Classifications

• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
  • A41G3/00—Wigs
  • A41G3/0083—Filaments for making wigs
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
  • D01D5/30—Conjugate filaments; Spinnerette packs therefor
  • D01D5/34—Core-skin structure; Spinnerette packs therefor
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/07—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
  • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
  • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • 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 having a core-sheath structure that can be used as a substitute for human hair, and a headdress product containing the same.
• Human hair has traditionally been used in headdress products such as wigs, hair wigs, hair wigs, hair bands, and doll hair.
• headdress products such as wigs, hair wigs, hair wigs, hair bands, and doll hair.
• the demand for artificial hair to replace human hair is increasing.
• synthetic fibers used for artificial hair include acrylic fibers, vinyl chloride fibers, vinylidene chloride fibers, polyester fibers, polyamide fibers, and polyolefin fibers.
• Patent Document 1 describes an artificial core-sheath structure as an artificial hair fiber having a tactile sensation similar to that of human hair, in which the core is made of a resin composition containing polyester and the sheath is made of a resin composition containing polyamide.
• a fiber for hair has been proposed, and further, it is described that flame retardancy is imparted by adding a brominated flame retardant to the core resin composition and / or the sheath resin composition.
• the core-sheath composite fiber for artificial hair described in Patent Document 1 has a texture similar to that of human hair, a large amount of a bromine-based flame retardant is added to the sheath resin composition containing polyamide for flame retardancy. Then, the texture and luster are far from those of human hair, and the combability is impaired. On the other hand, if the amount of the flame retardant is suppressed to be small in order to make the tactile sensation of the fiber similar to that of human hair, it is inferior to human hair in terms of flame retardancy. As described above, there remains a problem that it is difficult to achieve both flame retardancy and tactile sensation, gloss, and combability.
• the present invention provides an artificial hair fiber having a tactile sensation and luster close to that of human hair, and having good combability and flame retardancy, and a headdress product containing the same.
• the present invention is a core-sheath composite fiber for artificial hair including a core portion and a sheath portion covering the core portion in one or more embodiments, and the core portion is composed of a core portion resin composition containing a polyester resin.
• the sheath portion is composed of a sheath portion resin composition containing a polyamide-based resin, the core portion resin composition contains a brominated flame retardant and a flame retardant aid, and the sheath portion resin composition is a phosphorus-based flame retardant.
• the phosphorus-based flame retardant contains at least one selected from the group consisting of zinc phosphinate and a condensed phosphate ester-based compound
• the core-sheath composite fiber for artificial hair is a main component resin and a sheath of the core portion.
• the artificial hair core is characterized by containing 20 parts by weight or more and 40 parts by weight or less in total of the brominated flame retardant, the phosphorus flame retardant and the flame retardant aid.
• sheath composite fibers is characterized by containing 20 parts by weight or more and 40 parts by weight or less in total of the brominated flame retardant, the phosphorus flame retardant and the flame retardant aid.
• the present invention also relates to a headdress product containing the core-sheath composite fiber for artificial hair in one or more embodiments.
• a core-sheath composite fiber for artificial hair having a tactile sensation and luster close to that of human hair, and having good combability and flame retardancy, and a headdress product containing the same.
• the fiber for artificial hair has a core-sheath structure
• the core is composed of a core resin composition containing a polyester resin
• the sheath is a polyamide-based. It is composed of a sheath resin composition containing a resin, and by adding a predetermined flame retardant to each of the core resin composition and the sheath resin composition, the tactile sensation, gloss, and combability are impaired. It has been found that it is possible to provide a fiber for artificial hair having good flame retardancy.
• the core-sheath composite fiber for artificial hair has a core-sheath structure including a core portion and a sheath portion covering the core portion.
• the fiber may have a concentric structure in which the core portion may be present inside the sheath portion and the center point of the core portion coincides with the center point of the fiber, and the center point of the core portion does not coincide with the center point of the fiber. It may be an eccentric structure that is eccentric.
• the cross-sectional shape of the core-sheath composite fiber for artificial hair may be circular, or may be an irregular shape such as an elliptical shape or a multi-leaf shape.
• the cross-sectional shape of the core portion may be circular, or may be an irregular shape such as an ellipse or a multi-leaf shape.
• the cross-sectional shape of the core-sheath composite fiber for artificial hair and the cross-sectional shape of the core portion may be the same or different.
• the core-sheath ratio is within the above-mentioned range, peeling of the two components is unlikely to occur, and molding as a core-sheath composite fiber is easy.
• the core-sheath composite fiber for artificial hair is not particularly limited as long as the core portion is composed of a resin composition containing a polyester-based resin and the sheath portion is composed of a resin composition containing a polyamide-based resin.
• the core is composed of a polyester resin composition containing a polyester resin as a main component resin, and a sheath is provided.
• the portion is composed of a polyamide-based resin composition containing a polyamide-based resin as a main component resin
• the core portion is one or more selected from the group consisting of polyalkylene terephthalate and copolymerized polyester mainly composed of polyalkylene terephthalate.
• Polyamide-based resin composed of a polyester-based resin composition containing a polyester-based resin as a main component resin, and having a sheath portion mainly composed of at least one selected from the group consisting of nylon 6 and nylon 66 as a main component resin. It is more preferable to use a resin composition.
• the core contains a brominated flame retardant and a flame retardant aid, and the sheath contains at least a phosphorus flame retardant.
• flame retardancy is improved, gloss is good, and combability and tactile sensation are also excellent.
• a brominated flame retardant when the total of the main component resin in the core and the main component resin in the sheath is 100 parts by weight, a brominated flame retardant, It is preferable that the phosphorus-based flame retardant and the flame retardant aid are contained in a total amount of 20 parts by weight or more and 40 parts by weight or less, and 20 parts by weight or more and 30 parts by weight or less.
• the blending amount of the main component resin of the core in the core-sheath composite fiber for artificial hair and The blending amount of the main component resin in the sheath portion is calculated based on the core-sheath ratio. For example, when the core-sheath ratio is 5: 5, the main component resin of the core portion is 50 parts by weight, and when the core-sheath ratio is 7: 3, the main component resin of the sheath portion is 50 parts by weight. The main component resin is 70 parts by weight, and the main component resin of the sheath portion is 30 parts by weight.
• the "main component resin of the core portion” means a resin having the highest content in the resin contained in the core portion resin composition, and may be a polyester-based resin. preferable.
• the content of the main component resin is preferably more than 50% by weight, preferably 70% by weight or more, and more preferably 85% by weight or more. , 90% by weight or more, further preferably 95% by weight or more, and even more preferably 100% by weight.
• the core resin composition preferably contains a total of 20 parts by weight or more and 40 parts by weight or less of a brominated flame retardant and a flame retardant aid with respect to 100 parts by weight of the main component resin.
• the core resin composition is not particularly limited, but from the viewpoint of achieving both gloss and flame retardancy, it is preferable to contain 20 parts by weight or more and 35 parts by weight or less of the brominated flame retardant with respect to 100 parts by weight of the main component resin.
• the core resin composition is not particularly limited, but from the viewpoint of achieving both gloss and flame retardancy, it is preferable to contain 1 part by weight or more and 5 parts by weight or less of the flame retardant aid with respect to 100 parts by weight of the main component resin. It is more preferable to include 2 parts by weight or more and 3 parts by weight or less.
• the "main component resin of the sheath portion” means a resin having the highest content in the resin contained in the sheath portion resin composition, and may be a polyamide-based resin. preferable.
• the content of the main component resin is preferably more than 50% by weight, preferably 75% by weight or more, and more preferably 85% by weight or more. , 90% by weight or more, further preferably 95% by weight or more, and even more preferably 100% by weight.
• the sheath resin composition preferably contains 3 parts by weight or more and 20 parts by weight or less of the phosphorus-based flame retardant with respect to 100 parts by weight of the main component resin.
• the sheath resin composition preferably contains 5 parts by weight or more and 20 parts by weight or less of the brominated flame retardant with respect to 100 parts by weight of the main component resin. It is more preferable to include 15 parts by weight or less.
• the sheath resin composition preferably contains 1 part by weight or more and 5 parts by weight or less of the flame retardant aid with respect to 100 parts by weight of the main component resin. It is more preferable to include 3 parts by weight or less.
• the bromine-based flame retardant is not particularly limited, and for example, a brominated epoxy flame retardant; pentabromotoluene, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether, bis (tribromophenoxy) ethane, tetrabromobisphenol phthalic acid, and the like.
• Bromine-containing phosphate esters such as ethylenebis (tetrabromophthalimide), ethylenebis (pentabromophenyl), octabromotrimethylphenylindan, tris (tribromoneopentyl) phosphate; brominated polystyrenes; brominated polybenzyl acrylates Brominated phenoxy resin; Brominated polycarbonate oligomers; Tetrabromobisphenol A, Tetrabromobisphenol A-bis (2,3-dibromopropyl ether), Tetrabromobisphenol A-bis (allyl ether), Tetrabromobisphenol A-bis 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. Above all, from the
• 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 particularly high. Not limited to this, 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 the configuration represented by the chemical formula (1). It is preferably a unit.
• the brominated epoxy flame retardant may change its structure 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, etc., and the molecular end is bonded to the polyester component by an ester group. You may.
• 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 chemical formula (1). ) May be desorbed 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 brominated epoxy flame retardants manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. (trade name “SR-T2MP”). Commercially available products may be used.
• the flame retardant aid is not particularly limited, but from the viewpoint of flame retardancy, for example, it is preferable to use an antimony compound, a composite metal containing antimony, a composite metal containing zinc, or the like.
• the antimony compound include antimony trioxide, antimony tetroxide, antimony tetroxide, sodium antimonate, potassium antimonate, calcium antimonate and the like
• examples of the zinc-containing composite metal include zinc borate and tin acid. Examples include zinc. From the viewpoint of flame retardancy improving effect and influence on tactile sensation, one or more selected from the group consisting of antimony trioxide, antimony pentoxide, and sodium antimonate is preferable.
• the phosphorus-based flame retardant contains one or more selected from the group consisting of zinc phosphinate and a condensed phosphate ester-based compound.
• zinc phosphinate melts at the resin processing temperature of the polyamide-based resin, so that it is finely and uniformly dispersed in the resin.
• the tactile sensation and appearance of the fibers can be made to resemble that of human hair, and the combability can be improved.
• phosphinate using a metal other than zinc impairs the tactile sensation and luster, and cannot exhibit the tactile sensation and luster similar to human hair.
• Examples of the zinc phosphinate include zinc phosphinate as shown in the following general formula (3).
• a phosphorus-based flame retardant manufactured by Clariant Chemicals Co., Ltd. (trade name "EXOLIT (registered trademark) OP950").
• Clariant Chemicals Co., Ltd. trade name "EXOLIT (registered trademark) OP950”
• the phosphorus-based flame retardant manufactured by Clarant Chemicals Co., Ltd. (trade name "EXOLIT (registered trademark) OP950”) was developed especially for use in polyester-based resins, but surprisingly, it was added to polyamide-based resins. When melt-kneaded and melt-spun, the fibers are finely and uniformly dispersed in the polyamide resin, and the texture and appearance of the fibers are similar to those of human hair, and the combability can be improved.
• 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 to C6. Alkyl groups and / or aryl groups, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and / or phenyl.
• the zinc phosphinate is, for example, zinc dimethylphosphinate, zinc methylethylphosphinate, zinc diethylphosphinate, zinc methyl-n-propylphosphinate, zinc ethyl-n-propylphosphinate, zinc methylphenylphosphite, ethylphenyl.
• Examples thereof include zinc phosphinate and zinc diphenylphosphinate, preferably one or more selected from the group consisting of zinc dimethylphosphinate, zinc methylethylphosphinate, and zinc diethylphosphinate, and more preferably diethylphosphine. It is zinc acid.
• the condensed phosphate ester compound is, for example, 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 bisdichloroalkyl phosphate, aromatic-condensed phosphoric acid ester-based polymer, etc., from the viewpoint of good fiber molding processability, aromatic condensation A phosphoric acid ester-based polymer is preferable.
• the aromatic condensed phosphoric acid ester-based polymer may be, for example, a homopolymer or may take the form of a copolymerized aromatic condensed phosphoric acid ester-based polymer having two or more different repeating skeletons.
• the weight average molecular weight of the aromatic condensed phosphoric acid ester polymer is preferably 1,000 to 300,000 g / mol, preferably 5,000 to 200,000 g, from the viewpoint of dispersibility in the polyamide resin and heat resistance. / Mol is more preferable, and 10,000 to 150,000 g / mol is even more preferable.
• the weight average molecular weight shown here refers to the weight average molecular weight calculated from a calibration curve prepared by using dimethylformamide as a solvent and using a polyvinyl chloride resin in gel permeation chromatography (GPC).
• aromatic condensed phosphoric acid ester-based polymer for example, a commercially available product such as a phosphorus-based flame retardant manufactured by FRX POLYMER (trade name “Nofia HM1100”) may be used.
• Aromatic condensed phosphoric acid ester-based polymers represented by FRX POLYMER phosphorus-based flame retardants (trade name "Nofia HM1100”) can be melt-kneaded with polyamide resins due to their high heat resistance, and bleed. Since it is difficult to out, the tactile sensation as a fiber for artificial hair is good.
• the core resin composition is not particularly limited as long as it contains a polyester resin, and is, for example, a polyester resin, a polyamide resin, a modal acrylic resin, a polycarbonate resin, a polyolefin resin, a polyphenylene sulfide resin, or the like.
• One or more resins selected from the group consisting of the above can be contained as the main component resin.
• the core resin composition is preferably a polyester resin composition containing a polyester resin as a main component resin, and is a copolymerized polyester mainly composed of polyalkylene terephthalate and polyalkylene terephthalate.
• the polyester-based resin composition contains one or more polyester-based resins selected from the group consisting of the main components as the main component resin.
• the polyester-based resin composition may contain other resins in addition to the polyester-based resin which is the main component resin.
• the polyester resin as the main component resin is contained in an amount of 50% by weight or more, more preferably 70% by weight or more, and 85% by weight or more. It is further preferably contained, more preferably 90% by weight or more, further preferably 95% by weight or more, and even more preferably 100% by weight.
• 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 above 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.
• "Copolymerized polyester mainly containing polyalkylene terephthalate” refers to a copolymerized polyester containing 80 mol% or more of polyalkylene terephthalate.
• copolymerization components include, for example, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, pyromellitic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, and sevacinic acid.
• Polyvalent carboxylic acids such as dodecanedioic acid and their derivatives; dicarboxylic acids and their derivatives including sulfonates such as 5-sodium sulfoisophthalic acid, 5-sodium sulfoisophthalate dihydroxyethyl; 1,2-propanediol , 1,3-Propanediol, 1,4-Butanediol, 1,6-hexanediol, Neopentylglycol, 1,4-Cyclohexanedimethanol, Diethyleneglycol, Polyethylene glycol, Trimethylolpropane, Pentaerythritol, 4-Hydroxybenzoic acid Examples thereof include 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 small amount of other copolymerizable monomers or oligomers. It may be produced by polymerizing the one containing the component.
• the copolymerized polyester may be polycondensed with the above-mentioned other copolymerization components on the main chain and / or side chain of the main polyalkylene terephthalate, and the copolymerization method is not particularly limited.
• copolymerized polyester mainly composed of polyalkylene terephthalate include, for example, ethylene glycol ether of bisphenol A, 1,4-cyclohexadimethanol, isophthalic acid and dihydroxyethyl 5-sodium sulfoisophthalate mainly composed of polyethylene terephthalate.
• the copolymerized polyester mainly composed of polyalkylene terephthalate and polyalkylene terephthalate may be used alone or in combination of two or more.
• polyethylene terephthalate hereinafter, also referred to as PET
• polypropylene terephthalate polybutylene terephthalate
• polyethylene terephthalate polypropylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, and polyethylene terephthalate, dihydroxyethyl 5-sodium sulfoisophthalate.
• polyester or the like alone or in combination of two or more.
• Polyethylene terephthalate a polyester obtained by copolymerizing polyethylene terephthalate with ethylene glycol ether of bisphenol A; using polyethylene terephthalate as a main component and 1,4-cyclohexanedimethanol.
• Copolymerized polyester polyester mainly composed of polyethylene terephthalate and copolymerized with isophthalic acid; and polyester mainly composed of polyethylene terephthalate and copolymerized with dihydroxyethyl 5-sodium sulfoisophthalate, etc., alone or in combination of two or more. Is more preferable.
• the intrinsic viscosity (IV value) of the polyester resin is not particularly limited, but is preferably 0.3 or more and 1.2 or less, and more preferably 0.4 or more and 1.0 or less.
• the intrinsic viscosity is 0.3 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 or less, the molecular weight does not increase too much, the melt viscosity does not become too high, the melt spinning becomes easy, and the fineness tends to be uniform.
• the sheath resin composition is not particularly limited as long as it contains a polyamide resin, and is, for example, a polyester resin, a polyamide resin, a modal acrylic resin, a polycarbonate resin, a polyolefin resin, a polyphenylene sulfide resin, or the like.
• One or more resins selected from the group consisting of the above can be contained as the main component resin.
• the sheath resin composition is preferably a polyamide-based resin composition containing a polyamide-based resin as a main component resin.
• the polyamide-based resin composition may contain other resins in addition to the polyamide-based resin which is the main component resin.
• the polyamide resin as the main component resin is contained in an amount of 50% by weight or more, more preferably 70% by weight or more, and 85% by weight or more. It is further preferably contained, more preferably 90% by weight or more, further preferably 95% by weight or more, and even more preferably 100% by weight.
• the polyamide resin is nylon obtained by polymerizing one or more selected from the group consisting of lactam, a mixture of aminocarboxylic acid, dicarboxylic acid and diamine, a mixture of dicarboxylic acid derivative and diamine, and a salt of dicarboxylic acid and diamine. Means resin.
• lactam examples include, but are not limited to, 2-azetidinone, 2-pyrrolidinone, ⁇ -valerolactam, ⁇ -caprolactam, enantractam, caprilactam, undecalactam, laurolactam and the like. .. 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 are not particularly limited, but are, for example, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-. Aminododecanoic acid and the like can be mentioned. 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 a mixture of dicarboxylic acid and diamine, a mixture of dicarboxylic acid derivative and diamine, or a salt of dicarboxylic acid and diamine are not particularly limited, but for example, oxalic acid, malonic acid, succinic acid, and glutaric acid.
• Adipic acid Pimelic acid, Sveric acid, Azelaic acid, Sevacinic acid, Undecanedioic acid, Dodecanedioic acid, Brushphosphate, Tetradecanedioic acid, Pentadecanedioic acid, Octadecanedioic acid and other aliphatic dicarboxylic acids, Cyclohexanedicarboxylic acid, etc.
• aromatic dicarboxylic acids such as alicyclic dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.
• 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 a mixture of dicarboxylic acid and diamine, a mixture of dicarboxylic acid derivative and diamine, or a salt of dicarboxylic acid and diamine are not particularly limited, and are, for example, 1,4-diaminobutane and 1,5-diamino.
• Pentan 1,6-diaminohexane, 2-methyl-1,5-diaminopentane (MDP), 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-diaminohexadecane, 1,17-diaminoheptadecan , 1,18-Diaminooctadecane, 1,19-diaminononadecan, 1,20-diaminoeikosan and other aliphatic diamines, cyclohexanediamine, bis- (4-aminohexyl) methane and other
• the polyamide-based resin is not particularly limited, but for example, nylon 6 (hereinafter, also referred to as PA6), nylon 66 (hereinafter, also referred to as PA66), nylon 11, nylon 12, nylon 6, and the like. 10.
• Semi-aromatic nylon containing nylon 6/12, nylon 6T and / or 6I units, and copolymers of these nylon resins are preferably used, and at least one selected from the group consisting of nylon 6 and nylon 66. Seed-based polyamide resins are more preferred.
• the "polyamide-based resin mainly composed of at least one selected from the group consisting of nylon 6 and nylon 66" means a polyamide-based resin containing 80 mol% or more of nylon 6 and / or nylon 66.
• 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, reaction yield, and reaction time of the target polymer, but a low temperature is preferable in consideration of the quality of the finally obtained polyamide-based 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 concentrations of the terminal amino group and 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.
• Alicyclic monocarboxylic acids such as myristorenic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and araquinic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid, benzoic acid, toluic acid, ethyl.
• Aromatic monocarboxylic acids such as benzoic acid and phenylacetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelineic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brushphosphoric acid , Tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid and other aliphatic dicarboxylic acids, cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and other aromatic dicarboxylic acids. Can be mentioned.
• amine compound examples are not particularly limited, but for example, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetra.
• Aliper monoamines such as decylamine, pentadecylamine, hexadecylamine, octadecylamine, nonadecylamine, and icosylamine, alicyclic monoamines such as cyclohexylamine and methylcyclohexylamine, aromatic monoamines such as benzylamine and ⁇ -phenylethylamine, 1.
• the concentration of the terminal group of the polyamide resin is not particularly limited, but it is preferable that the concentration of the terminal amino group is high when it is necessary to improve the dyeability for fiber applications. 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. Further, when it is desired to suppress lactam regeneration during remelting and yarn breakage during melt spinning due to oligomer formation, it is preferable that both the terminal carboxyl group concentration and the terminal amino group concentration are low.
• 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. It is 2.0 ⁇ 10 -5 to 12.0 ⁇ 10 -5 eq / g, and particularly preferably 3.0 ⁇ 10 -5 to 11.0 ⁇ 10 -5 eq / g.
• a method of adding the terminal sequestering agent 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 core-sheath composite fiber for artificial hair is produced, for example, by melt-kneading the core resin composition and the sheath resin composition, respectively, to pelletize them, and then melt-spinning them using a core-sheath type composite mouthpiece.
• the kneader used for melt kneading include a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, and a kneader. Above all, a twin-screw extruder is preferable from the viewpoint of adjusting the kneading degree and easiness of operation.
• the temperature of the extruder, gear pump, mouthpiece, etc. is 250 ° C. or higher and 300 ° C. or higher.
• a spun yarn is obtained by melt-extruding at a temperature of 30 ° C. or lower and taking up at a rate of 30 m / min or more and 5000 m / min or less.
• the core resin composition is supplied by the core extruder
• the sheath resin composition is supplied by the sheath extruder
• the core-sheath type composite yarn having a predetermined shape is supplied.
• a spun yarn (undrawn yarn) is obtained by ejecting the molten polymer through a nozzle (hole).
• the cross-sectional shape of the core-sheath composite fiber and its core portion, the core-sheath ratio, and the like can be controlled by using, for example, a nozzle (hole) having a shape close to the desired cross-sectional shape.
• 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 base.
• the spun yarn (undrawn yarn) is drawn.
• the stretching may be performed by either a two-step method in which the spun yarn is wound once and then stretched, or a direct spun stretching method in which the spun yarn is continuously drawn without being wound. 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 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 softener 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 a silicone-based fiber treatment agent and a non-silicone-based fiber treatment agent for improving the tactile sensation and combability.
• the core-sheath composite fiber for artificial hair is, if necessary, a matting agent, a crystal nucleating agent, a dispersant, a lubricant, a heat resistant agent, a stabilizer, a fluorescent agent, an antioxidant, as long as it does not interfere with the object of the present invention. It may contain various additives such as antistatic agents and pigments.
• the core-sheath composite fiber for artificial hair may be processed by gear crimping.
• 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.
• gear crimp in general, the fiber is heated to a temperature higher than the softening temperature and passed between two meshed gears, and the shape of the gear is transferred to express the fiber bending.
• the core-sheath composite fiber for artificial hair preferably has a single fiber fineness of 10 dtex or more and 200 dtex or less, more preferably 30 dtex or more and 180 dtex or less, and further preferably, from the viewpoint of being suitably used as artificial hair as a substitute for human hair. Is 40 dtex or more and 150 dtex or less, and particularly preferably 50 dtex or more and 100 dtex or less.
• the core-sheath composite fiber for artificial hair as an aggregate of fibers, for example, a fiber bundle, all the fibers do not necessarily have the same fineness and cross-sectional shape, and fibers having different fineness and cross-sectional shape are mixed. May be good.
• the core-sheath composite fiber for artificial hair may be used alone as artificial hair, or may be used as artificial hair by combining other artificial hair fibers and natural fibers such as human hair and animal hair.
• the core-sheath composite fiber for artificial hair can be used for headdress products.
• the headdress product is not particularly limited, and examples thereof include hair wigs, wigs, weaving, hair extensions, blade hairs, hair accessories, and doll hairs.
• 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 and 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.
• Level A The number of fibers deformed or split through the comb 100 times is less than 10, and the comb passes through without resistance until the end.
• Level B The number of fibers deformed or split through the comb 100 times is 10 or more and less than 30.
• Level C The number of fibers deformed or split by passing the comb 100 times is 30 or more and less than 100, and the resistance becomes stronger in the middle and the comb does not pass once or more 20 times.
• Level D that occurs at a rate of less than 100 times: The number of fibers that have been deformed or split by passing through the comb 100 times is 100 or more, and the resistance becomes stronger in the middle, and the level at which the comb does not pass at a rate of 20 times or more ( Glossy) A visual sensory evaluation was performed, and the evaluation was made according to the following four criteria.
• B The gloss disappears well compared to the nylon single fiber, and it is close to the gloss of human hair.
• C Nylon single fiber. The gloss is not so much or too much disappeared compared to the fiber, which is different from the gloss of human hair.
• LOI value 0.5 / 8 x (number disappeared) + oxygen concentration (%) (1) Based on the measured LOI value, the flame retardancy was evaluated according to the following three criteria, and B or higher was regarded as acceptable.
• Example 1 29 parts by weight of brominated epoxy flame retardant (manufactured by Sakamoto Yakuhin Kogyo, trade name "SR-T2MP") for 100 parts by weight of polyethylene terephthalate pellets (manufactured by East West Chemical Private Limited, EastPET product name "A-12"),
• SR-T2MP brominated epoxy flame retardant
• polyethylene terephthalate pellets manufactured by East West Chemical Private Limited, EastPET product name "A-12"
• SA-A sodium antimonate
• black pigment masterbatch manufactured by Dainichi Seika Kogyo Co., Ltd., trade name "PESM22367BLACK (20)
• pigment 20 weights %
• Base resin polyester resin
• 2.1 parts by weight yellow pigment masterbatch (manufactured by Dainichi Seika Kogyo, trade name "PESM1001YELLOW (20)", pigment: 20% by weight, base resin: polyester resin) 0.
• nylon 6 manufactured by Unitica, trade name "A1030BRL”
• 10 parts by weight of phosphorus-based flame retardant A manufactured by Clarant Chemicals, trade name "EXOLIT (registered trademark) OP950", zinc diethylphosphinate
• Black pigment masterbatch manufactured by Dainichi Seika Kogyo, trade name "PESM22367BLACK (20)"
• yellow pigment masterbatch manufactured by Dainichi Seika Kogyo, trade name "PESM1001YELLOW (20)
• Add 0.6 parts by weight of red pigment masterbatch manufactured by Dainichi Seika Kogyo, trade name "PESM3005RED (20)
• the pellet-shaped polyester resin composition and the polyamide-based resin composition obtained above are supplied to the extruder, respectively, and a concentric core-sheath type composite spinning nozzle having a set temperature of 270 ° C. (120 holes). , Hole diameter 1.5 mm) and wound at a rate of 40 to 200 m / min, the polyester resin composition as the core, the polyamide resin composition as the sheath, and the core-sheath ratio is 5 in area ratio. : An undrawn yarn of the core-sheath composite fiber of 5 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 205 ° 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 (single fiber fineness 58 dtex).
• Example 2 In the core resin composition, 100 parts by weight of the brominated epoxy flame retardant and 2 parts by weight of sodium antimonate are added to 100 parts by weight of polyethylene terephthalate.
• the core is the same as in Example 1 except that the nylon 6 is changed to add 10 parts by weight of the brominated epoxy flame retardant, 2 parts by weight of the sodium antimonate, and 3 parts by weight of the phosphorus flame retardant A.
• a sheath composite fiber single fiber fineness 58 dtex
• Example 3 In the core resin composition, 100 parts by weight of the brominated epoxy flame retardant and 2 parts by weight of sodium antimonate are added to 100 parts by weight of polyethylene terephthalate.
• the core is the same as in Example 1 except that the nylon 6 is changed to add 10 parts by weight of the brominated epoxy flame retardant, 2 parts by weight of the sodium antimonate, and 5 parts by weight of the phosphorus flame retardant A.
• a sheath composite fiber single fiber fineness 58 dtex
• Example 4 In the sheath resin composition, for 100 parts by weight of nylon 6, a phosphorus-based flame retardant D (manufactured by FRX POLYMER, trade name "Nofia HM1100", aromatic condensed phosphoric acid ester-based polymer, homopolymer, weight average molecular weight A core-sheath composite fiber (single fiber fineness 58 dtex) was obtained in the same manner as in Example 1 except that 43000 g / mol) was added in an amount of 12 parts by weight.
• FRX POLYMER trade name "Nofia HM1100”
• Example 5 In the sheath resin composition, for 100 parts by weight of nylon 6, a phosphorus-based flame retardant D (manufactured by FRX POLYMER, trade name "Nofia HM1100", aromatic condensed phosphoric acid ester-based polymer, homopolymer, weight average molecular weight A core-sheath composite fiber (single fiber fineness 58 dtex) was obtained in the same manner as in Example 1 except that 43000 g / mol) was added in an amount of 20 parts by weight.
• FRX POLYMER trade name "Nofia HM1100”
• Example 1 Changed to add 10 parts by weight of phosphorus-based flame retardant B (manufactured by Clariant Chemicals, trade name "EXOLIT (registered trademark) OP1400", aluminum phosphinate) to 100 parts by weight of nylon 6 in the sheath resin composition.
• a core-sheath composite fiber (single fiber fineness 58 dtex) was obtained in the same manner as in Example 1.
• Example 2 Changed to add 10 parts by weight of phosphorus-based flame retardant C (manufactured by Clariant Chemicals, trade name "EXOLIT (registered trademark) OP935", aluminum phosphinate) to 100 parts by weight of nylon 6 in the sheath resin composition.
• a core-sheath composite fiber (single fiber fineness 58 dtex) was obtained in the same manner as in Example 1.
• Example 3 In the core resin composition, 100 parts by weight of the brominated epoxy flame retardant and 2 parts by weight of sodium antimonate are added to 100 parts by weight of polyethylene terephthalate. A core-sheath composite fiber (single fiber fineness 58 dtex) was added to nylon 6 in the same manner as in Example 1 except that the brominated epoxy flame retardant was added in an amount of 15 parts by weight and sodium antimonate was added in an amount of 2 parts by weight. Obtained.
• Example 4 In the core resin composition, 100 parts by weight of the brominated epoxy flame retardant and 2 parts by weight of sodium antimonate are added to 100 parts by weight of polyethylene terephthalate. A core-sheath composite fiber (single fiber fineness 58 dtex) was added to nylon 6 in the same manner as in Example 1 except that the brominated epoxy flame retardant was added in an amount of 20 parts by weight and sodium antimonate was added in an amount of 2 parts by weight. Obtained.
• Example 5 In the core resin composition, 100 parts by weight of the brominated epoxy flame retardant and 2 parts by weight of sodium antimonate are added to 100 parts by weight of polyethylene terephthalate.
• the core is the same as in Example 1 except that the nylon 6 is changed to add 10 parts by weight of the brominated epoxy flame retardant, 2 parts by weight of the sodium antimonate, and 3 parts by weight of the phosphorus flame retardant A.
• a sheath composite fiber single fiber fineness 58 dtex
• Example 6 In the core resin composition, 100 parts by weight of the brominated epoxy flame retardant and 2 parts by weight of sodium antimonate are added to 100 parts by weight of polyethylene terephthalate.
• the core is the same as in Example 1 except that the nylon 6 is changed to add 10 parts by weight of the brominated epoxy flame retardant, 2 parts by weight of the sodium antimonate, and 5 parts by weight of the phosphorus flame retardant A.
• a sheath composite fiber single fiber fineness 58 dtex
• Example 7 In the core resin composition, 100 parts by weight of the brominated epoxy flame retardant and 2 parts by weight of sodium antimonate are added to 100 parts by weight of polyethylene terephthalate. A core-sheath composite fiber (single fiber fineness 58 dtex) was obtained in the same manner as in Example 1 except that the brominated epoxy flame retardant was changed to 15 parts by weight and sodium antimonate was changed to 2 parts by weight with respect to nylon 6.
• Example 8 In the core resin composition, 100 parts by weight of the brominated epoxy flame retardant and 12 parts by weight of sodium antimonate are added to 100 parts by weight of polyethylene terephthalate. A core-sheath composite fiber (single fiber fineness 58 dtex) was obtained in the same manner as in Example 1 except that the brominated epoxy flame retardant was changed to 30 parts by weight and sodium antimonate was changed to 5 parts by weight with respect to nylon 6.
• the core-sheath composite fibers for artificial hair obtained in Examples 1 to 3 to which zinc phosphinate is added as a flame retardant in the sheath portion have a feel and appearance (gloss) similar to human hair. It had good combability and flame retardancy.
• the core-sheath composite fiber for artificial hair to which the aromatic condensed phosphate ester-based polymer obtained in Examples 4 and 5 is added as a flame retardant in the sheath portion also has a tactile sensation and appearance (gloss) similar to human hair. It also had good combability and flame retardancy.
• the core-sheath composite fibers for artificial hair obtained in Comparative Examples 1 and 2 to which aluminum phosphinate was added as a flame retardant in the sheath portion had a significantly different tactile sensation and appearance (gloss) from human hair, and were different from those of Example 1. The result was that the flame retardancy was also inferior in comparison.
• the tactile sensation and combability were inferior to those in Comparative Example 3, and it was difficult to achieve both flame retardancy, tactile sensation, gloss, and combability.
• the core-sheath composite fibers for artificial hair of Comparative Examples 5 to 7 were inferior in flame retardancy because the amount of the flame retardant added was small.
• the present invention is not particularly limited, but may include, for example, one or more embodiments described below.
• a core-sheath composite fiber for artificial hair including a core portion and a sheath portion covering the core portion.
• the core portion is composed of a core portion resin composition containing a polyester resin
• the sheath portion is composed of a sheath portion resin composition containing a polyamide resin.
• the core resin composition contains a brominated flame retardant and a flame retardant aid
• the sheath resin composition contains a phosphorus flame retardant.
• the phosphorus-based flame retardant contains one or more selected from the group consisting of zinc phosphinate and a condensed phosphoric acid ester-based compound.
• the core-sheath composite fiber for artificial hair contains a total of brominated flame retardants, phosphorus-based flame retardants, and flame retardant aids when the total of the main component resin of the core and the main component resin of the sheath is 100 parts by weight.
• a core-sheath composite fiber for artificial hair which comprises 20 parts by weight or more and 40 parts by weight or less.
• the core resin composition contains a total of 20 parts by weight or more and 40 parts by weight or less of a brominated flame retardant and a flame retardant aid with respect to 100 parts by weight of the main component resin, and the sheath resin composition is:
• Both the core resin composition and the sheath resin composition contain 1 part by weight or more and 5 parts by weight or less of the flame retardant aid with respect to 100 parts by weight of the main component resin [1] to [3]. ]
• the core-sheath composite fiber for artificial hair according to any one of.
• the core portion is composed of a resin composition containing at least one polyester-based resin selected from the group consisting of polyalkylene terephthalate and a copolymerized polyester mainly composed of polyalkylene terephthalate as a main component resin.
• the core-sheath composite fiber for artificial hair according to any one of [1] to [5].
• the sheath portion is composed of a resin composition containing a polyamide-based resin mainly composed of at least one selected from the group consisting of nylon 6 and nylon 66 as a main component resin, [1] to [6]. ]
• the core-sheath composite fiber for artificial hair according to any one of.
• a headdress product containing the core-sheath composite fiber for artificial hair according to any one of [1] to [7].

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Artificial Filaments (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Multicomponent Fibers (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=79315962

Family Applications (1)

Country Status (3)

Cited By (1)

Citations (3)

Family Cites Families (1)

• 2021
  • 2021-05-27 WO PCT/JP2021/020253 patent/WO2022004212A1/ja not_active Ceased
  • 2021-05-27 JP JP2022533747A patent/JP7685497B2/ja active Active
• 2022
  • 2022-11-17 US US17/988,984 patent/US12446643B2/en active Active

Patent Citations (3)

Also Published As

Similar Documents

Legal Events