. It is preferably a polyhedron with edges.
- the angle of the first side of the hollow portion with respect to the long axis of the fiber cross section is preferably 80 degrees or more and 100 degrees or less. Further, it is preferable that the angle of the second side of the hollow portion to be the long axis of the fiber cross section is 80 degrees or more and 100 degrees or less.
- the "angle of the first side of the hollow portion with respect to the long axis of the fiber cross section" refers to the average value of 30 arbitrarily selected fiber cross sections. In the 30 fiber cross sections selected arbitrarily, it is preferable that both the maximum value and the minimum value of the angle of the first side of the hollow portion with respect to the long axis are included in the above range.
- the "angle of the second side of the hollow portion with respect to the long axis of the fiber cross section” means an average value of 30 arbitrarily selected fiber cross sections.
- the 30 fiber cross sections selected arbitrarily it is preferable that both the maximum value and the minimum value of the angle of the second side of the hollow portion with respect to the long axis of the fiber cross section are included in the above range.
- first side and the second side of the hollow portion are substantially parallel in the fiber cross section, specifically,
- the angle between the first side and the second side is preferably in the range of 0 degrees or more and 40 degrees or less.
- the hollow portion has a first side substantially perpendicular to the long axis of the fiber cross section and a second side substantially perpendicular to the long axis of the fiber cross section as described above.
- the first side and the second side are polyhedrons that are substantially parallel to each other, and the specific shape is not particularly limited. From the viewpoints of possible points and points where surface reflection can be suppressed, for example, a quadrangle, a pentagon, a hexagon, a seven-sided shape, an octagonal shape, or the like is preferable.
- FIG. 2A shows an example of a quadrangle
- FIG. 2B shows an example of a hexagon.
- the first side and the second side of the hollow portion preferably have a length of 5 ⁇ m or more and 50 ⁇ m or less, and more preferably 10 ⁇ m or more and 30 ⁇ m or less.
- the length of the first side of the hollow portion means the average value in the cross section of 30 arbitrarily selected fibers. In the 30 fiber cross sections selected arbitrarily, it is preferable that both the maximum value and the minimum value of the length of the first side of the hollow portion are included in the above-mentioned range. Further, in the present invention, the "length of the second side of the hollow portion" refers to the average value in the cross section of 30 arbitrarily selected fibers.
- both the maximum value and the minimum value of the length of the second side of the hollow portion are included in the above-mentioned range.
- the length of the first side and the second side is 5 ⁇ m or more, the stress is not concentrated locally, the curl settability is good, the peeling of the core portion and the sheath portion is less likely to occur, and the fiber cross section is also formed. It becomes hard to collapse. In addition, entanglement of fibers is less likely to occur, and combability is improved.
- the length of the first side and the second side is 50 ⁇ m or less, the outer circumference of the fiber and the outer circumference of the hollow portion are separated from each other, so that the wall thickness does not become too thin, the curl setability is improved, and the core portion and the sheath portion are formed. Peeling is less likely to occur, and the fiber cross section is less likely to collapse. In addition, entanglement of fibers is less likely to occur, and combability is improved.
- the ratio of the area of the hollow portion to the total area of the fiber cross section (hereinafter, also referred to as the hollow ratio) is 5% or more and 30% or less.
- the total area of the fiber cross section refers to the area of the portion covered by the outer peripheral portion of the fiber in the cross section (cross section) in which the fiber is vertically sliced, and includes the area of the hollow portion.
- the presence of a hollow portion in the fiber cross section eliminates the need to heat or cool the center of the fiber when setting the hair iron, and shortens the cooling time.
- the weight becomes lighter than that of a fiber bundle using a fiber having no hollow portion, and the curl is curled over time due to its own weight.
- the phenomenon of growth can also be reduced.
- the hollow portion is large from the viewpoint of maintaining the curl shape, but on the other hand, when the hollow portion is large, the wall thickness becomes relatively thin, it becomes difficult to maintain the shape of the fiber cross section, and the pressure is increased. On the other hand, there is a high possibility that it will be deformed or collapsed.
- the hollow ratio of the fiber cross section is preferably 7% or more and 30% or less, more preferably 10% or more and 30% or less, and further preferably 10% or more and 25% or less.
- the "hollow ratio" refers to the average value of 30 arbitrarily selected fiber cross sections. In the 30 fiber cross sections selected arbitrarily, it is preferable that both the maximum value and the minimum value of the hollowness are included in the above-mentioned range.
- the cross-sectional shapes of the fibers, the core portion and the hollow portion described above can be controlled by using a nozzle (hole) having a shape close to the desired cross-sectional shape.
- the core-sheath ratio is in this range, the bending rigidity value as a physical property related to the tactile sensation and texture becomes close to that of human hair, so that a core-sheath composite fiber for artificial hair having the same quality as human hair can be obtained.
- the number of cores is less than this range, the bending rigidity value is lower than that of human hair, so that the core-sheath composite fiber for artificial hair of the same quality as human hair cannot be obtained.
- the range of: 3 is preferable, and the range of 4: 6 to 6: 4 is more preferable.
- the core-sheath composite fiber for artificial hair in order to prevent the core and the sheath from peeling off, it is preferable that the core is not exposed on the fiber surface and is completely covered by the sheath.
- the core-sheath composite fiber for artificial hair preferably has a single fiber fineness of 10 dtex or more and 150 dtex or less, more preferably 30 dtex or more and 120 dtex or less. It is more preferably 40 dtex or more and 100 dtex or less, and particularly preferably 50 dtex or more and 90 dtex or less.
- the core-sheath composite fiber for artificial hair does not necessarily have to have the same fineness, core-sheath ratio, and cross-sectional shape as an aggregate of fibers, for example, a fiber bundle. Fibers having different fineness, core-sheath ratio, and cross-sectional shape may be mixed.
- the core portion is composed of a polyester-based resin composition containing a polyester-based resin as a main component
- the sheath portion is a polyamide containing a polyamide-based resin as a main component. It is composed of a based resin composition.
- the polyester resin composition containing a polyester resin as a main component is 50% by weight or more of the polyester resin when the total weight of the polyester resin composition is 100% by weight. It means that it contains a large amount, and it is preferable to contain 60% by weight or more of the polyester resin, more preferably 70% by weight or more, further preferably 80% by weight or more, and further preferably 90% by weight or more. , 95% by weight or more is even more preferable.
- the polyester resin it is preferable to use one or more selected from the group consisting of polyalkylene terephthalate and copolymerized polyester mainly composed of polyalkylene terephthalate.
- the "copolymerized polyester mainly composed of polyalkylene terephthalate” refers to a copolymerized polyester containing 80 mol% or more of polyalkylene terephthalate.
- the polyalkylene terephthalate is not particularly limited, and examples thereof include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polycyclohexanedimethylene terephthalate.
- the copolymerized polyester mainly composed of the polyalkylene terephthalate is not particularly limited, but is mainly composed of polyalkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polycyclohexanedimethylene terephthalate, and other copolymerization components. Examples thereof include copolymerized polyester containing.
- Examples of the other copolymerization components include isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, pyromellitic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, and sebacine.
- Polyvalent carboxylic acids such as acids, dodecanedioic acids and their derivatives; dicarboxylic acids including sulfonates such as 5-sodium sulfoisophthalic acid, 5-sodium sulfoisophthalate dihydroxyethyl and their derivatives; 1,2-propane Didiol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, polyethylene glycol, trimethylolpropane, pentaerythritol, 4-hydroxy Examples thereof include benzoic acid, ⁇ -caprolactone, and ethylene glycol ether of bisphenol A.
- the copolymerized polyester is preferably produced by reacting the main polyalkylene terephthalate with a small amount of other copolymerizing components.
- the polyalkylene terephthalate a polymer of terephthalic acid and / or a derivative thereof (for example, methyl terephthalate) and alkylene glycol can be used.
- the copolymerized polyester is a mixture of terephthalic acid and / or a derivative thereof (for example, methyl terephthalate) used for the polymerization of the main polyalkylene terephthalate and alkylene glycol, and a monomer or a monomer which is a small amount of other copolymerization components. It may be produced by polymerizing a product containing an oligomer component.
- the copolymerized polyester may be polycondensed with the other copolymerization components on the main chain and / or side chain of the main polyalkylene terephthalate, and the copolymerization method and the like are not particularly limited.
- copolymerized polyester containing polyalkylene terephthalate as a main component examples include, for example, ethylene glycol ether of bisphenol A, 1,4-cyclohexadimethanol, isophthalic acid and dihydroxy 5-sodium sulfoisophthalate containing polyethylene terephthalate as a main component.
- the polyalkylene terephthalate and the copolymerized polyester mainly composed of the polyalkylene terephthalate may be used alone or in combination of two or more.
- polyester mainly composed of terephthalate and copolymerized with isophthalic acid and polyester mainly composed of polyethylene terephthalate and copolymerized with dihydroxyethyl 5-sodium sulfoisophthalate alone or in combination of two or more.
- the intrinsic viscosity (sometimes referred to as IV value) of the polyester resin is not particularly limited, but is preferably 0.3 dL / g or more and 1.2 dL / g or less, and 0.4 dL / g or more and 1.0 dL / g. It is more preferably g or less.
- the intrinsic viscosity is 0.3 dL / g or more, the mechanical strength of the obtained fiber does not decrease and there is no risk of drip during the combustion test.
- the intrinsic viscosity is 1.2 dL / g or less, the molecular weight does not increase too much, the melt viscosity does not become too high, melt spinning becomes easy, and the fineness tends to be uniform.
- the polyester-based resin composition constituting the core portion may contain other resins in addition to the polyester-based resin.
- other resins include polyamide-based resins, vinyl chloride-based resins, modaacrylic-based resins, polycarbonate-based resins, polyolefin-based resins, and polyphenylene sulfide-based resins.
- one type may be used alone, or two or more types may be used in combination.
- the polyamide-based resin composition containing a polyamide-based resin as a main component is more than 50% by weight when the total weight of the polyamide-based resin composition is 100% by weight. It means that the polyamide resin is contained in an amount of 60% by weight or more, more preferably 70% by weight or more, further preferably 80% by weight or more, still more preferably 90% by weight or more. It is even more preferable to contain 95% by weight or more.
- the polyamide-based resin used in the present invention is obtained by polymerizing one or more selected from the group consisting of lactam, aminocarboxylic acid, a mixture of dicarboxylic acid and diamine, a mixture of dicarboxylic acid derivative and diamine, and a salt of dicarboxylic acid and diamine. It means the nylon resin obtained by the above.
- lactam examples include, but are not limited to, 2-azetidinone, 2-pyrrolidinone, ⁇ -valerolactam, ⁇ -caprolactam, enantractam, caprilactam, undecalactam, laurolactam and the like. can. Of these, ⁇ -caprolactam, undecalactam, and laurolactam are preferable, and ⁇ -caprolactam is particularly preferable. These lactams may be used alone or in mixtures of two or more.
- aminocarboxylic acid examples are not particularly limited, but for example, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and the like.
- Examples include 12-aminododecanoic acid. Of these, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid are preferable, and 6-aminocaproic acid is particularly preferable.
- These aminocarboxylic acids may be used alone or in a mixture of two or more.
- dicarboxylic acid used in the mixture of dicarboxylic acid and diamine, the mixture of dicarboxylic acid derivative and diamine, or the salt of dicarboxylic acid and diamine are not particularly limited, but for example, oxalic acid, malonic acid, succinic acid, and the like.
- Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brushphosphoric acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, cyclohexanedicarboxylic acid
- aromatic dicarboxylic acids such as alicyclic dicarboxylic acids, phthalic acids, isophthalic acids, terephthalic acids, and naphthalenedicarboxylic acids.
- adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, and isophthalic acid are preferable, and adipic acid, terephthalic acid, and isophthalic acid are particularly preferable.
- These dicarboxylic acids may be used alone or in a mixture of two or more.
- diamine used in the mixture of dicarboxylic acid and diamine, the mixture of dicarboxylic acid derivative and diamine, or the salt of dicarboxylic acid and diamine are not particularly limited, but for example, 1,4-diaminobutane, 1,5.
- the polyamide-based resin (sometimes referred to as nylon resin) is not particularly limited, and is, for example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 6/10, nylon 6/12, nylon 6T and /.
- nylon resin is not particularly limited, and is, for example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 6/10, nylon 6/12, nylon 6T and /.
- semi-aromatic nylon containing 6I units a copolymer of these nylon resins, and the like.
- a copolymer of nylon 6, nylon 66, nylon 6 and nylon 66 is more preferable.
- the polyamide-based resin can be produced, for example, by a polyamide-based resin polymerization method in which a polyamide-based resin raw material is heated in the presence or absence of a catalyst. Stirring may or may not occur during the polymerization, but stirring is preferred to obtain a homogeneous product.
- the polymerization temperature can be arbitrarily set according to the degree of polymerization, the reaction yield, and the reaction time of the target polymer, but a low temperature is preferable in consideration of the quality of the finally obtained polyamide resin.
- the reaction rate can also be set arbitrarily. Although there is no limitation on the pressure, it is preferable to reduce the pressure inside the system in order to efficiently extract the volatile components to the outside of the system.
- the end of the polyamide resin may be blocked with a terminal blocking agent such as a carboxylic acid compound and an amine compound, if necessary.
- a terminal blocking agent such as a carboxylic acid compound and an amine compound
- the concentration of the terminal amino group or the terminal carboxyl group of the obtained nylon resin is lower than that when the terminal blocking agent is not used.
- the terminal is blocked with a dicarboxylic acid or diamine, the sum of the concentrations of the terminal amino group and the terminal carboxyl group does not change, but the ratio of the concentration of the terminal amino group to the terminal carboxyl group changes.
- carboxylic acid compound examples are not particularly limited, but are, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, and myristic acid.
- aliphatic monocarboxylic acids such as araquinic acid
- alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid
- benzoic acid toluic acid
- Aromatic monocarboxylic acids such as ethyl benzoic acid and phenylacetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brushlin Acids, aliphatic dicarboxylic acids such as tetradecanedioic acid, pentadecanedioic acid and octadecanedioic acid, alicyclic
- amine compound examples are not particularly limited, but for example, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, and the like.
- Alicyclic monoamines such as tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, nonadesylamine and icosylamine, alicyclic monoamines such as cyclohexylamine and methylcyclohexylamine, aromatic monoamines such as benzylamine and ⁇ -phenylethylamine.
- 1,4-diaminobutane 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1, 11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecan, 1,17-diaminoheptadecan, 1, , 18-Diaminooctadecane, 1,19-diaminononadecan, aliphatic diamines such as 1,20-diaminoeikosan, cyclohexanediamine, alicyclic diamines such as bis- (4-amino
- the concentration of terminal groups in the polyamide resin is not particularly limited, but the one with a higher terminal amino group concentration is used when it is necessary to improve dyeability for fiber applications or when designing a material suitable for alloying for resin applications. Is preferable. On the contrary, when it is desired to suppress coloring or gelation under long-term aging conditions, it is preferable that the terminal amino group concentration is low. Furthermore, if you want to suppress lactam regeneration during remelting, thread breakage during melt spinning due to oligomer formation, mold deposit during continuous injection molding, and die mark generation during continuous extrusion of film, both the terminal carboxyl group concentration and the terminal amino group concentration are both. Lower is preferable.
- the terminal group concentration may be adjusted depending on the intended use, but both the terminal amino group concentration and the terminal carboxyl group concentration are preferably 1.0 ⁇ 10 -5 to 15.0 ⁇ 10 -5 eq / g, more preferably. 2.0 ⁇ 10 -5 to 12.0 ⁇ 10 -5 eq / g, particularly preferably 3.0 ⁇ 10 -5 to 11.0 ⁇ 10 -5 eq / g.
- the numerical range indicated by "...-" includes both-end values as in the numerical range indicated by "... or more ... or less”.
- a method of adding the terminal blocker a method of adding the caprolactam at the same time as a raw material at the initial stage of polymerization, a method of adding it during the polymerization, and a method of adding the nylon resin when passing it through a vertical stirring thin film evaporator in a molten state. Etc. are adopted.
- the terminal blocker may be added as it is, or may be dissolved in a small amount of solvent and added.
- the polyamide-based resin composition constituting the sheath portion may contain other resins in addition to the polyamide-based resin.
- other resins include vinyl chloride resin, modal acrylic resin, polycarbonate resin, polyolefin resin, polyphenylene sulfide resin and the like.
- one type may be used alone, or two or more types may be used in combination.
- the core-sheath composite fiber for artificial hair has a core made of polyalkylene terephthalate and poly from the viewpoint of making the tactile sensation and appearance closer to human hair and further improving curl and curl retention. It is preferably composed of a polyester-based resin composition containing one or more polyester resins selected from the group consisting of a copolymerized polyester mainly composed of alkylene terephthalate as a main component, and the sheath portion is composed of a group consisting of nylon 6 and nylon 66. It is more preferable to use a polyamide-based resin composition containing at least one selected polyamide-based resin as a main component.
- the "polyamide-based resin mainly composed of at least one selected from the group consisting of nylon 6 and nylon 66" is a polyamide-based resin containing 80 mol% or more of nylon 6 and / or nylon 66. Means resin.
- a pigment may be contained in the core portion or the resin composition constituting the sheath portion in order to obtain a core-sheath composite fiber for artificial hair having a desired color.
- the pigment is not particularly limited, and for example, a general pigment such as carbon black or anthraquinone can be used.
- a pigment masterbatch can also be used.
- a pigment masterbatch is a mixture of a pigment and a resin composition that is kneaded using a kneader such as an extruder to be pelletized (sometimes referred to as compounding), and is generally difficult to handle because it is in the form of fine powder.
- the amount of the pigment added to the polyester resin composition constituting the core portion is not particularly limited, but it is preferable that the pigment is contained in an amount of 0.005 part by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the polyester resin. It is more preferable to include 01 parts by weight or more and 1 part by weight or less. Further, the amount of the pigment added to the polyamide resin composition constituting the sheath portion is not particularly limited, but it is preferable that the pigment is contained in an amount of 0.005 part by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the polyamide resin. It is more preferable to contain 0.01 parts by weight or more and 1 part by weight or less.
- the core is made of a polyester resin composition containing a brominated flame retardant
- the sheath is made of a polyamide resin composition containing a brominated flame retardant. It is possible to obtain core-sheath fibers for artificial hair having sex.
- the bromine-based flame retardant is not particularly limited, and is, for example, a brominated epoxy flame retardant; pentabromotoluene, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether, bis (tribromophenoxy) ethane, tetrabromobisphenol phthalic acid.
- Bromine-containing phosphate esters such as ethylenebis (tetrabromophthalimide), ethylenebis (pentabromophenyl), octabromotrimethylphenylindan, tris (tribromoneopentyl) phosphate; brominated polystyrenes; brominated polybenzyl acrylate Classes; brominated phenoxy resins; brominated polycarbonate oligomers; tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (allyl ether), tetrabromobisphenol A- Tetrabromobisphenol A derivatives such as bis (hydroxyethyl ether); bromine-containing triazine compounds such as tris (tribromophenoxy) triazine; bromine-containing isocyanuric acid compounds such as tris (2,3-dibromopropyl) isocyan
- a brominated epoxy flame retardant whose molecular terminal is composed of an epoxy group or tribromophenol can be used as a raw material, but the structure of the brominated epoxy flame retardant after melt-kneading is Not particularly limited, when the total number of the constituent units represented by the following chemical formula (1) and the constituent units in which at least a part of the following chemical formula (1) is modified is 100 mol%, 80 mol% or more is represented by the chemical formula (1). It is preferably a constituent unit.
- the structure of the brominated epoxy flame retardant may change at the molecular end after melt-kneading.
- the molecular end of the brominated epoxy flame retardant may be substituted with an epoxy group or a hydroxyl group other than tribromophenol, a phosphoric acid group, a phosphonic acid group, or the like, and the molecular end is bonded to the polyester component by an ester group. May be.
- a part of the structure other than the molecular terminal of the brominated epoxy flame retardant may be changed.
- the secondary hydroxyl group of the brominated epoxy flame retardant and the epoxy group may be bonded to form a branched structure, and if the bromine content in the brominated epoxy flame retardant molecule does not change significantly, the above chemical formula ( A part of the bromine of 1) may be eliminated or added.
- a polymer type brominated epoxy flame retardant as shown in the following general formula (2) is preferably used.
- m is 1 to 1000.
- examples of the polymer-type brominated epoxy flame retardant as shown in the following general formula (2) include a brominated epoxy flame retardant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. (trade name “SR-T2MP”). Commercially available products may be used.
- the brominated epoxy flame retardant is not particularly limited, but it is preferable that the core portion and / or the sheath portion contains, for example, 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.
- a polyamide resin composed of a polyester resin composition containing 5 parts by weight or more and 40 parts by weight or less of a fueling agent, and having a sheath portion mainly composed of at least one selected from the group consisting of nylon 6 and nylon 66, and bromine. It is preferably composed of a polyamide resin composition containing 5 parts by weight or more and 40 parts by weight or less of the copolymerized epoxy flame retardant.
- a flame retardant aid may be used in combination.
- the flame retardant aid is not particularly limited, but from the viewpoint of flame retardancy, it is preferable to use, for example, an antimony compound or a composite metal containing antimony in the core portion and / or the sheath portion.
- the antimony compound include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, potassium antimonate, calcium antimonate and the like.
- One or more selected from the group consisting of antimony trioxide, antimony pentoxide, and sodium antimonate is more preferable because of the flame retardancy improving effect and the influence on the tactile sensation.
- the flame retardant aid is not particularly limited, but for example, it is preferable to include 0.1 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the main component resin.
- a flame-retardant aid in the polyamide-based resin composition constituting the sheath portion, appropriate surface irregularities are formed on the fiber surface, and in addition to flame retardancy, it has a low-gloss appearance close to that of human hair. It is easy to obtain core-sheath composite fibers for artificial hair.
- the core-sheath composite fiber for artificial hair contains various additives such as a heat resistant agent, a stabilizer, a fluorescent agent, an antioxidant, and an antistatic agent, if necessary, within a range that does not impair the effects of the present invention. You may.
- the core-sheath composite fiber for artificial hair is obtained by melt-kneading the respective resin compositions constituting the core and the sheath using various general kneaders, and then melt-kneading the core and the sheath. It can be manufactured by melt spinning using a mold composite spinning nozzle.
- a polyester-based resin composition obtained by dry-blending each component such as the above-mentioned polyester resin and brominated epoxy-based flame retardant is melt-kneaded using various general kneaders to obtain a core resin composition.
- the polyamide-based resin composition obtained by dry-blending each component such as the above-mentioned polyamide-based resin, pigment, and brominated epoxy-based flame retardant is melt-kneaded using various general kneaders to obtain a sheath resin composition. It can be produced by melt-spinning using a core-sheath type composite spinning nozzle.
- the kneader include a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, a kneader, and the like. Above all, a twin-screw extruder is preferable from the viewpoint of adjusting the kneading degree and easiness of operation.
- the melt spinning method is preferable as the method for producing the fiber.
- the temperature of the extruder, gear pump, nozzle, etc. is 250 ° C. or higher and 300 ° C. or lower.
- the temperature of the extruder, gear pump, nozzle, etc. is set to 260 ° C or higher and 320 ° C or lower, and after melt-spinning, the temperature is cooled to the glass transition point or lower of each resin to 30 m / min or higher.
- a spun yarn (undrawn yarn) can be obtained by picking up at a speed of 5000 m / min or less.
- the polyester resin composition constituting the core portion is supplied by the core extruder extruder of the melt spinning machine, and the polyamide resin composition constituting the sheath portion is the sheath of the melt spinning machine.
- a spun yarn (undrawn yarn) is obtained by supplying the molten polymer with a core-sheath type composite spinning nozzle (hole) having a predetermined shape and supplying the melted polymer. It is preferable that the spun yarn (undrawn yarn) is heat-stretched, and the stretching is performed by a two-step method in which the spun yarn is once wound and then drawn, and the spun yarn is continuously wound without being wound. It may be carried out by any method of the direct spinning and stretching method of stretching. The thermal stretching is performed by a one-step stretching method or a multi-step stretching method of two or more steps.
- a heating roller As the heating means in the heat stretching, a heating roller, a heat plate, a steam jet device, a hot water tank, etc. can be used, and these can be used in combination as appropriate.
- An oil agent such as a fiber treatment agent or a softening agent may be applied to the core-sheath composite fiber for artificial hair to bring the texture and texture closer to human hair.
- the fiber treatment agent include silicone-based fiber treatment agents and non-silicone-based fiber treatment agents for improving tactile sensation and combability.
- the core-sheath composite fiber for artificial hair may be processed by a gear crimp.
- the fibers are gently bent, a natural appearance is obtained, and the adhesion between the fibers is lowered, so that the combability is also improved.
- the gear crimp in general, the fiber is passed between two meshed gears in a state where the fiber is heated to the softening temperature or higher, and the shape of the gear is transferred to develop the fiber bending. Further, if necessary, by heat-treating the core-sheath composite fiber for artificial hair at different temperatures in the fiber processing stage, curls having different shapes can be developed.
- the core-sheath composite fiber for artificial hair may be used alone as artificial hair, or may be used in combination with other artificial hair fibers or natural fibers such as human hair and animal hair. You may. Examples of other artificial hair fibers include acrylic fibers.
- the core-sheath composite fiber for artificial hair can be used without particular limitation as long as it is a headdress product.
- it can be used for hair wigs, wigs, weaving, hair extensions, blade hairs, hair accessories, doll hairs and the like.
- the headdress product may be composed only of the core-sheath composite fiber for artificial hair of the present invention. Further, the headdress product may be formed by combining the core-sheath composite fiber for artificial hair of the present invention with other fibers for artificial hair or natural fibers such as human hair and animal hair.
- the measurement method and evaluation method used in the examples and comparative examples are as follows.
- the length of the second side of the portion, the area of the hollow portion, the area of the core portion, the area of the sheath portion, and the area of the fiber cross section were measured.
- the ratio of the major axis of the fiber cross section to the first minor axis L / S1
- the ratio of the major axis of the core section to the first minor axis Lc / Sc1
- the hollow portion with respect to the major axis of the fiber cross section.
- each size in the fiber cross section such as the angle of the first side, the angle of the second side of the hollow portion with respect to the long axis of the fiber cross section, the length of the first side of the hollow portion, and the length of the second side of the hollow portion. Is the average value of the measured values of the 30 fiber cross sections selected arbitrarily.
- the bulkiness value of the hair sample was measured using the bulkiness measuring machine shown in FIGS. 3A to 3C.
- the bulkiness measuring machine 100 includes a support base 101 and pinches 102 and 103 arranged on the support base 101 to pinch the hair.
- a scale 104 is attached to the sandwiching tool 102 with a transparent tape (not shown).
- the support base 101 and the sandwiches 102 and 103 are all made of acrylic resin. As shown in FIG. 3C, the hair sample 40 is placed between the pinch 102 and the pinch 103 so that the center in the length direction of the pinch 102 and the center of the layer portion of the hair sample 40 coincide with each other. It was placed and the bulk value was measured.
- the limit oxygen index (LOI value) was measured according to the JIS L 1091 E method (oxygen index method test). Specifically, both ends of the filament (length 16 cm, weight 0.25 g) were lightly tied together with double-sided tape, sandwiched between twisters, and twisted. When it was twisted enough, it was folded in two in the middle. Both ends of the twisted filament were fastened with cellophane (registered trademark) tape so that the total length was 7 cm. The obtained sample was pre-dried at 105 ° C. for 60 minutes, and further dried in a desiccator for 30 minutes or more.
- the dried sample was adjusted to a predetermined oxygen concentration, and after 40 seconds, it was ignited from above with a gas igniter having a flame length reduced to 8 to 12 mm, and the igniter was released after ignition.
- the oxygen concentration that burned for 5 cm or more or continued to burn for 3 minutes or more was examined, and the test was repeated 3 times under the same conditions to obtain the LOI value, which was evaluated according to the following 4 grade criteria.
- C LOI value is 25 or more and less than 26
- D LOI value is less than 25
- Example 1 Brominated epoxy flame retardant (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name "SR-T2MP") for 100 parts by weight of polyethylene terephthalate pellets (manufactured by East West Chemical Private Limited, East PET product name "A-12", also referred to as PET).
- SR-T2MP brominated epoxy flame retardant
- PET East West Chemical Private Limited
- nylon 6 manufactured by Unitika, trade name "A1030BRL”, also referred to as PA6
- 12 parts by weight of brominated epoxy flame retardant manufactured by Sakamoto Yakuhin Kogyo, trade name "SR-T2MP”
- SR-T2MP brominated epoxy flame retardant
- SA-A Sodium antimonate
- black pigment masterbatch manufactured by Dainichi Seika Kogyo, trade name "PAM (F) 25005BLACK (20)
- Yellow pigment masterbatch manufactured by Dainichi Seika Kogyo, trade name "PAM (F) 28990YELLOW (20)
- Red pigment masterbatch manufactured by Dainichi Seika Kogyo, trade name "PAM (F) 28991RED
- 20) 0.5 parts by weight was added, and after
- the pellet-shaped polyester resin composition and the polyamide resin composition are supplied to the extruder, respectively, and extruded from a core-sheath type composite spinning nozzle (hole) having a nozzle shape shown in Table 1 below at a set temperature of 270 ° C. , 40-200 m / min, polyester resin composition as core, polyamide resin composition as sheath, core-sheath composite fiber with core-sheath ratio of 5: 5 A drawn yarn was obtained.
- the obtained undrawn yarn was drawn using a heat roll at 85 ° C. at a rate of 45 m / min to obtain a triple drawn yarn, and further continuously heated to 200 ° C. using a heat roll at 45 m / min. Take up and heat-treat at the speed of After adhering, it was dried to obtain a core-sheath composite fiber having a single fiber fineness shown in Table 1 below.
- Example 2 A core-sheath composite fiber was obtained in the same manner as in Example 1 except that the core-sheath type composite spinning nozzle (hole) having the nozzle shape shown in Table 1 below was used.
- Example 3 The resin used for the sheath is nylon 66 (manufactured by Toray Industries, Inc., trade name "Amiran CM3001", also referred to as PA66), the barrel set temperature at the time of pelletization is 280 ° C, the nozzle set temperature is 280 ° C, and the core sheath ratio is 7.
- a core-sheath composite fiber was obtained in the same manner as in Example 1 except that the ratio was 3.
- Example 4 The resin used for the core is polybutylene terephthalate (manufactured by Mitsubishi Chemical Corporation, trade name "Novaduran 5020", sometimes referred to as PBT), the barrel set temperature at the time of pelletization is 260 ° C, and the nozzle set temperature is 260 ° C.
- Core-sheath composite fibers were obtained in the same manner as in Example 1 except that the core-sheath ratio was 3: 7.
- Example 3 A core-sheath composite fiber was obtained in the same manner as in Example 1 except that the core-sheath type composite spinning nozzle (hole) having the nozzle shape shown in Table 1 below was used.
- Example 4 A core-sheath composite fiber was obtained in the same manner as in Example 1 except that the core-sheath type composite spinning nozzle (hole) having the nozzle shape shown in Table 1 below was used.
- red pigment master batch manufactured by Dainichi Seika Kogyo, trade name "PESM3005RED (20)", pigment: 20% by weight
- base resin polyester resin
- 0.2 parts by weight is added, and after dry blending, two It was supplied to a shaft extruder, melt-kneaded at a barrel set temperature of 280 ° C., and pelletized to obtain a polyester resin composition.
- nylon 6 manufactured by Unitika, trade name "A1030BRL”
- black pigment masterbatch manufactured by Dainichi Seika Kogyo, trade name "PESM22367BLACK (20)"
- the core-sheath composite fiber is the same as in Example 1 except that it is added, supplied to a twin-screw extruder after dry blending, melt-kneaded at a barrel set temperature of 260 ° C., and pelletized to obtain a polyamide-based resin composition.
- FIG. 4 is a laser micrograph of a cross section of the fiber of Example 1.
- both the fiber and the core portion have a flat bilobed shape, and the hollow portion has a substantially regular hexagonal cross-sectional shape.
- FIG. 5 is a laser micrograph of a cross section of the fiber of Comparative Example 3. As shown in FIG. 5, in the core-sheath composite fiber for artificial hair, the fiber, the core portion, and the hollow portion all have a substantially circular cross-sectional shape.
- the fibers of Examples 1 to 4 had a tactile sensation similar to that of human hair, and had good durability, curl settability, and flame retardancy.
- the fiber of Comparative Example 1 On the other hand, in the fiber of Comparative Example 1, the ratio of the sheath portion was too low, so that the core portion was exposed on the fiber surface, the tactile sensation and durability were very poor, and the fiber could not be molded as a good fiber.
- the fiber of Comparative Example 2 had a very poor curl settability because the ratio of the core portion was too low. Since the fiber of Comparative Example 3 has a round cross section and does not have irregularities on the fiber surface, it has an unnatural appearance and deteriorates in tactile sensation and durability. In addition, peeling was also observed at the core-sheath interface, and it could not be molded as a good fiber.
- the fiber of Comparative Example 4 Since the fiber of Comparative Example 4 has a round cross-sectional shape in the hollow portion and a low hollow ratio, the curl settability is deteriorated. Since the fiber of Comparative Example 5 does not contain a flame retardant in the core portion and the sheath portion, the flame retardancy becomes very poor.
- a core-sheath composite fiber for artificial hair including a core and a sheath.
- the core portion is composed of a polyester resin composition containing a polyester resin
- the sheath portion is composed of a polyamide resin composition containing a polyamide resin.
- the polyester-based resin composition and the polyamide-based resin composition contain a bromine-based flame retardant and contain a bromine-based flame retardant.
- the cross-sectional shape of the fiber cross section is a flat multi-leaf shape, the fiber cross section has a hollow portion, and the ratio of the area of the hollow portion to the total area of the fiber cross section is 5% or more and 30% or less, and the hollow portion.
- the core-sheath composite fiber for artificial hair a straight line having the maximum length among straight lines connecting arbitrary two points on the outer periphery of the fiber cross section so as to be parallel to the line symmetry axis and the line symmetry axis.
- the first fiber cross section which is a straight line connecting two points having the maximum length when connecting the length of the major axis and any two points on the outer circumference of the fiber section so as to be perpendicular to the long axis of the fiber section.
- the core-sheath composite fiber for artificial hair according to any one of [1] to [3], wherein the length of the minor axis satisfies the following formula (1).
- the core-sheath composite fiber for artificial hair which is the maximum length of the straight lines connecting arbitrary two points on the outer periphery of the core portion cross section so as to be parallel to the line symmetry axis and the line symmetry axis. It is a straight line connecting two points that are the maximum length when connecting the length of the long axis of the partial cross section and any two points on the outer circumference of the core cross section so as to be perpendicular to the long axis of the core section.
- the core-sheath composite fiber for artificial hair according to any one of [1] to [4], wherein the length of the first minor axis having a cross section of the core satisfies the following formula (2).
- Core cross-section long axis length / core cross-section first minor axis length 1.3 or more and 2.0 or less (2)
- the hollow portion has a first side having an angle of 80 degrees or more and 100 degrees or less with respect to the long axis of the fiber cross section and a second side having an angle of 80 degrees or more and 100 degrees or less with respect to the long axis of the fiber cross section.
- the core-sheath composite fiber for artificial hair according to any one of [1] to [5], which is a spheroid.
- polyester-based resin composition contains one or more polyester-based resins selected from the group consisting of polyalkylene terephthalates and copolymerized polyesters mainly composed of polyalkylene terephthalates. Core-sheath composite fiber for artificial hair described in Crab.
- polyamide-based resin composition contains a polyamide-based resin mainly composed of at least one selected from the group consisting of nylon 6 and nylon 66. Core sheath composite fiber.
- a headdress product comprising the core-sheath composite fiber for artificial hair according to any one of [1] to [10].
- a step of melt-spinning a polyester-based resin composition and a polyamide-based resin composition using a nozzle for core-sheath composite spinning is included, a polyhedron hollow portion is formed in the fiber cross section, and the hollow portion is formed with respect to the entire area of the fiber cross section.
- a method for producing a core-sheath composite fiber for artificial hair wherein the ratio of the area of the portion is 5% or more and 30% or less.
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Abstract
Description
本発明の1以上の実施形態の人工毛髪用芯鞘複合繊維は、芯部と鞘部を含み、扁平多葉形の断面形状を有する。本発明の1以上の実施形態の人工毛髪用芯鞘複合繊維において、芯部も扁平多葉形の断面形状を有することが好ましい。本発明の1以上の実施形態において、繊維断面と芯部断面は、繊維断面長軸方向と芯部断面長軸方向が略一致した同一の扁平多葉形の断面形状を有することがより好ましい。本発明の1以上の実施形態において、「繊維断面と芯部断面の長軸方向が略一致している」とは、繊維断面長軸と芯部長軸の成す角が15度未満であることを意味する。繊維断面と芯部断面の長軸方向が略一致した同一の扁平多葉形である場合、繊維断面において、繊維断面の外周形状と芯部断面の外周形状が相似形であるため、鞘の厚みが均一となり、人工毛髪として良好な触感と外観を維持した上で、芯部の表面への露出を防止することができる。扁平多葉形は、円形及び楕円形からなる群から選ばれる二つ以上の葉形が凹部を介して結合したものである。扁平多葉形において、円形及び/又は楕円形は、結合箇所において、部分的に重なっている。また、円形又は楕円形の形状は、必ずしも連続した弧を描く必要はなく、鋭角な角でなければ一部が変形した略円形又は略楕円形も含む。また、添加剤などを含むことにより繊維断面及び芯部外周に生じる2μm以下の凹凸は考慮しなくてもよい。
繊維断面長軸の長さ/繊維断面第1短軸の長さ=1.1以上2.0以下 (1)
芯部断面長軸の長さ/芯部断面第1短軸の長さ=1.3以上2.0以下 (2)
本発明の1以上の実施形態の人工毛髪用芯鞘複合繊維において、芯部はポリエステル系樹脂を主成分とするポリエステル系樹脂組成物で構成され、鞘部はポリアミド系樹脂を主成分とするポリアミド系樹脂組成物で構成される。
本発明の1以上の実施形態において、人工毛髪用芯鞘複合繊維は、芯部及び鞘部を構成するそれぞれの樹脂組成物を種々の一般的な混練機を用いて溶融混練した後、芯鞘型複合紡糸ノズルを用いて、溶融紡糸することにより作製することができる。例えば、上述したポリエステル樹脂、臭素化エポキシ系難燃剤などの各成分をドライブレンドしたポリエステル系樹脂組成物を、種々の一般的な混練機を用いて溶融混練して芯部樹脂組成物とする一方、上述したポリアミド系樹脂、顔料、臭素化エポキシ系難燃剤などの各成分をドライブレンドしたポリアミド系樹脂組成物を、種々の一般的な混練機を用いて溶融混練して鞘部樹脂組成物とし、芯鞘型複合紡糸ノズルを用いて溶融紡糸することにより作製することができる。前記混練機としては、例えば、一軸押出機、二軸押出機、ロール、バンバリーミキサー、ニーダーなどが挙げられる。中でも、二軸押出機が、混練度の調整、操作の簡便性の点から好ましい。
該ギアクリンプによる加工では、一般的に、繊維を軟化温度以上に加熱した状態で2つの噛み合った歯車の間を通過させ、この歯車の形状を転写させることで繊維屈曲を発現させる。また、必要に応じて、繊維加工段階において、異なる温度で前記人工毛髪用芯鞘複合繊維を熱処理することで、異なる形状のカールを発現することができる。
本発明の1以上の実施形態において、人工毛髪用芯鞘複合繊維は、単独で人工毛髪として用いてもよく、他の人工毛髪用繊維や人毛及び獣毛などの天然繊維と組み合わせても用いてもよい。他の人工毛髪用繊維としては、例えばアクリル系繊維などが挙げられる。
オートバイブロ式繊度測定器「DENIER COMPUTER タイプDC-11」(サーチ社製)を使用して測定し、30個のサンプルの測定値の平均値を算出して単繊維繊度とした。
室温(23℃)にて、繊維を長さ150mmの長さに切断し、切断した繊維0.7gを束ね、ゴム製チューブを通過させた後に80℃の熱をかけてチューブを収縮させて繊維束がズレないように固定した。その後、チューブの部分をカッターで輪切りにし、長さ5mmの断面観察用繊維束を作製した。この繊維束を、レーザー顕微鏡(株式会社キーエンス製、「VK-9500」)にて400倍の倍率で撮影し、繊維断面写真を得た。この繊維断面写真からランダムに30本の繊維断面を選定し、画像解析装置(三谷商事株式会社製、画像解析ソフト「Win ROOF」)を用いて、繊維断面の長軸の長さ、繊維断面の第1短軸の長さ、繊維断面の長軸に対する中空部の第1の辺の角度、繊維断面の長軸に対する中空部の第2の角度、中空部の第1の辺の長さ、中空部の第2の辺の長さ、中空部の面積、芯部の面積、鞘部の面積、繊維断面の面積(中空部、芯部及び鞘部の合計面積)を計測した。なお、ここで、繊維断面の長軸と第1短軸の比(L/S1)、芯部断面の長軸と第1短軸の比(Lc/Sc1)、繊維断面の長軸に対する中空部の第1辺の角度、繊維断面の長軸に対する中空部の第2辺の角度、中空部の第1辺の長さ、中空部の第2辺の長さなどの繊維断面における各サイズの値は、任意に選択した30本の繊維断面の測定値の平均値である。
専門美容師による官能評価を行い、以下の4段階の基準で評価した。
A:人毛と同等の非常に良好な触感
B:人毛に比べやや劣るが良好な触感
C:人毛に比べ劣るが良好な触感
D:人毛に比べ大きく劣る悪い触感
毛髪用試料に対して、以下の手順でダメージを付与し、ダメージ前後の嵩高値から算出される嵩高変化率で耐久性を評価した。
(1)繊維を束ねて繊維束の一方の端部をゴム紐で止めて根元とし、他方の端部において繊維が部分的にずれるようにしてレイヤー部を形成した毛髪用試料(全長16インチ、15g)のレイヤー部(4インチ)の初期嵩高値を測定した。
(2)毛髪用試料に対してブラシにて逆毛を立てて毛髪を絡ませた。
(3)手で根元を10回、レイヤー部を10回、全体を10回揉み込み、毛髪をさらに絡ませた。
(4)ブラシで絡まった毛髪を梳きほぐした。
(5)(2)~(4)の作業を10回繰り返し、ダメージを促進させた。
(6)ダメージ促進後の毛髪用試料のレイヤー部の嵩高値を測定し、ダメージ後の嵩高値とした。
(7)下記数式(3)に基づいて、ダメージ前後の嵩高変化率を算出し、以下の4段階の基準で評価した。
ダメージ後の嵩高変化率(%)=ダメージ後の嵩高値/初期嵩高値×100 (3)
A:嵩高変化率が200%未満
B:嵩高変化率が200%以上250%未満
C:嵩高変化率が250%以上300%未満
D:嵩高変化率が300%以上
(嵩高値の測定)
毛髪用試料の嵩高値は、図3A~Cに示した嵩高測定機を用いて測定した。図3A~Cに示されているように、嵩高測定機100は、支持台101と、支持台101の上に配置され、毛髪を挟む挟み具102、103を備えている。挟み具102には、目盛104が透明テープ(図示無し)で貼り付けられている。支持台101、挟み具102及び103は、いずれもアクリル系樹脂で構成されている。図3Cに示されているように、挟み具102と挟み具103の間に毛髪用試料40を、挟み具102の長さ方向の中心と毛髪用試料40のレイヤー部の中心が一致するように配置して嵩高値を測定した。
室温(23℃)にて、2.8gのフィラメントを25cmの蓑毛にし、φ32mmのパイプに捲きつけ、120℃で60分間カールセットし、室温(23℃)で60分間エイジングした後に、カールしたフィラメントの一端を固定し釣り下げ、カールセット後のフィラメント長を測定する。該フィラメント長をカールセット性の指標とし、以下の4段階の基準で評価した。
A:カールセット後のフィラメント長が14cm未満
B:カールセット後のフィラメント長が14cm以上15cm未満
C:カールセット後のフィラメント長が15cm以上17cm未満
D:カールセット後のフィラメント長が17cm以上
難燃性の評価指標として、JIS L 1091 E法(酸素指数法試験)に準じて限界酸素指数(LOI値)を測定した。具体的には、フィラメント(長さ16cm、重さ0.25g)の両端を軽く両面テープでまとめ、懸撚器で挟み撚りをかけた。十分に撚りがかかったら、真中で二つに折り撚り合わせた。撚り合わせたフィラメントの両端をセロファン(登録商標)テープで止め、全長7cmになるようにした。得られた試料は、105℃にて60分間前乾燥を行ない、さらにデシケーターで30分以上乾燥させた。乾燥した試料を所定の酸素濃度になるように調整し、40秒後炎長を8~12mmに絞ったガス点火器で、上部より着火し、着火後点火器を離した。5cm以上燃えるか、3分以上燃え続けた酸素濃度を調べ、同じ条件で試験を3回繰り返し、LOI値とし、以下の4段階の基準で評価した。
A:LOI値が27以上
B:LOI値が26以上27未満
C:LOI値が25以上26未満
D:LOI値が25未満
ポリエチレンテレフタレートペレット(East West Chemical Private Limited製、EastPET 商品名「A-12」、PETとも記す)100重量部に対し、臭素化エポキシ系難燃剤(阪本薬品工業製、商品名「SR-T2MP」)30重量部、アンチモン酸ナトリウム(日本精鉱製、商品名「SA-A」)3重量部、黒色顔料マスターバッチ(大日精化工業製、商品名「PESM22367BLACK(20)」、顔料:20重量%、ベース樹脂:ポリエステル系樹脂)3.0重量部、黄色顔料マスターバッチ(大日精化工業製、商品名「PESM1001YELLOW(20)」、顔料:20重量%、ベース樹脂:ポリエステル系樹脂)0.6重量部、赤色顔料マスターバッチ(大日精化工業製、商品名「PESM3005RED(20)」、顔料:20重量%、ベース樹脂:ポリエステル系樹脂)0.2重量部を添加し、ドライブレンド後に二軸押出機に供給し、バレル設定温度280℃にて溶融混練を行い、ペレット化してポリエステル系樹脂組成物を得た。
下記表1に記載のノズル形状の芯鞘型複合紡糸ノズル(孔)を用いた以外は実施例1と同様にして芯鞘複合繊維を得た。
鞘部に用いる樹脂をナイロン66(東レ社製、商品名「アミランCM3001」、PA66とも記す)とし、ペレット化時のバレル設定温度を280℃、ノズル設定温度を280℃とし、芯鞘比率を7:3とした以外は、実施例1と同様にして芯鞘複合繊維を得た。
芯部に用いる樹脂をポリブチレンテレフタレート(三菱ケミカル社製、商品名「ノバデュラン5020」、PBTと称す場合がある)とし、ペレット化時のバレル設定温度を260℃、ノズル設定温度を260℃とし、芯鞘比率を3:7とした以外は、実施例1と同様にして芯鞘複合繊維を得た。
芯鞘比率を9:1とした以外は、実施例1と同様にして芯鞘複合繊維を得た。
芯鞘比率を1:9とした以外は、実施例1と同様にして芯鞘複合繊維を得た。
下記表1に記載のノズル形状の芯鞘型複合紡糸ノズル(孔)を用いた以外は実施例1と同様にして芯鞘複合繊維を得た。
下記表1に記載のノズル形状の芯鞘型複合紡糸ノズル(孔)を用いた以外は実施例1と同様にして芯鞘複合繊維を得た。
ポリエチレンテレフタレートペレット(East West Chemical Private Limited製、EastPET 商品名「A-12」)100重量部に対し、黒色顔料マスターバッチ(大日精化工業製、商品名「PESM22367BLACK(20)」、顔料:20重量%、ベース樹脂:ポリエステル系樹脂)3.0重量部、黄色顔料マスターバッチ(大日精化工業製、商品名「PESM1001YELLOW(20)」、顔料:20重量%、ベース樹脂:ポリエステル系樹脂)0.6重量部、赤色顔料マスターバッチ(大日精化工業製、商品名「PESM3005RED(20)」、顔料:20重量%、ベース樹脂:ポリエステル系樹脂)0.2重量部を添加し、ドライブレンド後に二軸押出機に供給し、バレル設定温度280℃にて溶融混練を行い、ペレット化してポリエステル系樹脂組成物を得た。
[1] 芯部及び鞘部を含む人工毛髪用芯鞘複合繊維であって、
前記芯部はポリエステル系樹脂を含むポリエステル系樹脂組成物で構成され、前記鞘部はポリアミド系樹脂を含むポリアミド系樹脂組成物で構成されており、
前記ポリエステル系樹脂組成物及びポリアミド系樹脂組成物は臭素系難燃剤を含み、
前記人工毛髪用芯鞘複合繊維において、芯鞘比率は面積比で芯部:鞘部=2:8~8:2であり、
前記繊維断面の断面形状は扁平多葉形であり、繊維断面は中空部を有し、前記繊維断面の全体面積に対する前記中空部の面積の割合は5%以上30%以下であり、前記中空部は多辺形であることを特徴とする人工毛髪用芯鞘複合繊維。
[2] 前記人工毛髪用芯鞘複合繊維は、扁平二葉形の断面形状を有する、[1]に記載の人工毛髪用芯鞘複合繊維。
[3] 前記芯部は、扁平二葉形の断面形状を有する、[1]又は[2]に記載の人工毛髪用芯鞘複合繊維。
[4] 前記人工毛髪用芯鞘複合繊維において、線対称軸及び線対称軸に平行するように繊維断面の外周の任意の二点を結んだ直線のうち、最大長となる直線である繊維断面長軸の長さと、前記繊維断面長軸に対して垂直になるように繊維断面の外周の任意の二つの点を結んだ際、最大長となる二つの点を結ぶ直線である繊維断面第1短軸の長さが下記式(1)を満たす、[1]~[3]のいずれかに記載の人工毛髪用芯鞘複合繊維。
繊維断面長軸の長さ/繊維断面第1短軸の長さ=1.1以上2.0以下 (1)
[5] 前記人工毛髪用芯鞘複合繊維において、線対称軸及び線対称軸に平行するように芯部断面の外周の任意の二点を結んだ直線のうち、最大長となる直線である芯部断面長軸の長さと、前記芯部断面長軸に対して垂直になるように芯部断面の外周の任意の二つの点を結んだ際、最大長となる二つの点を結ぶ直線である芯部断面第1短軸の長さが下記式(2)を満たす、[1]~[4]のいずれかに記載の人工毛髪用芯鞘複合繊維。
芯部断面長軸の長さ/芯部断面第1短軸の長さ=1.3以上2.0以下 (2)
[6] 前記中空部は、繊維断面の長軸に対する角度が80度以上100度以下の第1の辺及び繊維断面の長軸に対する角度が80度以上100度以下の第2の辺を有する多辺形である、[1]~[5]のいずれかに記載の人工毛髪用芯鞘複合繊維。
[7] 前記第1の辺と前記第2の辺の間の角度が0度以上40度以下の範囲である、[6]に記載の人工毛髪用芯鞘複合繊維。
[8] 前記中空部は、四角形、五角形、六角形、七角形及び八角形からなる群から選ばれる一つ以上の多辺形である、[1]~[7]のいずれかに記載の人工毛髪用芯鞘複合繊維。
[9] 前記ポリエステル系樹脂組成物は、ポリアルキレンテレフタレート及びポリアルキレンテレフタレートを主体とした共重合ポリエステルからなる群から選ばれる1種以上のポリエステル系樹脂を含む、[1]~[8]のいずれかに記載の人工毛髪用芯鞘複合繊維。
[10] 前記ポリアミド系樹脂組成物は、ナイロン6及びナイロン66からなる群から選ばれる少なくとも1種を主体とするポリアミド系樹脂を含む、[1]~[9]のいずれかに記載の人工毛髪用芯鞘複合繊維。
[11] [1]~[10]のいずれかに記載の人工毛髪用芯鞘複合繊維を含むことを特徴とする頭飾製品。
[12] 前記頭飾製品が、ヘアーウィッグ、かつら、ウィービング、ヘアーエクステンション、ブレードヘアー、ヘアーアクセサリー及びドールヘアーからなる群から選ばれる一つである、[11]に記載の頭飾製品。
[13] [1]~[10]のいずれかに記載の人工毛髪用芯鞘複合繊維の製造方法であって、
ポリエステル系樹脂組成物及びポリアミド系樹脂組成物を芯鞘複合紡糸用ノズルを用いて溶融紡糸する工程を含み、繊維断面に多辺形の中空部を形成し、前記繊維断面の全体面積に対する前記中空部の面積の割合を5%以上30%以下にすることを特徴とする人工毛髪用芯鞘複合繊維の製造方法。
10 鞘部
11 繊維断面長軸
12 繊維断面第1短軸
20 芯部
21 芯部断面長軸
22 芯部断面第1短軸
30 中空部
31a 中空部の第1の辺
31b 中空部の第2の辺
40 毛髪用試料
100 嵩高測定器
101 支持台
102、103 挟み具
104 目盛
Claims (13)
- 芯部及び鞘部を含む人工毛髪用芯鞘複合繊維であって、
前記芯部はポリエステル系樹脂を含むポリエステル系樹脂組成物で構成され、前記鞘部はポリアミド系樹脂を含むポリアミド系樹脂組成物で構成されており、
前記ポリエステル系樹脂組成物及びポリアミド系樹脂組成物は臭素系難燃剤を含み、
前記人工毛髪用芯鞘複合繊維において、芯鞘比率は面積比で芯部:鞘部=2:8~8:2であり、
前記繊維断面の断面形状は扁平多葉形であり、繊維断面は中空部を有し、前記繊維断面の全体面積に対する前記中空部の面積の割合は5%以上30%以下であり、前記中空部は多辺形であることを特徴とする人工毛髪用芯鞘複合繊維。 - 前記人工毛髪用芯鞘複合繊維は、扁平二葉形の断面形状を有する、請求項1に記載の人工毛髪用芯鞘複合繊維。
- 前記芯部は、扁平二葉形の断面形状を有する、請求項1又は2に記載の人工毛髪用芯鞘複合繊維。
- 前記人工毛髪用芯鞘複合繊維において、線対称軸及び線対称軸に平行するように繊維断面の外周の任意の二点を結んだ直線のうち、最大長となる直線である繊維断面長軸の長さと、前記繊維断面長軸に対して垂直になるように繊維断面の外周の任意の二つの点を結んだ際、最大長となる二つの点を結ぶ直線である繊維断面第1短軸の長さが下記式(1)を満たす、請求項1~3のいずれかに記載の人工毛髪用芯鞘複合繊維。
繊維断面長軸の長さ/繊維断面第1短軸の長さ=1.1以上2.0以下 (1) - 前記人工毛髪用芯鞘複合繊維において、線対称軸及び線対称軸に平行するように芯部断面の外周の任意の二点を結んだ直線のうち、最大長となる直線である芯部断面長軸の長さと、前記芯部断面長軸に対して垂直になるように芯部断面の外周の任意の二つの点を結んだ際、最大長となる二つの点を結ぶ直線である芯部断面第1短軸の長さが下記式(2)を満たす、請求項1~4のいずれかに記載の人工毛髪用芯鞘複合繊維。
芯部断面長軸の長さ/芯部断面第1短軸の長さ=1.3以上2.0以下 (2) - 前記中空部は、繊維断面の長軸に対する角度が80度以上100度以下の第1の辺及び繊維断面の長軸に対する角度が80度以上100度以下の第2の辺を有する多辺形である、請求項1~5のいずれかに記載の人工毛髪用芯鞘複合繊維。
- 前記第1の辺と前記第2の辺の間の角度が0度以上40度以下の範囲である、請求項6に記載の人工毛髪用芯鞘複合繊維。
- 前記中空部は、四角形、五角形、六角形、七角形及び八角形からなる群から選ばれる一つ以上の多辺形である、請求項1~7のいずれかに記載の人工毛髪用芯鞘複合繊維。
- 前記ポリエステル系樹脂組成物は、ポリアルキレンテレフタレート及びポリアルキレンテレフタレートを主体とした共重合ポリエステルからなる群から選ばれる1種以上のポリエステル系樹脂を含む、請求項1~8のいずれかに記載の人工毛髪用芯鞘複合繊維。
- 前記ポリアミド系樹脂組成物は、ナイロン6及びナイロン66からなる群から選ばれる少なくとも1種を主体とするポリアミド系樹脂を含む、請求項1~9のいずれかに記載の人工毛髪用芯鞘複合繊維。
- 請求項1~10のいずれかに記載の人工毛髪用芯鞘複合繊維を含むことを特徴とする頭飾製品。
- 前記頭飾製品が、ヘアーウィッグ、かつら、ウィービング、ヘアーエクステンション、ブレードヘアー、ヘアーアクセサリー及びドールヘアーからなる群から選ばれる一つである、請求項11に記載の頭飾製品。
- 請求項1~10のいずれかに記載の人工毛髪用芯鞘複合繊維の製造方法であって、
ポリエステル系樹脂組成物及びポリアミド系樹脂組成物を芯鞘複合紡糸用ノズルを用いて溶融紡糸する工程を含み、繊維断面に多辺形の中空部を形成し、前記繊維断面の全体面積に対する前記中空部の面積の割合を5%以上30%以下にすることを特徴とする人工毛髪用芯鞘複合繊維の製造方法。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS6312716A (ja) * | 1986-06-30 | 1988-01-20 | Kuraray Co Ltd | 人工毛髪及び製造方法 |
WO2014196642A1 (ja) * | 2013-06-06 | 2014-12-11 | 株式会社カネカ | 人工毛髪用繊維及びそれを含む頭飾製品 |
WO2018179803A1 (ja) * | 2017-03-30 | 2018-10-04 | 株式会社カネカ | 人工毛髪用芯鞘複合繊維及びそれを含む頭飾製品 |
WO2020166262A1 (ja) * | 2019-02-15 | 2020-08-20 | 株式会社カネカ | 人工毛髪用芯鞘複合繊維、それを含む頭飾製品及びその製造方法 |
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JPS6312716A (ja) * | 1986-06-30 | 1988-01-20 | Kuraray Co Ltd | 人工毛髪及び製造方法 |
WO2014196642A1 (ja) * | 2013-06-06 | 2014-12-11 | 株式会社カネカ | 人工毛髪用繊維及びそれを含む頭飾製品 |
WO2018179803A1 (ja) * | 2017-03-30 | 2018-10-04 | 株式会社カネカ | 人工毛髪用芯鞘複合繊維及びそれを含む頭飾製品 |
WO2020166262A1 (ja) * | 2019-02-15 | 2020-08-20 | 株式会社カネカ | 人工毛髪用芯鞘複合繊維、それを含む頭飾製品及びその製造方法 |
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