WO2022172766A1 - 人工毛髪用ポリアミド系中空繊維、それを含む頭飾製品及び人工毛髪用ポリアミド系中空繊維の製造方法 - Google Patents

人工毛髪用ポリアミド系中空繊維、それを含む頭飾製品及び人工毛髪用ポリアミド系中空繊維の製造方法 Download PDF

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Publication number
WO2022172766A1
WO2022172766A1 PCT/JP2022/003149 JP2022003149W WO2022172766A1 WO 2022172766 A1 WO2022172766 A1 WO 2022172766A1 JP 2022003149 W JP2022003149 W JP 2022003149W WO 2022172766 A1 WO2022172766 A1 WO 2022172766A1
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WIPO (PCT)
Prior art keywords
fiber
polyamide
artificial hair
resin
hair
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Ceased
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PCT/JP2022/003149
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English (en)
French (fr)
Japanese (ja)
Inventor
仁志 島本
賢 穴原
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Kaneka Corp
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Kaneka Corp
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Priority to JP2022581311A priority Critical patent/JPWO2022172766A1/ja
Publication of WO2022172766A1 publication Critical patent/WO2022172766A1/ja
Priority to US18/449,690 priority patent/US20230380532A1/en
Anticipated expiration legal-status Critical
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    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
    • A41G3/00—Wigs
    • A41G3/0083—Filaments for making wigs
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
    • A41G3/00—Wigs
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
    • A41G5/00—Hair pieces, inserts, rolls, pads, or the like; Toupées
    • A41G5/004—Hair pieces
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • 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
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/14—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics using grooved rollers or gear-wheel-type members
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
    • D02J13/005—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass by contact with at least one rotating roll
    • 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
    • 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
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/062—Load-responsive characteristics stiff, shape retention
    • 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 polyamide hollow fiber for artificial hair that can be used as a substitute for human hair, a head ornament product containing the same, and a method for producing a polyamide hollow fiber for artificial hair.
  • Synthetic fibers for artificial hair include acrylic fibers, vinyl chloride fibers, vinylidene chloride fibers, polyester fibers, polyamide fibers, polyolefin fibers, and the like. Synthetic hair is required to have properties such as feel and appearance similar to human hair, combing properties, curl setting properties, and flame resistance. Light weight is also required.
  • a lightweight fiber for artificial hair for example, a hollow fiber for artificial hair having a flat multilobal cross-sectional shape with a void in the central portion of the fiber cross section is described (Patent Document 1).
  • Patent Document 1 discloses polyester fibers and polyamide fibers as hollow fibers for artificial hair.
  • polyester fibers although they are lightweight and have an appearance similar to human hair, the hollow fibers make it difficult to obtain a soft texture similar to human hair. There was still a problem in achieving both a comfortable feel and light weight.
  • polyamide-based fibers lightness can be obtained by making the fibers hollow, but artificial hair fibers having a sufficient lightness such that the hollowness exceeds 15%, for example, have not yet been achieved.
  • there was room for improvement for these reasons, there has been a continuing strong demand for fibers for artificial hair that are both soft to the touch and lightweight, comparable to human hair.
  • the present invention is a polyamide hollow fiber for artificial hair, the fiber is composed of a resin composition containing a polyamide resin as a main component resin, has a hollowness of 15 to 40%, and has a fiber specific gravity of 0.80. 1.10 and a bending stiffness of 1.5 ⁇ 10 ⁇ 3 to 5.5 ⁇ 10 ⁇ 3 gf ⁇ cm 2 /yarn.
  • an artificial hair fiber that has a soft feel and appearance similar to human hair and is light in weight, a head ornament product containing the same, and a method for producing the artificial hair fiber. .
  • FIG. 1 is a laser micrograph of a fiber cross section of the fiber of Example 1.
  • the cross-sectional profile of the polyamide-based hollow fiber for artificial hair may be circular, or may be an irregular shape such as oval, flat, or multi-lobed flat.
  • a flat multi-lobed cross-sectional shape is preferable from the viewpoint of a soft touch and appearance similar to human hair, and combability, and two or more flat multi-lobed shapes are selected from the group consisting of circular and elliptical shapes. The leaf shape of the is combined through the recess.
  • the circular or elliptical shape does not necessarily have to draw a continuous arc, and includes partially deformed substantially circular or substantially elliptical shapes as long as the corners are not sharp. Further, irregularities of 2 ⁇ m or less that occur on the cross section of the fiber and on the outer periphery of the core due to inclusion of an additive or the like need not be taken into consideration. Among them, a flat bilobed shape in which two circular or two elliptical shapes are connected through a recess is particularly preferable.
  • the fiber has a void (referred to as a hollow portion), and in the fiber, the center position of the hollow portion coincides with the center position of the cross section of the fiber. It may be a structure, or an eccentric structure in which the center position of the hollow portion does not match the center position of the fiber cross section and may be eccentric, but it is preferable that the center position of the hollow portion matches the center position of the fiber cross section. Also, the cross-sectional shape of the hollow portion and the outer shape of the fiber may be the same or different. In the cross section of the fiber, the cross-linking portion may be present in the hollow portion, or the cross-linking portion may be absent.
  • the shape of the hollow portion is not particularly limited. is preferably a polygon with sides of . Furthermore, it is preferable that the first side and the second side are substantially parallel polygons, and the specific shape is not particularly limited. For example, quadrangle, pentagon, hexagon, heptagon, octagon, etc. are preferable from the viewpoint of being able to suppress surface reflection.
  • the hollow part has such a shape, when pressure is applied to the fiber, the pressure is applied not only to a specific local area (point) but also to the line (first side and second side). is given, deformation and collapse of the fiber can be suppressed.
  • the first side and the second side of the hollow portion preferably have a length of 1 ⁇ m or more and 150 ⁇ m or less, more preferably 3 ⁇ m or more and 140 ⁇ m or less.
  • the "length of the first side of the hollow portion” refers to the average value of cross sections of 30 arbitrarily selected fibers. In the arbitrarily selected 30 fiber cross sections, both the maximum and minimum values of the length of the first side of the hollow portion are preferably within the range described above.
  • the “length of the second side of the hollow portion” refers to the average value of cross sections of 30 arbitrarily selected fibers.
  • both the maximum and minimum values of the length of the second side of the hollow portion are preferably within the range described above.
  • the length of the first side and the second side is 1 ⁇ m or more, the pressure is not concentrated locally, the feel is good, the fiber cross section is less likely to break, and the fiber cross section is less likely to collapse.
  • entanglement of fibers is less likely to occur, and combability is improved.
  • the length of the first side and the second side is 150 ⁇ m or less, the outer periphery of the fiber and the outer periphery of the hollow portion are separated from each other, so that the thickness is not too thin, the lightness is good, and the fiber cross section is broken. It becomes difficult to bend, and the fiber cross section becomes difficult to collapse.
  • entanglement of fibers is less likely to occur, and combability is improved.
  • the hollowness is 15-40%, preferably 15-35%, more preferably 18-35%, still more preferably 18-30%.
  • the "hollow ratio" in the present invention means the average ratio of the area of the hollow part to the total area of the cross section in a cross section of 30 arbitrarily selected fibers cut vertically.
  • the total area of the cross section refers to the area of the portion covered with the outer periphery of the fiber, and includes the area of the hollow portion.
  • both the maximum value and the minimum value of the hollowness ratio of the 30 arbitrarily selected fiber cross sections are included in the range described above.
  • the hollow ratio can be appropriately adjusted by the nozzle shape, nozzle temperature, spinning speed, discharge amount during spinning, quench conditions, draft ratio, draw ratio, melt viscosity of the resin composition, and the like.
  • the fiber specific gravity is one index for measuring lightness, and the smaller the value, the more excellent the lightness.
  • the fiber specific gravity is calculated based on the Archimedes method, and the value of the fiber specific gravity is 0.80 to 1.10, preferably 0.80 to 1.05, more preferably 0.85 to 1.05. .
  • the specific gravity of the fiber is within such a range, the fiber has a sufficiently light weight, and the fiber cross section rarely has a portion where the thickness is extremely thin, so that the spinning property is improved.
  • the fiber specific gravity can be adjusted mainly by changing the hollowness.
  • the bending stiffness is one index for measuring tactile sensation, and is preferably 1.5 ⁇ 10 ⁇ 3 to 5.5 ⁇ 10 ⁇ 3 gf ⁇ cm 2 /yarn, It is more preferably 2.0 ⁇ 10 ⁇ 3 to 5.5 ⁇ 10 ⁇ 3 gf ⁇ cm 2 /yarn, and 2.0 ⁇ 10 ⁇ 3 to 5.0 ⁇ 10 ⁇ 3 gf ⁇ cm 2 /yarn. It is even more preferable to have Within such a range, the soft touch feeling is excellent, and the touch feeling similar to that of human hair can be obtained.
  • the flexural rigidity can be appropriately adjusted by the cross-sectional shape of the outer peripheral portion of the fiber, the cross-sectional shape of the hollow portion, the hollow ratio, the single fiber fineness, the compounding conditions of the resin composition, the crystallinity of the resin, and the like.
  • the single fiber fineness is preferably 10 dtex or more and 150 dtex or less, more preferably 15 dtex or more and 100 dtex or less, and 20 dtex or more and 80 dtex, from the viewpoint of being suitably used as a substitute for human hair. More preferably: Within such a range, the tactile sensation and appearance similar to those of human hair can be obtained, and the spinnability is also improved.
  • the resin composition that constitutes the fibers for artificial hair is a resin composition containing a polyamide-based resin as a main component resin, from the viewpoint of providing a soft feel similar to that of human hair.
  • the "main component resin” means a resin contained in the resin composition with the highest resin content.
  • the resin composition may contain other resins in addition to the polyamide-based resin that is the main component resin. Examples of other resins include polyester-based resins, modacrylic-based resins, polycarbonate-based resins, polyolefin-based resins, polystyrene-based resins, and polyphenylene sulfide-based resins.
  • the total amount of the resin in the resin composition is 100% by weight, it preferably contains more than 60% by weight of the polyamide resin that is the main component resin, more preferably 70% by weight or more, and 75% by weight or more. is more preferable, and it is particularly preferable to contain 80% by weight or more.
  • the melt viscosity of the resin composition is not particularly limited, but is preferably 100 to 700 Pa ⁇ s, more preferably 200 to 600 Pa ⁇ s, still more preferably 300 to 600 Pa ⁇ s, and particularly preferably 350 to 550 Pa ⁇ s. If the melt viscosity is within such a range, a hollow shape equivalent to that of the spinning nozzle can be obtained in the cross section of the fiber, and the hollow ratio is kept high, so that the weight is improved. In addition, the spinning property is stabilized, and yarn breakage and fineness unevenness can be reduced.
  • the melt viscosity shown here refers to the melt viscosity measured at a temperature of 280° C. and a shear rate of 50 mm/min using a resin composition after dehumidification and drying as a sample.
  • the resin composition that constitutes the artificial hair fibers contains a polyamide-based resin as a main component resin.
  • Polyamide-based resins are selected from the group consisting of lactams, aminocarboxylic acids, mixtures of dicarboxylic acids and diamines, mixtures of dicarboxylic acid derivatives and diamines, and salts of dicarboxylic acids and diamines. Polyamide obtained by polymerizing one or more. system resin.
  • lactams include, but are not limited to, 2-azetidinone, 2-pyrrolidinone, ⁇ -valerolactam, ⁇ -caprolactam, enantholactam, capryllactam, undecalactam, and laurolactam. .
  • ⁇ -caprolactam, undecalactam and laurolactam are preferred, and ⁇ -caprolactam is particularly preferred.
  • These lactams may be used singly or as a mixture of two or more.
  • aminocarboxylic acids are not particularly limited, but include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12 -aminododecanoic acid and the like. Among these, 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and 6-aminocaproic acid is particularly preferred. These aminocarboxylic acids may be used singly or as a mixture of two or more.
  • dicarboxylic acids used in mixtures of dicarboxylic acids and diamines, mixtures of dicarboxylic acid derivatives and diamines, or salts of dicarboxylic acids and diamines are not particularly limited, but include oxalic acid, malonic acid, succinic acid, glutaric acid, acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and other aliphatic dicarboxylic acids, cyclohexanedicarboxylic acid, etc.
  • alicyclic dicarboxylic acids phthalic acid, isophthalic acid, terephthalic acid, and aromatic dicarboxylic acids such as naphthalene dicarboxylic acid.
  • adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid and isophthalic acid are preferred, and adipic acid, terephthalic acid and isophthalic acid are particularly preferred.
  • These dicarboxylic acids may be used singly or as a mixture of two or more.
  • diamine used in a mixture of a dicarboxylic acid and a diamine a mixture of a dicarboxylic acid derivative and a diamine, or a salt of a dicarboxylic acid and a diamine are not particularly limited.
  • nylon resins examples include nylon 6 (hereinafter also referred to as PA6), nylon 66 (hereinafter also referred to as PA66), nylon 11, nylon 12, nylon 6-10, nylon 6- 12, nylon 4/10, nylon 46, nylon 6T, nylon 9T, nylon 10T, nylon MXD6, and copolymers of these nylon resins.
  • polyamide mainly composed of at least one selected from the group consisting of nylon 6, nylon 66, nylon 6.10, nylon 6.12, nylon 4.10, and nylon MXD6 system resin is more preferred.
  • a polyamide-based resin mainly composed of at least one selected from the group consisting of nylon 6 and nylon 66 is more preferable.
  • Polyamide resin mainly composed of at least one selected from the group consisting of nylon 6 and nylon 66 means a polyamide resin containing 80 mol% or more of nylon 6 and/or nylon 66.
  • the viscosity of the polyamide resin is not particularly limited, but the sulfuric acid relative viscosity is preferably 2.0 or more and 4.0 or less, more preferably 2.5 or more and 3.8 or less, and 2.6 or more and 3.6 or less. is more preferred. Within such a range, the mechanical strength of the obtained fiber does not decrease, and the hollowness can be maintained at a high level. In addition, the drip resistance during combustion is improved, melt spinning is facilitated, productivity is improved, and the fineness tends to be uniform.
  • the sulfuric acid relative viscosity refers to the relative viscosity measured at 25° C. for a solution of 0.25 g of polyamide resin dissolved in 25 ml of 98% sulfuric acid.
  • Polyamide-based resins 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 be used during the polymerization, but stirring is preferred in order to obtain a homogeneous product.
  • the polymerization temperature can be arbitrarily set according to the degree of polymerization of the target polymer, the reaction yield and the reaction time, but a lower temperature is preferable in consideration of the quality of the finally obtained polyamide resin.
  • the reaction rate can also be set arbitrarily.
  • the pressure is not limited, it is preferable to reduce the pressure in the system in order to efficiently extract the volatile components out of the system.
  • the polyamide resin may be terminally blocked with an terminal blocking agent such as a carboxylic acid compound and an amine compound.
  • an terminal blocking agent such as a carboxylic acid compound and an amine compound.
  • a monocarboxylic acid or monoamine is added to block the ends, the terminal amino group or terminal carboxyl group concentration of the resulting nylon resin is reduced compared to 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 concentrations of the terminal amino group and the terminal carboxyl group changes.
  • terminal group concentration of polyamide-based resins there are no particular restrictions on the terminal group concentration of polyamide-based resins, but when it is necessary to improve dyeability for fiber applications or when designing materials suitable for alloying for resin applications, a higher terminal amino group concentration is recommended. preferable. On the other hand, 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 adjusted. Lower is preferred.
  • the terminal group concentration may be adjusted depending on the application, 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 1.0 ⁇ 10 ⁇ 5 to 15.0 ⁇ 10 ⁇ 5 eq/g. 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 terminal blocker may be added at the same time as raw materials such as caprolactam at the beginning of the polymerization, added during the polymerization, or added when the molten nylon resin is passed through a vertical stirring thin film evaporator. etc. are adopted.
  • the terminal blocking agent may be added as it is, or may be added after being dissolved in a small amount of solvent.
  • a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, or the like can be suitably used. It is preferred to use a flame retardant. Moreover, a nitrogen-based flame retardant can also be used together.
  • Brominated flame retardants include, but are not limited to, brominated epoxy flame retardants; Bromine-containing phosphate esters such as ethylenebis(tetrabromophthalimide), ethylenebis(pentabromophenyl), octabromotrimethylphenylindane, tris(tribromoneopentyl)phosphate; brominated polystyrenes; brominated polybenzyl acrylates brominated phenoxy resin; brominated polycarbonate oligomers; tetrabromobisphenol A derivatives such as (hydroxyethyl ether); bromine-containing triazine compounds such as tris(tribromophenoxy)triazine; bromine-containing isocyanuric acid compounds such as tris(2,3-dibromopropyl)isocyanurate; be done. Among them, it is preferable to use a brominated epoxy flame retardant from the viewpoint of heat resistance and flame retardancy.
  • Bromine-containing phosphate esters
  • a brominated epoxy flame retardant having an epoxy group or tribromophenol at the molecular end can be used as a raw material for the brominated epoxy flame retardant.
  • the total number of structural units represented by the following chemical formula (1) and structural units in which at least a part of the following chemical formula (1) is modified is 100 mol%, 80 mol% or more of the structure represented by the chemical formula (1) Units are preferred.
  • the structure of the brominated epoxy flame retardant may change at the molecular terminal 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, etc., and the molecular end is bound to the polyester component with an ester group.
  • part of the structure other than the molecular terminal of the brominated epoxy flame retardant may change.
  • the secondary hydroxyl group and the epoxy group of the brominated epoxy flame retardant may be bonded to form a branched structure. ) may be partially eliminated or added.
  • a polymer-type brominated epoxy flame retardant represented by the following general formula (2) is preferably used.
  • m is 1-1000.
  • examples of the polymer-type brominated epoxy flame retardant represented by the following general formula (2) include a brominated epoxy flame retardant manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. (trade name “SR-T2MP”). may be used.
  • Examples of phosphorus-based flame retardants include red phosphorus, phosphoric acid ester compounds, condensed phosphoric acid ester compounds, phosphoric acid ester amide compounds, organic cyclic phosphorus compounds, metal phosphinates, and polyphosphates. .
  • the phosphorus-based flame retardant is preferably one or more selected from the group consisting of condensed phosphoric acid ester compounds and metal phosphinates from the viewpoint of a touch and appearance similar to human hair, and from the viewpoint of heat resistance, a metal phosphinate Salt is more preferred.
  • condensed phosphoric ester compound examples include, but are not limited to, 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), 2 , 2-bis (chloromethyl) trimethylene bis (bis (2-chloroethyl) phosphate), polyoxyalkylene bis dichloroalkyl phosphate, aromatic condensed phosphate ester polymers, etc., and have good fiber moldability. From this point of view, aromatic condensed phosphate polymers are preferable. Further, the aromatic condensed phosphate polymer may take the form of a copolymerization type aromatic condensed phosphate polymer having two or more different repeating skeletons, for example.
  • the metal phosphinate is not particularly limited, but examples include aluminum phosphinate, magnesium phosphinate, barium phosphinate, calcium phosphinate, and zinc phosphinate.
  • zinc phosphinate whose metal atom is zinc, unlike other metal salts (aluminum, magnesium, barium, calcium, etc.) other than zinc, melts at the resin processing temperature, so it is finely and uniformly dispersed in the resin.
  • zinc phosphinate examples include compounds represented by the following general formula (3).
  • commercially available products such as phosphorus-based flame retardants manufactured by Clariant Chemicals Co., Ltd. (trade name "EXOLIT OP950”) may be used.
  • R 1 and R 2 are the same or different and are linear or branched alkyl groups, phenyl groups and/or aryl groups, preferably linear or branched C1-C6 alkyl groups, and /or an aryl group, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and/or phenyl.
  • Examples of the zinc phosphinate include zinc dimethylphosphinate, zinc methylethylphosphinate, zinc diethylphosphinate, zinc methyl-n-propylphosphinate, zinc ethyl-n-propylphosphinate, zinc methylphenylphosphinate, zinc ethylphenylphosphinate, zinc diphenylphosphinate, and the like, preferably one or more selected from the group consisting of zinc dimethylphosphinate, zinc methylethylphosphinate, and zinc diethylphosphinate; more preferably, diethyl zinc phosphinate.
  • nitrogen-based flame retardants include melamine, melamine derivatives, triazine-based compounds, isocyanuric acid-based compounds, azoalkane-based compounds, guanidine-based compounds, and phosphazene-based compounds.
  • Melamine derivatives include, for example, melam, melem, melamine cyanurate, melamine oxalate, melamine phthalate, melamine sulfate, and melamine phosphate compounds (eg, melamine polyphosphate, melamine pyrophosphate, dimelamine phosphate).
  • melamine derivatives one or more selected from the group consisting of melamine cyanurate and melamine phosphate compounds are preferable from the viewpoint of heat resistance and availability.
  • the amount of the flame retardant is not particularly limited, but from the viewpoint of achieving both flame retardancy and feel and appearance, it is preferable to include 5 parts by weight or more and 30 parts by weight or less of the flame retardant with respect to 100 parts by weight of the main component resin. It is more preferable to contain 10 to 25 parts by weight, more preferably 10 to 25 parts by weight.
  • the auxiliary flame retardant is not particularly limited, but it is preferable to use an antimony-based flame-retardant auxiliary and/or a zinc-based flame-retardant auxiliary from the viewpoint of achieving both flame retardancy, feel, and appearance.
  • Antimony-based flame retardant aids include, for example, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, potassium antimonate, and calcium antimonate.
  • Zinc-based flame retardant aids include, for example, zinc borate, zinc phosphate, zinc stannate, calcium zinc molybdate, and the like.
  • One or more selected from the group consisting of antimony trioxide, antimony pentoxide, and sodium antimonate is more preferable from the viewpoint of the effect of improving flame retardancy and the effect on touch. These compounds may be used alone or in combination of two or more.
  • the amount of the auxiliary flame retardant is not particularly limited, but from the viewpoint of achieving both flame retardancy, feel, and appearance, the amount of the auxiliary flame retardant is 0.1 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the main component resin. It is preferably contained, more preferably 0.5 to 5 parts by weight, and even more preferably 1 to 4 parts by weight.
  • the average particle size of the flame retardant aid is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, more preferably 0.2 ⁇ m or more and 8 ⁇ m or less, and even more preferably 0.5 ⁇ m or more and 5 ⁇ m or less. By setting it to such a range, the tactile sensation and combability are improved.
  • the resin composition constituting the fiber of the present invention is not particularly limited, but it contains a stabilizer from the viewpoint of reducing yellowing due to thermal deterioration of the resin, deterioration of physical properties of the fiber, deterioration of touch due to the generation of protrusions, etc. preferably.
  • the stabilizer include copper compounds, alkali halide compounds, fatty acid metal salts, inorganic metal particles (those containing one or more elements selected from the group consisting of zinc, aluminum, and magnesium elements are preferably used), Phosphorus-based stabilizers, hindered phenol-based antioxidants, hindered amine-based stabilizers, etc. may be mentioned, and these compounds may be used alone or in combination of two or more.
  • a compound having an amide group in the molecular skeleton is preferable as the hindered phenol-based antioxidant or hindered amine-based stabilizer. Since such a compound has excellent compatibility in the polyamide resin, the feel and appearance of the fiber are improved, and the moldability is also improved.
  • Examples of the compound having an amide group in the molecular skeleton include, but are not limited to, N,N'-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide ] (CAS number: 23128-74-7, product name: IRGANOX1098) and N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl) isophthalamide (CAS number: 42774-15 -2, product name: NYLOSTAB S-EED).
  • the content of the stabilizer is preferably 0.01 parts by weight or more and 5 parts by weight or less, more preferably 0.05 parts by weight or more and 3 parts by weight or less, and 0.1 parts by weight with respect to 100 parts by weight of the main component resin. 1 part by weight or less is more preferable. Within this range, a sufficient effect as a stabilizer can be obtained, and the feel and appearance of the fiber can be maintained.
  • the fiber of the present invention may contain one or more particles selected from inorganic particles, organic resin particles, and inorganic-organic resin composite particles from the viewpoint of making the appearance similar to human hair. .
  • the particles fine unevenness is formed on the surface of the obtained fiber, the luster peculiar to plastic is suppressed, and an appearance resembling human hair can be imparted.
  • the inorganic particles include calcium carbonate, calcium phosphate, a composite of calcium carbonate and calcium phosphate, magnesium carbonate, silicon oxide, titanium oxide, aluminum oxide, magnesium oxide, magnesium hydroxide, zinc oxide, talc, carion, montmorillonite, and bentonite. , mica and the like.
  • organic resin particles examples include crosslinked acrylic resin particles, crosslinked nitrile resin particles, crosslinked polystyrene resin particles, crosslinked polyester resin particles, crosslinked polyamide resin particles, polycarbonate resin particles, polyarylate resin particles, polyolefin resin particles, and melamine resin particles. , fluororesin particles and silicone resin particles, but from the viewpoint of dispersibility in the resin and appearance similar to human hair, at least one selected from crosslinked acrylic resin particles, crosslinked nitrile resin particles, and crosslinked polyamide resin particles. The above is preferable.
  • the inorganic-organic resin composite particles are particles formed by combining an inorganic compound and an organic resin, and examples thereof include composite particles of melamine resin and silica.
  • the particles may be surface-treated with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound, or the like, in order to enhance adhesion with the resin component.
  • the particles may be used singly or in combination of two or more.
  • the average particle diameter of the particles is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, more preferably 0.2 ⁇ m or more and 8 ⁇ m or less, and even more preferably 0.5 ⁇ m or more and 5 ⁇ m or less.
  • the content of the particles is preferably 0.05 parts by weight or more and 20 parts by weight or less, more preferably 0.1 parts by weight or more and 10 parts by weight or less, and 0.1 parts by weight or more with respect to 100 parts by weight of the main component resin. 5 parts by weight or less is more preferable. By setting it to such a range, the effect of suppressing luster can be sufficiently obtained, and a touch similar to human hair and good combability can be maintained.
  • additives such as crystal nucleating agents, dispersants, lubricants, fluorescent agents, antistatic agents, and pigments may be contained within a range that does not impair the effects of the present invention.
  • the method for producing the fiber for artificial hair is not particularly limited as long as it can produce a fiber having a continuous hollow portion in the fiber axis direction.
  • a conjugate nozzle to blow air through the center to form a hollow portion
  • a method of forming a hollow portion by eluting the composition of the portion, a method of laminating materials extruded from a plurality of holes, and the like directly below the discharge hole can be used.
  • the method of laminating materials extruded through a plurality of holes directly under the discharge holes is preferred.
  • a method of laminating materials extruded from a plurality of holes directly under the discharge hole for example, a method of providing a grid in the land of the nozzle, dividing the fibers into two or more, and then heat-sealing them to form a void. etc. can be used.
  • the artificial hair fiber of the present invention can be produced, for example, by melt-kneading and pelletizing a resin composition and then melt-spinning it using a spinneret. etc. can be appropriately added during melt-kneading.
  • kneaders used for melt-kneading include single-screw extruders, twin-screw extruders, rolls, Banbury mixers, and kneaders. Among them, a twin-screw extruder is preferable from the viewpoint of adjustment of kneading degree and simplicity of operation.
  • melt-spinning a resin composition containing a polyamide-based resin as a main component resin the temperature of the extruder, gear pump, spinneret, etc. is set to 230 ° C. or higher and 300 ° C. or lower, and melt extrusion is performed at a speed of 30 m / min or higher and 5000 m / min or lower.
  • a spun yarn (undrawn yarn) is obtained by taking it off at a high speed.
  • a resin composition is supplied by an extruder, and a spun yarn (undrawn yarn) is obtained by discharging a molten polymer through a spinning nozzle (hole) having a predetermined shape. be done.
  • the number of filaments discharged from the same spinning nozzle is not particularly limited, it is preferably in the range of 20 to 300. If the number of filaments is less than 20, the productivity will be low, and if it exceeds 300, the cooling efficiency will be reduced and the fineness will tend to vary.
  • the fineness of the spun yarn can be controlled by, for example, cooling using a cooling water tank or cooling by blowing air.
  • the temperature and length of the heating cylinder, the temperature and blowing amount of the cooling air, the temperature of the cooling water tank, the cooling time and the take-up speed can be appropriately adjusted according to the discharge amount of the polymer and the number of holes in the die.
  • the spun yarn (undrawn yarn) is preferably drawn.
  • the drawing may be carried out by either a two-step method in which the spun yarn is once wound up and then drawn, or a direct spinning drawing method in which the spun yarn is continuously drawn without being wound up.
  • the drawing is performed by a single-stage drawing method or a multi-stage drawing method with two or more steps.
  • a heating means for stretching a heating roller, a heat plate, a steam jet device, a hot water tank, etc. can be used, and these can also be used in combination as appropriate.
  • a fiber treatment agent, softening agent, or other oil may be added to the artificial hair fibers to make the feel and texture more similar to that of human hair.
  • fiber treatment agents include silicone-based fiber treatment agents and non-silicone-based fiber treatment agents for improving touch and combability.
  • the artificial hair fibers may be dyed to appropriately adjust the color of the fibers.
  • Articleificial hair fibers may be processed by gear crimping. As a result, the fibers are gently bent, a natural appearance is obtained, and the adhesion between the fibers is lowered, so that the combability can be further improved. In this gear crimping process, the fiber is generally heated to a softening temperature or higher and passed between two meshed gears, and the shape of the gear is transferred to make the fiber bend.
  • fibers possessed by artificial hair fibers such as a fiber bundle
  • fibers having different fineness and cross-sectional shape may be mixed.
  • Head ornament products include, but are not limited to, hair wigs, wigs, weaving, hair extensions, braided hair, hair accessories and doll hair.
  • the headdress product may consist only of the artificial hair fiber of the present invention.
  • the head ornament product may be configured by combining the artificial hair fiber of the present invention with other artificial hair fibers or natural fibers such as human hair and animal hair.
  • fiber specific gravity Using an electronic densimeter (MDS-300, manufactured by Alpha Mirage), water was used as a medium, and the specific gravity of the fibers was measured at room temperature based on the Archimedes method as follows. First, the fibers were cut to a length of 5 cm and a weight of about 0.5 to 1.0 g to prepare a fiber bundle. Next, the fiber bundle was submerged in water as a medium, and the specific gravity was calculated. When the specific gravity of the fiber is smaller than that of water, the fiber bundle was fixed in water using the attached angle and measured.
  • MDS-300 electronic densimeter
  • bending stiffness Using a KES-FB2 pure bending tester (manufactured by Kato Tech), bending stiffness was measured as follows. First, 49 fibers (single yarns) were attached to a backing paper at intervals of 1 mm, and the top and bottom of the attached fibers were fixed with cellophane tape so as not to loosen. The obtained sample was fixed to a jig of an apparatus, and measured at a deformation rate of 0.5 cm/sec in a curvature range of ⁇ 2.5 to +2.5 (cm ⁇ 1 ) under normal temperature and normal humidity. The average repulsive force was measured at a curvature of 0.5 to 1.5 (cm ⁇ 1 ), and the value per fiber was calculated as the flexural rigidity.
  • Fiber specific gravity is 1.00 or less
  • gloss A visual sensory evaluation was performed and evaluated according to the following four-grade criteria. A: The gloss has disappeared very well, and is very similar to human hair. B: The gloss has disappeared well, and it resembles human hair. C: The gloss has not disappeared or has disappeared too much, and is different from human hair D: The gloss has not disappeared or has disappeared too much, and is quite different from human hair.
  • the fibers were cut to a length of 70 cm while the curl was completely stretched, and 25 g of the obtained fibers having a fiber length of 70 cm were bundled. After that, the center of the fiber bundle was bound with a string, folded in two, and the string portion was fixed to prepare a fiber bundle for hair ironing. Next, with a hair iron ("IZUNAMI ITC450 flat iron" manufactured by IZUNAMI INC, USA) heated to 180°C, the heating operation is performed 5 times while crimping from the root to the tip of the hair fixing the fiber bundle. A fiber bundle for evaluation of combability was repeatedly produced.
  • IZUNAMI ITC450 flat iron manufactured by IZUNAMI INC, USA
  • Example 1 For 100 parts by weight of nylon 6 (manufactured by Unitika, product name "A1030BRF”) dried overnight at 70 ° C., brominated epoxy flame retardant (manufactured by Sakamoto Chemical Industry, product name “SR-T2MP”) 15 parts by weight, flame retardant 2 parts by weight of sodium antimonate (manufactured by Nippon Seiko, trade name "SA-A”) and 0.75 parts by weight of a stabilizer (manufactured by Clariant Chemicals, trade name "NYLOSTAB S-EED”) are added as auxiliaries, and dried.
  • SR-T2MP brominated epoxy flame retardant
  • SA-A sodium antimonate
  • SA-A sodium antimonate
  • a stabilizer manufactured by Clariant Chemicals, trade name "NYLOSTAB S-EED
  • the mixture was supplied to a twin-screw extruder, melt-kneaded at a set temperature of 260° C., and pelletized to obtain a resin composition.
  • the pellets obtained were dried overnight at 70°C.
  • the dried pellets were supplied to an extruder, extruded through a spinneret (120 holes) set at a temperature of 260° C., and taken up at a speed of 100 m/min to obtain an undrawn yarn.
  • a hollow fiber having a hollow portion inside the fiber was produced by using a method in which a lattice was provided in the land of the nozzle and the fiber was once divided into two or more, and then heat-sealed to form a hollow portion. .
  • the obtained undrawn yarn is drawn 3 times using a heat roll at 110°C, and further heat-treated continuously using a heat roll heated to 200°C.
  • a flat bilobal polyamide fiber having a hollow portion of 1 was obtained (Fig. 1).
  • the single fiber fineness of the fiber was 56 dtex.
  • Example 2 The conditions were the same as in Example 1, except that the set temperature of the spinneret was 245°C. The single fiber fineness of the fiber was 56 dtex.
  • Example 3 The conditions were the same as in Example 2, except that the take-up speed during spinning was 105 m/min. The single fiber fineness of the fiber was 53 dtex.
  • Example 4 The conditions were the same as in Example 2, except that the take-up speed during spinning was 110 m/min. The single fiber fineness of the fiber was 49 dtex.
  • Example 1 The conditions were the same as in Example 1, except that the nozzle hole shape was changed.
  • the single fiber fineness of the fiber was 55 dtex.
  • Example 2 The conditions were the same as in Example 1, except that a nozzle having a non-hollow fiber structure was used.
  • the single fiber fineness of the fiber was 68 dtex.
  • the dried pellets were supplied to an extruder, extruded through a spinneret (120 holes) set at a temperature of 260° C., and taken up at a speed of 100 m/min to obtain an undrawn yarn.
  • a spinneret 120 holes set at a temperature of 260° C.
  • hollow fibers having voids in the fibers were produced by using a method in which a grid was provided in the land of the nozzle, and the fibers were once divided into two or more, and then heat-sealed to form voids.
  • the obtained undrawn yarn is drawn 3 times using a heat roll at 85 ° C., further heat-treated continuously using a heat roll heated to 205 ° C., a processing oil is applied, dried, and a fiber A polyester fiber having voids inside was obtained.
  • the single fiber fineness of the fiber was 59 dtex.
  • Comparative Example 4 The conditions were the same as in Comparative Example 3, except that a nozzle in which the fibers had a non-hollow structure was used. The single fiber fineness of the fiber was 63 dtex.
  • FIG. 1 is a laser micrograph of the cross section of the fiber of Example 1.
  • the fiber has a flat bilobal shape and has a hollow portion, and the shape of the hollow portion is quadrilateral.
  • the polyamide-based hollow fibers for artificial hair described in Example 1 had a relatively high hollowness, good light weight, and a soft feel similar to human hair. .
  • the polyamide-based hollow fibers for artificial hair described in Examples 2, 3, and 4 had a sufficiently high hollowness, excellent light weight, and a soft feel similar to human hair.
  • the polyamide-based hollow fiber for artificial hair described in Comparative Example 1 had a soft feel similar to that of human hair, but had a low hollowness and insufficient lightness.
  • the polyamide-based fiber for artificial hair described in Comparative Example 2 had a soft feel similar to that of human hair, but was not hollow and had insufficient lightness.
  • the polyester-based hollow fiber for artificial hair described in Comparative Example 3 was far from a soft feel similar to that of human hair, and was also insufficient in lightness.
  • the polyester fiber for artificial hair described in Comparative Example 4 was far from the soft feel similar to that of human hair, and was significantly inferior in lightness.

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PCT/JP2022/003149 2021-02-15 2022-01-27 人工毛髪用ポリアミド系中空繊維、それを含む頭飾製品及び人工毛髪用ポリアミド系中空繊維の製造方法 Ceased WO2022172766A1 (ja)

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