WO2006038447A1 - Vinyl chloride resin composition, vinyl chloride fiber, process for producing the same, and fiber for artificial hair - Google Patents

Vinyl chloride resin composition, vinyl chloride fiber, process for producing the same, and fiber for artificial hair Download PDF

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Publication number
WO2006038447A1
WO2006038447A1 PCT/JP2005/017048 JP2005017048W WO2006038447A1 WO 2006038447 A1 WO2006038447 A1 WO 2006038447A1 JP 2005017048 W JP2005017048 W JP 2005017048W WO 2006038447 A1 WO2006038447 A1 WO 2006038447A1
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WIPO (PCT)
Prior art keywords
fiber
vinyl
vinyl chloride
mass
copolymer
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Application number
PCT/JP2005/017048
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French (fr)
Japanese (ja)
Inventor
Atsushi Horihata
Akira Sakurai
Original Assignee
Denki Kagaku Kogyo Kabushiki Kaisha
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Application filed by Denki Kagaku Kogyo Kabushiki Kaisha filed Critical Denki Kagaku Kogyo Kabushiki Kaisha
Priority to JP2006539210A priority Critical patent/JP4890256B2/en
Publication of WO2006038447A1 publication Critical patent/WO2006038447A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene

Definitions

  • Chlorinated boule based resin composition Chlorinated boule based fiber and method for producing the same, and fiber for artificial hair
  • the present invention relates to a human hair like eyebrow, hue, and texture used in the manufacture of a vinyl chloride resin composition and a hair decoration product such as a wig, a hairpiece, a blade, a gesture hair and the like.
  • the present invention relates to a vinyl chloride-based fiber comprising the vinyl chloride-based resin composition.
  • a polyvinyl chloride-based fiber obtained by spinning a polyvinyl chloride-based resin is excellent in transparency and flexibility, so it is often used as a fiber for artificial hair constituting a hair decoration product. It has been.
  • a method using a solvent there are a method using a solvent and a method not using a solvent.
  • a wet spinning method and a dry spinning method are known, and as the above-mentioned "method not using a solvent”, a melt spinning method is known.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 10-102317
  • melt-spinning is a spinning method in which a resin is extruded at high temperature and pressure using an extruder, but salt-like boule based resins have high melt viscosity and extremely high spinnability. Since it is low, it has been difficult to melt and spin salted boule based resin to obtain a constant quality salted boule fiber. And, since the specific gravity of vinyl chloride fiber, which is the raw material of vinyl chloride fiber, is large, heat treatment is applied to this to make it curled by making it into a hair decoration product.
  • the proximal part of the near part is stretched by its own weight, For this reason, there is a problem in that the shape of the curl becomes different between the part to be worn on the head and the part at the tip apart from the head force, and the uniformity of the carnore becomes worse. Therefore, the caustic vinyl chloride fibers are not suitable for styling wigs or weavings where uniform loose curl shapes are required.
  • the present invention aims to solve these problems.
  • the object of the present invention is to provide a vinyl chloride-based fiber having a uniform and loose curl shape required as a fiber for artificial hair.
  • the invention described in claim 2 relates to the invention described in claim 1, wherein the aromatic bule monomer (a) is a force styrene, and the cyanide bule (b) Is acrylonitrile, and the (meth) acrylic acid ester (c) is a methyl methacrylate compound.
  • the invention described in claim 3 is the invention described in claim 1 or 2, wherein the bi - Le based copolymer, a styrene 70-90 mass 0/0, acrylonitrile 30-10 wt 0/0, and is characterized in that a copolymer containing a polymerization.
  • the invention described in claim 4 is the invention described in claim 1 or 2, wherein the bi - Le based copolymer, styrene 10 to 40 weight 0/0, methyl methallyl rate 90 50 mass 0/0, acrylonitrile 0: is characterized in that the LO wt% is a copolymer containing polymerized.
  • the invention described in claim 5 is a vinyl chloride-based fiber comprising the vinyl chloride-based resin composition according to any one of claims 1 to 4 .
  • the invention recited in claim 6 is the vinyl chloride-based vinyl compound according to any one of claims 1 to 4.
  • a resin composition is melt-spun at a temperature of 170 to 190 ° C., which is a method for producing a chloride-based fiber.
  • the invention described in claim 7 is the method according to the invention described in claim 6, under an air atmosphere in which the melt-spun salted boule fiber is maintained at a temperature of 90 to 120 ° C. After stretching to 4 times, heat-relaxing this stretched chloride-based fiber at a temperature of 110 to 140 ° C. in an air atmosphere to a length of 60 to 100% before stretching. It is a feature.
  • the invention described in claim 8 is a fiber for artificial hair characterized in that the vinyl chloride-based fiber according to claim 5 is used as a fiber for artificial hair.
  • the aromatic vinyl monomer (a) is styrene and the cyanide bule (b) is acrylonitrile, the cocoon during spinning is It becomes easy to adjust the oil pressure, so that the screw load can be reduced, and thus, the long run property of melt spinning can be ensured.
  • the (meth) acrylic ester (c) is a methyl methacrylate
  • the methyl metatalylate has a solubility parameter close to that of a vinyl chloride resin, so it is possible to make the fiber transparent. It can be improved that way.
  • the vinyl copolymer is a copolymer containing 70 to 90% by mass of styrene and 30 to 50% by mass of acrylonitrile:
  • the compatibility of the boule-based copolymer with the salt-like bole-based resin is improved to improve the spinnability, and as a result, more stable productivity can be obtained.
  • the boule-based copolymer polymerizes 10 to 40% by mass of styrene, 90 to 50% by mass of methyl methacrylate, and 0 to 10% by mass of acrylonitrile. Since it is a copolymer contained, the compatibility between the vinyl-based copolymer and the vinyl chloride-based resin is improved to improve the spinnability, and as a result, more stable productivity can be obtained.
  • a chloride-vinyl-based fiber comprising the chloride-based resin composition according to any one of claims 1 to 4 As a result, it becomes a vinyl chloride-based fiber having a uniform loose curl shape required as a fiber for artificial hair.
  • melt spinning of the vinyl chloride resin composition according to any one of claims 1 to 4 is carried out at a temperature of 170 to 190 ° C. Therefore, the long runnability of melt spinning can be secured, and hence the productivity of vinyl chloride fiber can be improved.
  • the stretched film is stretched.
  • the heat-relaxation of the chlorinated boule fibers to a length of 60 to 100% before stretching in an air atmosphere maintained at a temperature of 110 to 140 ° C. results in strength, elongation, and thermal contraction rate of It can be a balanced vinyl chloride fiber.
  • the vinyl chloride fiber according to claim 5 is used as a fiber for artificial hair, the uniform loose, curled shape required as a fiber for artificial hair Can be used as an artificial hair fiber.
  • units such as “parts” indicating the composition of the chloride-based resin composition of the present invention are not particularly limited unless otherwise specified. It shall be displayed on a mass basis.
  • the vinyl chloride-based resin composition of the present invention comprises (A) 100 parts by weight of a salt-based vinyl resin, and (B) an aromatic group monomer (a), and cyanide salt. 5 to 50 parts by mass of a vinyl copolymer comprising one or more vinyl monomers selected from (b) and (meth) acrylic acid ester (c) Contains
  • a vinyl-based coweight comprising (a) and one or more vinyl monomers selected from cyanide vinyl (b) and (meth) acrylic acid ester
  • c) When 5 to 50 parts by mass of coalesced is contained, it is possible to provide a salty-vinyl-based fiber having a uniform loose curl shape required as a fiber for artificial hair.
  • the productivity of salt vinyl fibers can be improved.
  • the blending amount of the vinyl copolymer when the blending amount of the vinyl copolymer is less than 5 parts by mass, the specific gravity of the obtained fiber can not be reduced, and when it is more than 50 parts by mass. Thread breakage frequency increases. Therefore, the blending amount of the vinyl copolymer is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass.
  • the aromatic vinyl monomer (a) constituting the vinyl-based copolymer improves the compatibility between the vinyl-based copolymer and the salt-based resin, and thus the vinyl-based copolymer contains the vinyl-based copolymer.
  • the spinnability of the chlorinated boule based resin composition of the present invention can be improved.
  • the aromatic vinyl monomer (a) constituting the vinyl-based copolymer is, for example, styrene, ⁇ -substituted styrene such as oc-methylstyrene, butyltoluene, ethylstyrene, t-butylstyrene, chlorstyrene, bromstyrene, distyrene Among them are aromatic ring-substituted styrenes such as bromostyrene and tribromostyrene, among which styrene is particularly preferred.
  • the above-mentioned styrene makes it possible to reduce the screw load since adjustment of the resin pressure at the time of spinning is easy, so that it is possible to secure the long run property of melt spinning for a longer time.
  • the vinyl cyanide monomer (b) constituting the above-mentioned vinyl copolymer is, for example, attril nitrile, metataryl trill-tolyl and crotal acrylonitrile having a force of these. Trill is particularly preferred.
  • the acrylonitrile is easy to adjust the resin pressure at the time of spinning, so that it is possible to reduce the screw load, and therefore, it is possible to ensure the long run property of melt spinning for a longer time.
  • methyl methacrylate and ethyl methacrylate are particularly preferable methyl methacrylate of these.
  • the methyl metatarylate can improve the transparency of the fiber because the solubility parameter is close to that of salt-based veal resin.
  • the aromatic boule alone is preferably used.
  • the mer (a) is preferably styrene, and the cyanide (b) is preferably acryloyl-tolyl, and the (meth) acrylic ester (c) is preferably , Methyl meta atarilate.
  • the aromatic boule monomer (a) is styrene and the cyanide boule (b) is acrylonitrile, adjustment of the resin pressure at the time of spinning becomes easy, and therefore, The screw load can be reduced, thus ensuring long and long runnability of melt spinning.
  • the methyl metatalylate has a solubility parameter close to that of the salt-like resin, and therefore the fiber transparency is improved. That can be improved.
  • the boule-based copolymer is a copolymer which polymerizes and contains 70 to 90% by mass of styrene and 30 to: 50% by mass of acrylonitrile.
  • styrene 75 to 85 weight 0/0, acrylonitrile 25-15 wt 0/0 is a copolymer containing a polymerization.
  • the vinyl copolymer is a copolymer containing 70 to 90% by mass of styrene and 30 to: 50% by mass of acrylonitrile
  • the vinyl copolymer and the salt thereof are mixed with each other.
  • the compatibility with the boule based resin is improved to improve the spinnability, and as a result, more stable productivity can be obtained.
  • the vinyl copolymer preferably contains 10 to 40% by mass of styrene, 90 to 50% by mass of methyl methacrylate, and 0 to 10% by mass of acrylonitrile.
  • the power which is a copolymer More preferably, it is a copolymer which polymerizes and contains 15-30 mass% of styrene, 85-60 mass% of methyl methacrylate, and 0-10 mass% of acrylonitrile.
  • the Bulle based copolymer, styrene 10 to 40 weight 0/0, and methyl Metarireto 90 to 50 wt% if it is a copolymer of polymerizing containing acrylonitrile 0 to 10 mass%, the The compatibility between the block copolymer and the vinyl chloride resin is improved to improve the spinnability, and as a result, more stable productivity can be obtained.
  • the "chlorinated vinyl resin” in the present invention is obtained by means of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. In view of the above, it is preferably produced by suspension polymerization.
  • the “salt-to-vinyl salt” is preferably a homopolymer salt which is a homopolymer of a salt-to-be-known conventionally known salt, or a copolymer salt of a conventionally known salt. As long as the purpose of the present invention is not violated, Even other salt and vinyl based resins do not force.
  • copolymer resin conventionally known copolymer resins can be used, but preferably, vinyl chloride-acetate copolymer resin, chloride-bibulide propionate copolymer resin, etc.
  • Copolymer resins with acid esters Chlorinated ethylene copolymer resins, Chlorinated vinyl-propylene copolymers, etc.
  • homopolymer-copolymers which are homopolymers of chloride-vinyl, which are homopolymers of chloride-vinyl, and copolymers of ethylene-copolymer-resin, preferably chloride-biol.
  • Copolymer resins such as butyl acetate copolymer resins.
  • the content of the comonomer is not particularly limited, and can be determined according to the required quality such as molding processability and yarn properties.
  • the viscosity average degree of polymerization of the "salt-and-bullet-based resin” in the present invention is preferably 600 to 1600. If the viscosity average degree of polymerization of “salt-and-bule-based resin” is less than 600, the melt viscosity is lowered, so that the resulting vinyl chloride-based fiber may be easily thermally shrunk. On the other hand, if the viscosity average degree of polymerization of “salt-and-bulb-based resin” exceeds 1600, the melt viscosity of the vinyl chloride-based resin will be high, and the nozzle pressure will be high, which makes safe spinning difficult.
  • viscosity average degree of polymerization is obtained by dissolving 200 g of resin in 50 ml of -trobenzene, measuring the specific viscosity using a Ubbelohde viscometer in a 30 ° C thermostatic bath, according to JIS-K6721. It is calculated.
  • additives used in vinyl chloride-based fat composition may be blended according to the purpose.
  • additives include heat stabilizers, plasticizers, lubricants, compatibilizers, processing aids, toughening agents, UV absorbers, antioxidants, antistatic agents, fillers, flame retardants, pigments, and initial color improvement.
  • additives such as agents, conductivity imparting agents, surface treatment agents, light stabilizers, and perfumes.
  • the weight-average molecular weight of the “bul-based copolymer” in the present invention is preferably 50,000 to 110,000, more preferably 60,000 to 100,000. If the weight-average molecular weight of the “vinyl-based copolymer” is less than 50,000 or over 110,000, the compatibility with the salt-based resin is deteriorated, so the physical properties Come down.
  • the adjustment of the weight average molecular weight of the “vinyl copolymer” is performed using a known chain transfer agent.
  • the chain transfer agent include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan and n-octy mercaptan; terpenes such as dipentene and terpinorene; halogenated hydrocarbons such as cromoform and broroform. And ⁇ - Methylstyrene dimers Among them, mercaptans are particularly preferred.
  • the method for producing the “vinyl-based copolymer” is not particularly limited.
  • polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization and the like can be adopted.
  • the method for producing the “vinyl-based copolymer” is not limited by either the polymerization method or the continuous polymerization method.
  • the "vinyl chloride-based fiber” of the present invention comprises the vinyl chloride-based resin composition according to any one of claims 1 to 4.
  • the "salt-vinyl-based fiber” of the present invention has the strength of the salt-like vinyl-based resin composition according to any one of claims 1-4, it becomes a fiber for artificial hair. It becomes a vinyl chloride-based fiber having the required uniform curl shape.
  • the thickness of one “vinyl chloride-based fiber” of the present invention is preferably 20 to: LOO denier, and more preferably 50 to 80 denier.
  • LOO denier the thickness of a single chloride boule fiber is 20 to 20: LOO denier, it becomes comparable to natural hair, and the thickness of one chloride boule fiber is 50 to 80 denier. In such a case, the feeling and feel will be improved.
  • the cross-sectional shape of the "salt vinyl-based fiber" of the present invention may be any shape, for example, circular, oval, glasses, star, U-shaped, T-shaped, U-shaped, triangular, square, It may be cruciform, heart-shaped, horseshoe-shaped, or a combination of these. Moreover, these hollow bodies may be sufficient.
  • the "vinyl chloride fiber” of the present invention comprises melt spinning the vinyl chloride resin composition according to any one of claims 1 to 4 at a temperature of 170 to 190 ° C.
  • the "salt-and-bullet-based fiber” of the present invention melts the salt-and-fill resin composition according to any one of claims 1 to 4 at a temperature of 170 to 190 ° C.
  • the productivity of chloride fiber is ensured. Can be improved.
  • a powder compound obtained by mixing a vinyl chloride-based resin composition with a mixer such as a shell mixer or ribbon platen, or melting thereof is used. Melt-spinning the mixed pellet compound at a temperature of 170 to 190 ° C. using a melt extruder such as a single-screw extruder, a counter-rotating twin-screw extruder, a conical twin-screw extruder, etc. Ru.
  • a conventionally known extruder can be used.
  • an extruder such as a single-screw extruder, a counter-rotating twin-screw extruder, or a co-Carni shaft extruder can be used, preferably a single-screw extruder having a diameter of about 35 to 85 ⁇ . It is preferable to use an extruder or a conical extruder having a diameter of about 35 to 50 ⁇ . If the bore diameter is too large, the amount of extrusion will increase and the nozzle pressure will become too large, so the flow rate of the undrawn yarn may become too fast, which may make it difficult to wind up later. .
  • the melt-spun vinyl chloride-based fiber was stretched to 2 to 4 times in an air atmosphere maintained at a temperature of 90 to 120 ° C. After that, the drawn vinyl chloride-based fibers are thermally relaxed in an air atmosphere maintained at a temperature of 110 to 140 ° C. to a length of 60 to LOO% before stretching.
  • the drawn chloride-vinyl fibers can be 110 to 140
  • the strength, elongation, and heat shrinkage rate of balanced salt vinyl chloride It can be a fiber base.
  • the "fiber for artificial hair” of the present invention is a fiber according to claim 5, which is a fiber for artificial hair.
  • the vinyl chloride-based fiber according to claim 5 is used as a fiber for artificial hair, it is for artificial hair having a uniform loose curl shape required as a fiber for artificial hair. It can be fiber.
  • Example 1 Examples of the present invention and comparative examples will be described below, but these examples and comparative examples are all illustrative and do not limit the contents of the present invention.
  • Example 1 Example 1
  • Example 1 (a) Styrene 20 mass fraction of the monomers constituting the vinyl copolymer in ⁇ composition of step 0/0, acrylonitrile 5 mass 0/0, and, with 75 weight% methyl meth Tali rate A vinyl chloride-based fiber was obtained in the same manner as in Example 1 except for the above.
  • a salt was prepared in the same manner as in Example 1 except that the proportions of the monomers constituting the vinyl copolymer in the resin composition in step (a) of Example 1 were 70% by mass of styrene and 30% by mass of acrylonitrile.
  • the vinyl fiber was obtained.
  • Example 1 was repeated except that the proportion of the monomers constituting the vinyl copolymer in the resin composition of step (a) of Example 1 was 10% by mass of styrene and 90% by mass of methyl methacrylate. In the same manner, vinyl chloride-based fibers were obtained.
  • a vinyl chloride-based fiber was obtained in the same manner as in Example 1, except that the blending amount of the vinyl copolymer in the resin composition in the step (a) of Example 1 was changed to 60 parts by mass.
  • “Curl uniformity” in Table 1 was evaluated by the following procedure. That is, a fiber bundle (hot-rolled yarn), which is a single fiber strength of 120 fibers of bible fiber, is cut into a fixed length, and this is cut into diameters.
  • the both ends were fixed by winding around an aluminum cylinder made of 20 mm, and then the whole aluminum cylinder was placed in an air circulating oven at 90 ° C. and heated for 30 minutes. Then, the aluminum cylinder wound with the fiber bundle was left to stand in a temperature-controlled room at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours. Next, remove the fiber bundle from the stainless steel cylinder and fixate and suspend one end, in which case, the angle of the curled valley (valley) of the root and the curled valley of the tip ( The angle of the valley portion was calculated, and the curl uniformity was evaluated by a value (angle ratio) obtained by dividing the angle of the curl shape of the tip portion by the angle of the curl shape of the root portion. The closer the angle ratio is to 1, the more evenly the curls that the difference in the angle becomes, which means that.
  • Curl uniformity of salt-based fibers is evaluated according to the following evaluation criteria
  • the “spinning property” in Table 1 was evaluated by the number of times single thread breakage (several 120 out of 120) occurred when melt spinning was performed. That is, the curling uniformity of the chloride-based fiber is calculated by converting the number of occurrences of single yarn breakage into the yarn breakage frequency (number of hours Z hours) per hour, and the following evaluation criteria
  • the curl uniformity and the spinnability were both usable levels, and were the target chloride-type fibers.
  • the curl uniformity and spinnability were both at good levels.
  • the salted boule based fibers obtained in Examples 3 and 4 have a somewhat difficult spinnability compared to the vinyl chloride fibers obtained in Examples 1 and 2, and the curl uniformity is It was at a good level.
  • the curling uniformity of the chloride-based fiber obtained in Comparative Example 1 was poor because the blending amount of the vinyl-based copolymer was small.
  • the vinyl chloride-based fiber obtained using the vinyl chloride-based resin composition of the present invention is, for example, for hair decoration of wigs, hair pieces, blades, doll hair, extension hair, etc. It can be used for artificial hair fibers of

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A vinyl chloride resin composition which comprises (A) 100 parts by mass of a vinyl chloride resin and (B) 5-50 parts by mass of a vinyl copolymer comprising units of an aromatic vinyl monomer (a) and units of one or more vinyl monomers selected among vinyl cyanide (b) and (meth)acrylic esters (c). The vinyl copolymer preferably is a copolymer obtained by polymerizing 70-90 mass% styrene with 30-10 mass% acrylonitrile. When vinyl chloride fibers comprising this vinyl chloride resin composition are used as artificial-hair fibers, the fibers can have a loosely curled uniform shape because the fibers can be lightweight. When the vinyl chloride resin composition is subjected to melt spinning, long-run melt spinning is ensured and, hence, satisfactory and stable productivity is obtained.

Description

明 細 書  Specification
塩化ビュル系樹脂組成物、塩化ビュル系繊維及びその製造方法、並び に、人工毛髪用繊維  Chlorinated boule based resin composition, chlorinated boule based fiber and method for producing the same, and fiber for artificial hair
技術分野  Technical field
[0001] 本発明は、塩化ビニル系榭脂組成物、並びに、ウイッグ、ヘアピース、ブレード、ェ タステンションヘアー等の頭髪装飾製品の製造において用いられる人毛に似た艷、 色相、及び、風合いを有する該塩化ビニル系榭脂組成物からなる塩化ビニル系繊維 に関するものである。  [0001] The present invention relates to a human hair like eyebrow, hue, and texture used in the manufacture of a vinyl chloride resin composition and a hair decoration product such as a wig, a hairpiece, a blade, a gesture hair and the like. The present invention relates to a vinyl chloride-based fiber comprising the vinyl chloride-based resin composition.
背景技術  Background art
[0002] 塩ィ匕ビュル系榭脂を紡糸して得た塩ィ匕ビュル系繊維は、透明性及び柔軟性に優 れているので、頭髪装飾製品を構成する人工毛髪用繊維として、多く使用されている 。この人工毛髪用繊維を工業的に製造するには、溶剤を用いる方法と溶媒を使用し ない方法とがある。前記「溶剤を用いる方法」としては、湿式紡糸法及び乾式紡糸法 が知られており、また、前記「溶媒を使用しない方法」としては、溶融紡糸法が知られ ている。  [0002] A polyvinyl chloride-based fiber obtained by spinning a polyvinyl chloride-based resin is excellent in transparency and flexibility, so it is often used as a fiber for artificial hair constituting a hair decoration product. It has been. In order to industrially produce this artificial hair fiber, there are a method using a solvent and a method not using a solvent. As the above-mentioned "method using a solvent", a wet spinning method and a dry spinning method are known, and as the above-mentioned "method not using a solvent", a melt spinning method is known.
[0003] 前記「溶融紡糸法」としては、塩化ビニル榭脂、塩素化塩ィ匕ビュル榭脂及びェチレ ン ·酢ビ Z塩ビグラフト重合榭脂を有する塩ィ匕ビ二ル系榭脂組成物を溶融紡糸するも のが提案されている (特許文献 1を参照。 ) o  [0003] As the above-mentioned "melt spinning method", a vinyl chloride resin composition having vinyl chloride resin, chlorinated salt vinyl ether resin, ethylene vinyl acetate Z-vinyl chloride graft polymer resin. It has been proposed to melt spinner (see Patent Document 1) o
特許文献 1 :特開平 10— 102317号公報  Patent Document 1: Japanese Patent Application Laid-Open No. 10-102317
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problem that invention tries to solve
[0004] しかしながら、溶融紡糸法は、押出機を使用し榭脂を高温高圧で押出す紡糸法で あるが、塩ィ匕ビュル系榭脂は、溶融粘度が高ぐ且つ、曳糸性が極めて低いので、塩 化ビュル系榭脂を溶融紡糸して一定品質の塩ィ匕ビュル繊維とすることは、難 、と!ヽ う問題があった。そして、塩化ビニル系繊維は、その原料である塩ィ匕ビ二ル系榭脂の 比重が大きいので、これに熱処理を施してカールさせることにより頭髪装飾製品とし た時に、頭に装着する側に近い部分の根元部分が繊維自重により伸びてしまい、そ のために、頭に装着する側の部分と頭力 離れた先端の部分とでは、カールの形状 が異なったものとなって、カーノレの均一'性が悪くなつてしまうという問題があった。そ れ故、カゝかる塩ィ匕ビニル繊維は、均一なゆるいカール形状が要求されるようなスタイ ノレのウイッグやウィービングには不向きとなっていた。 However, melt-spinning is a spinning method in which a resin is extruded at high temperature and pressure using an extruder, but salt-like boule based resins have high melt viscosity and extremely high spinnability. Since it is low, it has been difficult to melt and spin salted boule based resin to obtain a constant quality salted boule fiber. And, since the specific gravity of vinyl chloride fiber, which is the raw material of vinyl chloride fiber, is large, heat treatment is applied to this to make it curled by making it into a hair decoration product. The proximal part of the near part is stretched by its own weight, For this reason, there is a problem in that the shape of the curl becomes different between the part to be worn on the head and the part at the tip apart from the head force, and the uniformity of the carnore becomes worse. Therefore, the caustic vinyl chloride fibers are not suitable for styling wigs or weavings where uniform loose curl shapes are required.
[0005] 本発明は、これらの問題を解決することを目的としている。  The present invention aims to solve these problems.
[0006] 即ち、本発明は、人工毛髪用繊維として必要とされる均一なゆるいカール形状を持 ち合わせた塩化ビニル系繊維を提供することを目的として!/ヽる。  That is, the object of the present invention is to provide a vinyl chloride-based fiber having a uniform and loose curl shape required as a fiber for artificial hair.
課題を解決するための手段  Means to solve the problem
[0007] 即ち、請求項 1に記載された発明は、前記目的を達成するために、 That is, in order to achieve the above object, the invention described in claim 1
(A)塩ィ匕ビュル系榭脂 100質量部、並びに、  (A) 100 parts by mass of salt-based resin, and
(B)芳香族ビニル単量体 (a)と、シアンィ匕ビニル (b)及び (メタ)クリル酸エステル (c) 力 選択される 1種又は 2種以上のビュル系単量体と、で構成されるビュル系共重合 体 5〜50質量部、  (B) Aromatic vinyl monomer (a) and cyanide vinyl (b) and (meth) acrylic acid ester (c) Force One or two or more boule monomers selected 5 to 50 parts by mass of the boule based copolymer,
を含有することを特徴とする塩ィ匕ビ二ル系榭脂組成物である。  And a vinyl chloride resin composition characterized by containing
[0008] 請求項 2に記載された発明は、請求項 1に記載された発明にお!/ヽて、前記芳香族 ビュル単量体（a)力 スチレンであり、前記シアン化ビュル (b)が、アクリロニトリルで あり、そして、前記 (メタ)クリル酸エステル (c)が、メチルメタアタリレートであることを特 徴とするちのである。 [0008] The invention described in claim 2 relates to the invention described in claim 1, wherein the aromatic bule monomer (a) is a force styrene, and the cyanide bule (b) Is acrylonitrile, and the (meth) acrylic acid ester (c) is a methyl methacrylate compound.
[0009] 請求項 3に記載された発明は、請求項 1又は 2に記載された発明において、前記ビ -ル系共重合体が、スチレン 70〜90質量0 /0と、アクリロニトリル 30〜10質量0 /0と、を 重合含有する共重合体であることを特徴とするものである。 [0009] The invention described in claim 3 is the invention described in claim 1 or 2, wherein the bi - Le based copolymer, a styrene 70-90 mass 0/0, acrylonitrile 30-10 wt 0/0, and is characterized in that a copolymer containing a polymerization.
[0010] 請求項 4に記載された発明は、請求項 1又は 2に記載された発明において、前記ビ -ル系共重合体が、スチレン 10〜40質量0 /0と、メチルメタリレート 90〜50質量0 /0と、 アクリロニトリル 0〜： LO質量％とを重合含有する共重合体であることを特徴とするもの である。 [0010] The invention described in claim 4 is the invention described in claim 1 or 2, wherein the bi - Le based copolymer, styrene 10 to 40 weight 0/0, methyl methallyl rate 90 50 mass 0/0, acrylonitrile 0: is characterized in that the LO wt% is a copolymer containing polymerized.
[0011] 請求項 5に記載された発明は、請求項 1〜4のいずれか 1項に記載の塩ィ匕ビニル系 榭脂組成物からなることを特徴とする塩ィ匕ビニル系繊維である。  [0011] The invention described in claim 5 is a vinyl chloride-based fiber comprising the vinyl chloride-based resin composition according to any one of claims 1 to 4 .
[0012] 請求項 6に記載された発明は、請求項 1〜4のいずれか 1項に記載の塩ィ匕ビニル系 榭脂組成物を 170〜 190°Cの温度で溶融紡糸することを特徴とする塩ィ匕ビ二ル系繊 維の製造方法である。 [0012] The invention recited in claim 6 is the vinyl chloride-based vinyl compound according to any one of claims 1 to 4. A resin composition is melt-spun at a temperature of 170 to 190 ° C., which is a method for producing a chloride-based fiber.
[0013] 請求項 7に記載された発明は、請求項 6に記載された発明において、前記溶融紡 糸した塩ィ匕ビュル系繊維を 90〜120°Cの温度に保持した空気雰囲気下で 2〜4倍 まで延伸した後、この延伸した塩ィ匕ビュル系繊維を 110〜140°Cの温度に保持した 空気雰囲気下で延伸前の 60〜 100%の長さになるまで熱弛緩させることを特徴とす るものである。  [0013] The invention described in claim 7 is the method according to the invention described in claim 6, under an air atmosphere in which the melt-spun salted boule fiber is maintained at a temperature of 90 to 120 ° C. After stretching to 4 times, heat-relaxing this stretched chloride-based fiber at a temperature of 110 to 140 ° C. in an air atmosphere to a length of 60 to 100% before stretching. It is a feature.
[0014] 請求項 8に記載された発明は、請求項 5に記載の塩ィ匕ビニル系繊維を人工毛髪用 繊維としたことを特徴とする人工毛髪用繊維である。  [0014] The invention described in claim 8 is a fiber for artificial hair characterized in that the vinyl chloride-based fiber according to claim 5 is used as a fiber for artificial hair.
発明の効果  Effect of the invention
[0015] 請求項 1に記載された発明によれば、（A)塩ィ匕ビュル系榭脂 100質量部、並びに、  [0015] According to the invention described in claim 1, (A) 100 parts by mass of a salt-and-bure based resin, and
(B)芳香族ビニル単量体 (a)と、シアンィ匕ビニル (b)及び (メタ)クリル酸エステル (c) 力 選択される 1種又は 2種以上のビュル系単量体と、で構成されるビュル系共重合 体 5〜50質量部、を含有しているので、人工毛髪用繊維として必要とされる均一なゆ るいカール形状を持ち合わせた塩ィ匕ビュル系繊維を提供することができる。また、溶 融紡糸のロングラン性を確保することができるので、塩ィ匕ビュル繊維の生産性を向上 させることがでさる。  (B) Aromatic vinyl monomer (a) and cyanide vinyl (b) and (meth) acrylic acid ester (c) Force One or two or more boule monomers selected Since it contains 5 to 50 parts by mass of the boule-based copolymer, it is possible to provide a salt boule-based fiber having a uniform gentle curl shape required as a fiber for artificial hair. . In addition, since the long run property of melt spinning can be secured, it is possible to improve the productivity of salted burle fibers.
[0016] 請求項 2に記載された発明によれば、前記芳香族ビニル単量体 (a)がスチレンであ り、そして、前記シアンィ匕ビュル (b)がアクリロニトリルであるので、紡糸時の榭脂圧の 調整が容易となり、そのために、スクリュー負荷を下げることができ、よって、溶融紡糸 のいつそう長時間のロングラン性を確保することができる。また、前記 (メタ)クリル酸ェ ステル (c)がメチルメタアタリレートであるところ、該メチルメタタリレートは塩ィ匕ビニル 系榭脂と溶解度パラメータが近 、ので、繊維の透明性を 、つそう向上させることがで きる。  [0016] According to the invention described in claim 2, since the aromatic vinyl monomer (a) is styrene and the cyanide bule (b) is acrylonitrile, the cocoon during spinning is It becomes easy to adjust the oil pressure, so that the screw load can be reduced, and thus, the long run property of melt spinning can be ensured. Also, where the (meth) acrylic ester (c) is a methyl methacrylate, the methyl metatalylate has a solubility parameter close to that of a vinyl chloride resin, so it is possible to make the fiber transparent. It can be improved that way.
[0017] 請求項 3に記載された発明によれば、前記ビニル系共重合体が、スチレン 70〜90 質量％と、アクリロニトリル 30〜： LO質量％と、を重合含有する共重合体であるので、 該ビュル系共重合体と塩ィ匕ビュル系榭脂との相溶性が向上して紡糸性が向上し、そ のために、さらに安定した生産性が得られる。 [0018] 請求項 4に記載された発明によれば、前記ビュル系共重合体が、スチレン 10〜40 質量％と、メチルメタリレート 90〜50質量％と、アクリロニトリル 0〜10質量％とを重合 含有する共重合体であるので、該ビニル系共重合体と塩化ビニル系榭脂との相溶性 が向上して紡糸性が向上し、そのために、さらに安定した生産性が得られる。 [0017] According to the invention described in claim 3, since the vinyl copolymer is a copolymer containing 70 to 90% by mass of styrene and 30 to 50% by mass of acrylonitrile: The compatibility of the boule-based copolymer with the salt-like bole-based resin is improved to improve the spinnability, and as a result, more stable productivity can be obtained. According to the invention described in claim 4, the boule-based copolymer polymerizes 10 to 40% by mass of styrene, 90 to 50% by mass of methyl methacrylate, and 0 to 10% by mass of acrylonitrile. Since it is a copolymer contained, the compatibility between the vinyl-based copolymer and the vinyl chloride-based resin is improved to improve the spinnability, and as a result, more stable productivity can be obtained.
[0019] 請求項 5に記載された発明によれば、請求項 1〜4のいずれか 1項に記載の塩ィ匕ビ -ル系榭脂組成物カゝらなる塩ィ匕ビニル系繊維であるので、人工毛髪用繊維として必 要とされる均一なゆるいカール形状を持ち合わせた塩ィ匕ビニル系繊維となる。  [0019] According to the invention described in claim 5, a chloride-vinyl-based fiber comprising the chloride-based resin composition according to any one of claims 1 to 4 As a result, it becomes a vinyl chloride-based fiber having a uniform loose curl shape required as a fiber for artificial hair.
[0020] 請求項 6に記載された発明によれば、請求項 1〜4の 、ずれか 1項に記載の塩化ビ -ル系榭脂組成物を 170〜190°Cの温度で溶融紡糸するので、溶融紡糸のロングラ ン性を確保することができ、そのために、塩化ビニル繊維の生産性を向上させること ができる。  [0020] According to the invention described in claim 6, melt spinning of the vinyl chloride resin composition according to any one of claims 1 to 4 is carried out at a temperature of 170 to 190 ° C. Therefore, the long runnability of melt spinning can be secured, and hence the productivity of vinyl chloride fiber can be improved.
[0021] 請求項 7に記載された発明によれば、前記溶融紡糸した塩化ビニル系繊維を 90〜 120°Cの温度に保持した空気雰囲気下で 2〜4倍まで延伸した後、この延伸した塩 化ビュル系繊維を 110〜140°Cの温度に保持した空気雰囲気下で延伸前の 60〜1 00%の長さになるまで熱弛緩させるので、強度、伸度、及び、熱収縮率のバランスの とれた塩ィ匕ビニル系繊維とすることができる。  [0021] According to the invention described in claim 7, after the melt spun vinyl chloride fiber is stretched to 2 to 4 times in an air atmosphere maintained at a temperature of 90 to 120 ° C., the stretched film is stretched The heat-relaxation of the chlorinated boule fibers to a length of 60 to 100% before stretching in an air atmosphere maintained at a temperature of 110 to 140 ° C. results in strength, elongation, and thermal contraction rate of It can be a balanced vinyl chloride fiber.
[0022] 請求項 8に記載された発明によれば、請求項 5に記載の塩化ビニル系繊維を人工 毛髪用繊維としたので、人工毛髪用繊維として必要とされる均一なゆる 、カール形 状を持ち合わせた人工毛髪用繊維とすることができる。  [0022] According to the invention described in claim 8, since the vinyl chloride fiber according to claim 5 is used as a fiber for artificial hair, the uniform loose, curled shape required as a fiber for artificial hair Can be used as an artificial hair fiber.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0023] 以下、本発明の実施の形態を説明する力 本明細書においては、本発明の塩化ビ -ル系榭脂組成物の配合組成を示す「部」等の単位は、特に断らない限り質量基準 で表示するものとする。 Hereinafter, in the present specification, units such as “parts” indicating the composition of the chloride-based resin composition of the present invention are not particularly limited unless otherwise specified. It shall be displayed on a mass basis.
[0024] 本発明の塩化ビニル系榭脂組成物は、（A)塩ィ匕ビ二ル系榭脂 100質量部、並び に、（B)芳香族ビュル単量体 (a)と、シアンィ匕ビュル (b)、及び、（メタ)クリル酸エステ ル (c)から選択される 1種又は 2種以上のビニル系単量体と、で構成されるビニル系 共重合体 5〜50質量部、を含有している。  The vinyl chloride-based resin composition of the present invention comprises (A) 100 parts by weight of a salt-based vinyl resin, and (B) an aromatic group monomer (a), and cyanide salt. 5 to 50 parts by mass of a vinyl copolymer comprising one or more vinyl monomers selected from (b) and (meth) acrylic acid ester (c) Contains
[0025] このように、（A)塩ィ匕ビュル系榭脂 100質量部、並びに、（B)芳香族ビニル単量体 (a)と、シアンィ匕ビニル (b)、及び、（メタ)クリル酸エステル (c)から選択される 1種又 は 2種以上のビニル系単量体と、で構成されるビニル系共重合体 5〜50質量部、を 含有していると、人工毛髪用繊維として必要とされる均一なゆるいカール形状を持ち 合わせた塩ィ匕ビニル系繊維を提供することができる。また、溶融紡糸のロングラン性 を確保することができるので、塩ィ匕ビニル繊維の生産性を向上させることができる。 Thus, (A) 100 parts by weight of salt-based resin, and (B) aromatic vinyl monomer A vinyl-based coweight comprising (a) and one or more vinyl monomers selected from cyanide vinyl (b) and (meth) acrylic acid ester (c) When 5 to 50 parts by mass of coalesced is contained, it is possible to provide a salty-vinyl-based fiber having a uniform loose curl shape required as a fiber for artificial hair. In addition, since the long run property of melt spinning can be secured, the productivity of salt vinyl fibers can be improved.
[0026] 本発明にお 、ては、ビニル系共重合体の配合量が 5質量部より少な 、と、得られた 繊維の比重を小さくすることができなくなり、また、 50質量部より多いと糸切れ頻度が 多くなる。したがって、ビニル系共重合体の配合量は、好ましくは、 5〜50質量部であ る力 さらに好ましくは、 10〜40質量部である。  In the present invention, when the blending amount of the vinyl copolymer is less than 5 parts by mass, the specific gravity of the obtained fiber can not be reduced, and when it is more than 50 parts by mass. Thread breakage frequency increases. Therefore, the blending amount of the vinyl copolymer is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass.
[0027] 前記ビニル系共重合体を構成する芳香族ビニル単量体 (a)は、該ビニル系共重合 体と塩ィ匕ビュル系榭脂との相溶性を向上させるので、これらを含有する本発明の塩 化ビュル系榭脂組成物の紡糸性を向上させることができる。そして、前記ビニル系共 重合体を構成する芳香族ビニル単量体 (a)は、例えば、スチレン、 ocーメチルスチレ ン等の α置換スチレン、ビュルトルエン、ェチルスチレン、 tーブチルスチレン、クロル スチレン、ブロムスチレン、ジブロムスチレン、及び、トリブロムスチレン等の芳香環置 換スチレンであるが、これらのうちでスチレンが特に好ましい。前記スチレンは、紡糸 時の榭脂圧の調整が容易であるので、スクリュー負荷を下げることができ、そのため に、溶融紡糸のいっそう長時間のロングラン性を確保することができる。  The aromatic vinyl monomer (a) constituting the vinyl-based copolymer improves the compatibility between the vinyl-based copolymer and the salt-based resin, and thus the vinyl-based copolymer contains the vinyl-based copolymer. The spinnability of the chlorinated boule based resin composition of the present invention can be improved. And, the aromatic vinyl monomer (a) constituting the vinyl-based copolymer is, for example, styrene, α-substituted styrene such as oc-methylstyrene, butyltoluene, ethylstyrene, t-butylstyrene, chlorstyrene, bromstyrene, distyrene Among them are aromatic ring-substituted styrenes such as bromostyrene and tribromostyrene, among which styrene is particularly preferred. The above-mentioned styrene makes it possible to reduce the screw load since adjustment of the resin pressure at the time of spinning is easy, so that it is possible to secure the long run property of melt spinning for a longer time.
[0028] 前記ビニル系共重合体を構成するシアン化ビニル単量体 (b)は、例えば、アタリ口 二トリル、メタタリ口-トリル、及び、クロ口アクリロニトリルである力 これらのうちでアタリ 口-トリルが特に好ましい。前記アクリロニトリルは、紡糸時の榭脂圧の調整が容易で あるので、スクリュー負荷を下げることができ、そのために、溶融紡糸のいっそう長時 間のロングラン性を確保することができる。  The vinyl cyanide monomer (b) constituting the above-mentioned vinyl copolymer is, for example, attril nitrile, metataryl trill-tolyl and crotal acrylonitrile having a force of these. Trill is particularly preferred. The acrylonitrile is easy to adjust the resin pressure at the time of spinning, so that it is possible to reduce the screw load, and therefore, it is possible to ensure the long run property of melt spinning for a longer time.
[0029] 前記ビュル系共重合体を構成する (メタ)クリル酸エステル (c)は、例えば、メチルメ タクリレート、及び、ェチルメタタリレートである力 これらのうちメチルメタタリレートが 特に好ましい。前記メチルメタタリレートは、塩ィ匕ビュル系榭脂と溶解度パラメータが 近いので、繊維の透明性を向上させることができる。  Among the (meth) acrylic esters (c) that constitute the boule-based copolymer, for example, methyl methacrylate and ethyl methacrylate are particularly preferable methyl methacrylate of these. The methyl metatarylate can improve the transparency of the fiber because the solubility parameter is close to that of salt-based veal resin.
[0030] したがって、本発明の塩ィ匕ビュル系榭脂組成物にぉ 、ては、前記芳香族ビュル単 量体 (a)は、好ましくは、スチレンであり、前記シアンィ匕ビュル (b)は、好ましくは、ァク リロ-トリルであり、そして、前記 (メタ)クリル酸エステル (c)は、好ましくは、メチルメタ アタリレートである。このように、前記芳香族ビュル単量体 (a)がスチレンであり、そし て、前記シアン化ビュル (b)がアクリロニトリルであるので、紡糸時の榭脂圧の調整が 容易となり、そのために、スクリュー負荷を下げることができ、よって、溶融紡糸のいつ そう長時間のロングラン性を確保することができる。また、前記 (メタ)クリル酸エステル (c)カ^チルメタアタリレートであるところ、該メチルメタタリレートは塩ィ匕ビュル系榭脂 と溶解度パラメータが近 、ので、繊維の透明性を 、つそう向上させることができる。 [0030] Therefore, in the salt-and-bullet-based resin composition of the present invention, the aromatic boule alone is preferably used. The mer (a) is preferably styrene, and the cyanide (b) is preferably acryloyl-tolyl, and the (meth) acrylic ester (c) is preferably , Methyl meta atarilate. Thus, since the aromatic boule monomer (a) is styrene and the cyanide boule (b) is acrylonitrile, adjustment of the resin pressure at the time of spinning becomes easy, and therefore, The screw load can be reduced, thus ensuring long and long runnability of melt spinning. Further, in the case of the (meth) acrylic ester (c) (C) methyl metatalylate, the methyl metatalylate has a solubility parameter close to that of the salt-like resin, and therefore the fiber transparency is improved. That can be improved.
[0031] 本発明においては、前記ビュル系共重合体は、好ましくは、スチレン 70〜90質量 %と、アクリロニトリル 30〜： LO質量％と、を重合含有する共重合体である力 さらに好 ましくは、スチレン 75〜85質量0 /0と、アクリロニトリル 25〜15質量0 /0と、を重合含有 する共重合体である。このように、前記ビニル系共重合体が、スチレン 70〜90質量 %と、アクリロニトリル 30〜： LO質量％と、を重合含有する共重合体であると、該ビニル 系共重合体と塩ィ匕ビュル系榭脂との相溶性が向上して紡糸性が向上し、そのために 、さらに安定した生産性が得られる。 In the present invention, preferably, the boule-based copolymer is a copolymer which polymerizes and contains 70 to 90% by mass of styrene and 30 to: 50% by mass of acrylonitrile. is styrene 75 to 85 weight 0/0, acrylonitrile 25-15 wt 0/0, is a copolymer containing a polymerization. Thus, when the vinyl copolymer is a copolymer containing 70 to 90% by mass of styrene and 30 to: 50% by mass of acrylonitrile, the vinyl copolymer and the salt thereof are mixed with each other. The compatibility with the boule based resin is improved to improve the spinnability, and as a result, more stable productivity can be obtained.
[0032] また、本発明においては、前記ビニル系共重合体は、好ましくは、スチレン 10〜40 質量％と、メチルメタリレート 90〜50質量％と、アクリロニトリル 0〜10質量％とを重合 含有する共重合体である力 さらに好ましくは、スチレン 15〜30質量％と、メチルメタ タリレート 85〜60質量％と、アクリロニトリル 0〜10質量％と、を重合含有する共重合 体である。このように、前記ビュル系共重合体が、スチレン 10〜40質量0 /0と、メチル メタリレート 90〜50質量％と、アクリロニトリル 0〜10質量％とを重合含有する共重合 体であると、該ビュル系共重合体と塩ィ匕ビ二ル系榭脂との相溶性が向上して紡糸性 が向上し、そのために、さらに安定した生産性が得られる。 In the present invention, the vinyl copolymer preferably contains 10 to 40% by mass of styrene, 90 to 50% by mass of methyl methacrylate, and 0 to 10% by mass of acrylonitrile. The power which is a copolymer More preferably, it is a copolymer which polymerizes and contains 15-30 mass% of styrene, 85-60 mass% of methyl methacrylate, and 0-10 mass% of acrylonitrile. Thus, the Bulle based copolymer, styrene 10 to 40 weight 0/0, and methyl Metarireto 90 to 50 wt%, if it is a copolymer of polymerizing containing acrylonitrile 0 to 10 mass%, the The compatibility between the block copolymer and the vinyl chloride resin is improved to improve the spinnability, and as a result, more stable productivity can be obtained.
[0033] 本発明における「塩ィ匕ビ二ル系榭脂」は、塊状重合、溶液重合、懸濁重合、乳化重 合等の手段によって得られたものであるが、繊維の初期着色性等を勘案すると、好ま しくは、懸濁重合によって製造したものである。本発明における「塩ィ匕ビ二ル系榭脂」 は、好ましくは、従来公知の塩ィ匕ビュルの単独重合物であるホモポリマー榭脂、又は 、従来公知の各種のコポリマー榭脂である力 本発明の目的に反しない限り、これら 以外の塩ィ匕ビ二ル系榭脂であっても力まわない。前記「コポリマー榭脂」としては、従 来公知のコポリマー榭脂を使用することができるが、好ましくは、塩化ビニル—酢酸ビ -ルコポリマー榭脂、塩ィ匕ビュル一プロピオン酸ビュルコポリマー榭脂等の塩ィ匕ビ- ルとビニルエステル類とのコポリマー榭脂、塩化ビニルーアクリル酸ブチルコポリマー 榭脂、塩ィ匕ビュル一アクリル酸 2ェチルへキシルコポリマー榭脂等の塩ィ匕ビュルとァ クリル酸エステル類とのコポリマー榭脂、塩ィ匕ビュル エチレンコポリマー榭脂、塩ィ匕 ビュル一プロピレンコポリマー榭脂等の塩ィ匕ビ二ルとォレフイン類とのコポリマー榭脂[0033] The "chlorinated vinyl resin" in the present invention is obtained by means of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. In view of the above, it is preferably produced by suspension polymerization. In the present invention, the “salt-to-vinyl salt” is preferably a homopolymer salt which is a homopolymer of a salt-to-be-known conventionally known salt, or a copolymer salt of a conventionally known salt. As long as the purpose of the present invention is not violated, Even other salt and vinyl based resins do not force. As the above-mentioned “copolymer resin”, conventionally known copolymer resins can be used, but preferably, vinyl chloride-acetate copolymer resin, chloride-bibulide propionate copolymer resin, etc. Copolymers of vinyl chloride with vinyl esters, vinyl chloride-butyl acrylate copolymer, butter, polyvinyl chloride-butyl methacrylate, acrylic acid 2-ethylhexyl copolymer copolymers, etc. Copolymer resins with acid esters, Chlorinated ethylene copolymer resins, Chlorinated vinyl-propylene copolymers, etc.
、及び、塩ィ匕ビュル一アクリロニトリルコポリマー榭脂であり、さらに好ましくは、塩ィ匕ビ -ルの単独重合物であるホモポリマー榭脂、塩ィ匕ビュル エチレンコポリマー榭脂、 塩ィ匕ビュル—酢酸ビュルコポリマー榭脂等のコポリマー榭脂である。前記「コポリマ ー榭脂」においては、コモノマーの含有量は、特に限定されず、成型加工性、糸特性 等の要求品質に応じて決めることができる。 And homopolymer-copolymers which are homopolymers of chloride-vinyl, which are homopolymers of chloride-vinyl, and copolymers of ethylene-copolymer-resin, preferably chloride-biol. Copolymer resins such as butyl acetate copolymer resins. In the above-mentioned “copolymer resin”, the content of the comonomer is not particularly limited, and can be determined according to the required quality such as molding processability and yarn properties.
[0034] 本発明における「塩ィ匕ビュル系榭脂」の粘度平均重合度は、好ましくは、 600〜16 00である。「塩ィ匕ビュル系榭脂」の粘度平均重合度が 600未満であると、溶融粘度が 低下するので、得られた塩ィ匕ビニル系繊維は熱収縮しやすくなる恐れがある。一方、 「塩ィ匕ビュル系榭脂」の粘度平均重合度が 1600を超えると、塩化ビニル系榭脂の溶 融粘度が高くなるので、ノズル圧力が高くなり、そのために、安全な紡糸が困難にな る恐れがある。前記「粘度平均重合度」は、榭脂 200gを-トロベンゼン 50mlに溶解 させ、このポリマー溶液を 30°C恒温槽中、ウベローデ型粘度計を用いて比粘度を測 定し、 JIS—K6721により算出したものである。  [0034] The viscosity average degree of polymerization of the "salt-and-bullet-based resin" in the present invention is preferably 600 to 1600. If the viscosity average degree of polymerization of “salt-and-bule-based resin” is less than 600, the melt viscosity is lowered, so that the resulting vinyl chloride-based fiber may be easily thermally shrunk. On the other hand, if the viscosity average degree of polymerization of “salt-and-bulb-based resin” exceeds 1600, the melt viscosity of the vinyl chloride-based resin will be high, and the nozzle pressure will be high, which makes safe spinning difficult. There is a risk of The above "viscosity average degree of polymerization" is obtained by dissolving 200 g of resin in 50 ml of -trobenzene, measuring the specific viscosity using a Ubbelohde viscometer in a 30 ° C thermostatic bath, according to JIS-K6721. It is calculated.
[0035] 本発明の塩ィ匕ビ二ル系榭脂組成物にぉ ヽては、 目的に応じて、塩化ビニル榭脂組 成物に使用される従来公知の添加剤を配合してもよい。これらの添加剤としては、熱 安定剤、可塑剤、滑剤、相溶化剤、加工助剤、強化剤、紫外線吸収剤、酸化防止剤 、帯電防止剤、充填剤、難燃剤、顔料、初期着色改善剤、導電性付与剤、表面処理 剤、光安定剤、香料等の添加剤がある。  [0035] In the salt-type vinyl-based fat composition of the present invention, conventionally known additives used in vinyl chloride-based fat composition may be blended according to the purpose. . These additives include heat stabilizers, plasticizers, lubricants, compatibilizers, processing aids, toughening agents, UV absorbers, antioxidants, antistatic agents, fillers, flame retardants, pigments, and initial color improvement. There are additives such as agents, conductivity imparting agents, surface treatment agents, light stabilizers, and perfumes.
[0036] 本発明における「ビュル系共重合体」の重量平均分子量は、好ましくは、 5万〜 11 万、さらに好ましくは、 6万〜 10万である。「ビニル系共重合体」の重量平均分子量が 5万未満又は 11万を超えると、塩ィ匕ビュル系榭脂との相溶性が悪くなるので、物性 低下を来す。 The weight-average molecular weight of the “bul-based copolymer” in the present invention is preferably 50,000 to 110,000, more preferably 60,000 to 100,000. If the weight-average molecular weight of the “vinyl-based copolymer” is less than 50,000 or over 110,000, the compatibility with the salt-based resin is deteriorated, so the physical properties Come down.
[0037] 前記「ビニル系共重合体」の重量平均分子量の調整は、公知の連鎖移動剤を用い て行う。カゝかる連鎖移動剤は、例えば、 n—ドデシルメルカプタン、 tードデシルメル力 プタン、 n—ォクチルメルカプタン等のメルカプタン類、ジペンテン、ターピノーレン等 のテルペン類、クロ口ホルム、ブロロホルム等のハロゲン化炭化水素類、及び、 α—メ チルスチレンダイマーである力 それらのうちでも、メルカプタン類が特に好ましい。 The adjustment of the weight average molecular weight of the “vinyl copolymer” is performed using a known chain transfer agent. Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan and n-octy mercaptan; terpenes such as dipentene and terpinorene; halogenated hydrocarbons such as cromoform and broroform. And α- Methylstyrene dimers Among them, mercaptans are particularly preferred.
[0038] 前記「ビニル系共重合体」の製造方法は、特に制限はなぐ例えば、乳化重合、懸 濁重合、塊状重合、溶液重合等の重合方法が採用できる。また、前記「ビニル系共 重合体」の製造方法は、回文法、連続法いずれの重合法によるものであっても力まわ ない。  The method for producing the “vinyl-based copolymer” is not particularly limited. For example, polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization and the like can be adopted. Further, the method for producing the “vinyl-based copolymer” is not limited by either the polymerization method or the continuous polymerization method.
[0039] 本発明の「塩化ビニル系繊維」は、請求項 1〜4の 、ずれか 1項に記載の塩化ビ- ル系榭脂組成物からなる。このように、本発明の「塩ィ匕ビニル系繊維」が請求項 1〜4 の!、ずれか 1項に記載の塩ィ匕ビ二ル系榭脂組成物力 なると、人工毛髪用繊維とし て必要とされる均一なゆるいカール形状を持ち合わせた塩ィ匕ビニル系繊維となる。  [0039] The "vinyl chloride-based fiber" of the present invention comprises the vinyl chloride-based resin composition according to any one of claims 1 to 4. Thus, when the "salt-vinyl-based fiber" of the present invention has the strength of the salt-like vinyl-based resin composition according to any one of claims 1-4, it becomes a fiber for artificial hair. It becomes a vinyl chloride-based fiber having the required uniform curl shape.
[0040] 本発明の「塩化ビニル系繊維」は、その一本の太さが、好ましくは， 20〜： LOOデニ ールであり、さら〖こ好ましくは、 50〜80デニールである。このように、塩化ビュル繊維 一本の太さが 20〜： LOOデニールであると、天然の毛髪と遜色がないものとなり、そし て、塩ィ匕ビュル繊維一本の太さが 50〜80デニールであると、それにカ卩えて、触感及 び風合いが向上したものとなる。  The thickness of one “vinyl chloride-based fiber” of the present invention is preferably 20 to: LOO denier, and more preferably 50 to 80 denier. Thus, when the thickness of a single chloride boule fiber is 20 to 20: LOO denier, it becomes comparable to natural hair, and the thickness of one chloride boule fiber is 50 to 80 denier. In such a case, the feeling and feel will be improved.
[0041] 本発明の「塩ィ匕ビニル系繊維」の断面形状は、いかなるものでもよぐ例えば、円形 、楕円形、メガネ形、星形、 Η字形、丁字形、 Υ字形、三角形、四角形、十字形、ハー ト形、馬蹄形、又は、これらの組み合わせでもよい。また、これらの中空体であっても よい。  [0041] The cross-sectional shape of the "salt vinyl-based fiber" of the present invention may be any shape, for example, circular, oval, glasses, star, U-shaped, T-shaped, U-shaped, triangular, square, It may be cruciform, heart-shaped, horseshoe-shaped, or a combination of these. Moreover, these hollow bodies may be sufficient.
[0042] 本発明の「塩化ビニル系繊維」は、請求項 1〜4の 、ずれか 1項に記載の塩化ビ- ル系榭脂組成物を 170〜190°Cの温度で溶融紡糸することにより製造される。このよ うに、本発明の「塩ィ匕ビュル系繊維」が請求項 1〜4のいずれか 1項に記載の塩ィ匕ビ -ル系榭脂組成物を 170〜190°Cの温度で溶融紡糸することにより製造されると、溶 融紡糸のロングラン性を確保することができ、そのために、塩ィ匕ビュル繊維の生産性 を向上させることができる。 [0042] The "vinyl chloride fiber" of the present invention comprises melt spinning the vinyl chloride resin composition according to any one of claims 1 to 4 at a temperature of 170 to 190 ° C. Manufactured by Thus, the "salt-and-bullet-based fiber" of the present invention melts the salt-and-fill resin composition according to any one of claims 1 to 4 at a temperature of 170 to 190 ° C. When manufactured by spinning, it is possible to ensure the long-run property of melt spinning, and for that reason, the productivity of chloride fiber is ensured. Can be improved.
[0043] 本発明の「塩化ビニル系繊維」の製造にぉ ヽては、塩化ビニル系榭脂組成物をへ ンシェルミキサ、リボンプレンダ等の混合機を使用して混合したパウダーコンパウンド 、又は、これを溶融混合したペレットコンパゥンドを、単軸押出機、異方向二軸押出機 、コニカルニ軸押出機等の溶融押出機を使用して、 170〜190°Cの温度で溶融紡糸 すること〖こより製造される。  In the production of the “vinyl chloride-based fiber” of the present invention, a powder compound obtained by mixing a vinyl chloride-based resin composition with a mixer such as a shell mixer or ribbon platen, or melting thereof is used. Melt-spinning the mixed pellet compound at a temperature of 170 to 190 ° C. using a melt extruder such as a single-screw extruder, a counter-rotating twin-screw extruder, a conical twin-screw extruder, etc. Ru.
[0044] カゝかる塩ィ匕ビュル系榭脂組成物を溶融紡糸して繊維状の未延伸糸にする際には、 従来公知の押出機を使用できる。このような押出機としては、単軸押出機、異方向二 軸押出機、コ-カルニ軸押出機等の押出機を使用することができるが、好ましくは、 口径が 35〜85πιπιΦ程度の単軸押出機、又は、口径が 35〜50πιπιΦ程度のコニ カル押出機を使用するのが良い。 口径が過大になると、押出し量が多くなり、又、ノズ ル圧力が過大になるので、未延伸糸の流出速度が速過ぎとなり、そのために、後ェ 程の巻き取りが困難になることがある。  [0044] When melt spinning of a salt-in-the-bulb-based resin composition to make a fibrous undrawn yarn, a conventionally known extruder can be used. As such an extruder, an extruder such as a single-screw extruder, a counter-rotating twin-screw extruder, or a co-Carni shaft extruder can be used, preferably a single-screw extruder having a diameter of about 35 to 85πιπιφ. It is preferable to use an extruder or a conical extruder having a diameter of about 35 to 50πιπιφ. If the bore diameter is too large, the amount of extrusion will increase and the nozzle pressure will become too large, so the flow rate of the undrawn yarn may become too fast, which may make it difficult to wind up later. .
[0045] 本発明の「塩化ビニル系繊維」の製造にぉ ヽては、前記溶融紡糸した塩化ビニル 系繊維を 90〜120°Cの温度に保持した空気雰囲気下で 2〜4倍まで延伸した後、こ の延伸した塩ィ匕ビニル系繊維を 110〜140°Cの温度に保持した空気雰囲気下で延 伸前の 60〜： LOO%の長さになるまで熱弛緩させる。このように、前記溶融紡糸した塩 化ビュル系繊維を 90〜 120°Cの温度に保持した空気雰囲気下で 2〜4倍まで延伸 した後、この延伸した塩ィ匕ビニル系繊維を 110〜140°Cの温度に保持した空気雰囲 気下で延伸前の 60〜 100%の長さになるまで熱弛緩させると、強度、伸度、及び、 熱収縮率のバランスのとれた塩ィ匕ビニル系繊維とすることができる。  In the production of the “vinyl chloride-based fiber” of the present invention, the melt-spun vinyl chloride-based fiber was stretched to 2 to 4 times in an air atmosphere maintained at a temperature of 90 to 120 ° C. After that, the drawn vinyl chloride-based fibers are thermally relaxed in an air atmosphere maintained at a temperature of 110 to 140 ° C. to a length of 60 to LOO% before stretching. Thus, after drawing the melt spun chloride-based fibers to 2 to 4 times in an air atmosphere maintained at a temperature of 90 to 120 ° C., the drawn chloride-vinyl fibers can be 110 to 140 When heat-relaxed to a length of 60 to 100% before stretching in an air atmosphere kept at a temperature of ° C, the strength, elongation, and heat shrinkage rate of balanced salt vinyl chloride It can be a fiber base.
[0046] 本発明の「人工毛髪用繊維」は、請求項 5に記載の塩ィ匕ビュル系繊維を人工毛髪 用繊維としたものである。このように、請求項 5に記載の塩ィ匕ビニル系繊維を人工毛 髪用繊維としたものであると、人工毛髪用繊維として必要とされる均一なゆるいカー ル形状を持ち合わせた人工毛髪用繊維とすることができる。  [0046] The "fiber for artificial hair" of the present invention is a fiber according to claim 5, which is a fiber for artificial hair. Thus, when the vinyl chloride-based fiber according to claim 5 is used as a fiber for artificial hair, it is for artificial hair having a uniform loose curl shape required as a fiber for artificial hair. It can be fiber.
実施例  Example
[0047] 以下に、本発明の実施例及び比較例を説明するが、これらの実施例及び比較例は 、いずれも例示的なものであって、本発明の内容を限定するものではない。 [0048] (実施例 1) Examples of the present invention and comparative examples will be described below, but these examples and comparative examples are all illustrative and do not limit the contents of the present invention. Example 1
(a)塩ィ匕ビ二ル系榭脂 (大洋塩ビ株式会社製、 TH- 1000) 100質量部、ビニル系 共重合体を構成するモノマーの割合がスチレン 80質量0 /0及びアクリロニトリル 20質 量％であるビニル系共重合体 (電気化学工業株式会社製、 AS— 3) 20質量部、ノ、ィ ドロタルサイト熱安定剤及び Ca— Zn金属石鹼安定剤にポリエチレンワックス及び特 殊脂肪酸エステルの滑剤をパック化して得た複合安定剤 ·滑剤 (日産化学工業株式 会社製、 CP—410A) 8質量部、並びに、亜リン酸エステル熱安定剤 (旭電化工業株 式会社製、アデカスタブ 1500) 1質量部を配合してなる榭脂組成物をヘンシェルミキ サで混合する工程、（b)前記混合した榭脂組成物をノズル断面積 0. 06mm2、孔数 120、及び、金型温度 180°Cの紡糸金型から押出し量 lOkgZ時間で溶融紡糸して 150デニールの繊維とする工程、（c)前記溶融紡糸した繊維を 100°Cの空気雰囲気 下で 300%に延伸して 50デニールの繊維とする工程、そして、（d)前記延伸した繊 維に 120°Cの空気雰囲気下で繊維全長が処理前の 75%の長さに収縮するまで熱 弛緩処理を施す工程を順次経て、 67デニールの塩ィ匕ビニル系繊維を得た。 (a) Shioi匕Bi sulfonyl system榭脂(Taiyo Vinyl Corp., TH- 1000) 100 parts by weight, the proportion of monomers constituting the vinyl copolymer is a styrene 80 mass 0/0 and acrylonitrile 20 Mass % Vinyl copolymer (manufactured by Denki Kagaku Kogyo Co., Ltd., AS-3), 20 parts by mass, no, idrotalcite heat stabilizer and Ca--Zn metal stoma stabilizer, polyethylene wax and special fatty acid ester 8 parts by mass of a combined stabilizer and lubricant (manufactured by Nissan Chemical Industries, Ltd., CP-410A) and a phosphite thermal stabilizer (manufactured by Asahi Denka Kogyo Co., Ltd., Adekastab 1500) Mixing a resin composition comprising 1 part by mass with a Henschel mixer, (b) mixing the resin composition with a nozzle cross-sectional area of 0.06 mm, a hole number of 120, and a mold temperature of 180 ° The amount of extrusion from the spinning mold of C l Melt spinning with lOkgz time, with 150 denier fibers (C) drawing the melt-spun fibers to 300% in an air atmosphere at 100 ° C. to make 50 denier fibers, and (d) drawing 120 ° C. air to the drawn fibers. Through the steps of heat relaxation treatment under the atmosphere until the total length of the fibers was shrunk to a length of 75% before the treatment, 67 denier chloride vinyl fibers were obtained.
[0049] (実施例 2)  Example 2
実施例 1の（a)工程の榭脂組成物におけるビニル系共重合体を構成するモノマー の割合をスチレン 20質量0 /0、アクリロニトリル 5質量0 /0、及び、メチルメタタリレート 75 質量％とした以外は、実施例 1と同様にして塩ィ匕ビニル系繊維を得た。 Example 1 (a) Styrene 20 mass fraction of the monomers constituting the vinyl copolymer in榭脂composition of step 0/0, acrylonitrile 5 mass 0/0, and, with 75 weight% methyl meth Tali rate A vinyl chloride-based fiber was obtained in the same manner as in Example 1 except for the above.
[0050] (実施例 3)  Example 3
実施例 1の（a)工程の榭脂組成物におけるビニル系共重合体を構成するモノマー の割合をスチレン 70質量％、及び、アクリロニトリル 30質量％とした以外は、実施例 1 と同様にして塩ィ匕ビニル系繊維を得た。  A salt was prepared in the same manner as in Example 1 except that the proportions of the monomers constituting the vinyl copolymer in the resin composition in step (a) of Example 1 were 70% by mass of styrene and 30% by mass of acrylonitrile. The vinyl fiber was obtained.
[0051] (実施例 4)  Example 4
実施例 1の（a)工程の榭脂組成物におけるビニル系共重合体を構成するモノマー の割合をスチレン 10質量％、及び、メチルメタタリレート 90質量％とした以外は、実 施例 1と同様にして塩ィ匕ビニル系繊維を得た。  Example 1 was repeated except that the proportion of the monomers constituting the vinyl copolymer in the resin composition of step (a) of Example 1 was 10% by mass of styrene and 90% by mass of methyl methacrylate. In the same manner, vinyl chloride-based fibers were obtained.
[0052] (比較例 1)  Comparative Example 1
実施例 1の（a)工程の榭脂組成物におけるビニル系共重合体の配合量を 3質量部 とした以外は、実施例 1と同様にして塩ィ匕ビニル系繊維を得た。 3 parts by mass of a vinyl-based copolymer in the resin composition of step (a) of Example 1 A vinyl chloride-based fiber was obtained in the same manner as in Example 1 except that
[0053] (比較例 2) Comparative Example 2
実施例 1の（a)工程の榭脂組成物におけるビニル系共重合体の配合量を 60質量 部とした以外は、実施例 1と同様にして塩ィ匕ビニル系繊維を得た。  A vinyl chloride-based fiber was obtained in the same manner as in Example 1, except that the blending amount of the vinyl copolymer in the resin composition in the step (a) of Example 1 was changed to 60 parts by mass.
[0054] 以上、実施例 1〜4及び比較例 1〜2で得られた塩ィ匕ビニル系繊維のカール均一性 と紡糸性を評価した。評価結果は、次の表 1に示される。 The curl uniformity and the spinnability of the vinyl chloride-based fibers obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated above. The evaluation results are shown in Table 1 below.
[0055] [表 1] [Table 1]
Figure imgf000012_0001
Figure imgf000012_0001
[0056] 表 1における「カール均一性」は、次のような手順で評価した。即ち、 120本の塩ィ匕 ビュル系繊維の単繊維力 なる繊維束 (延熱糸）を一定の長さに切断し、これを直径“Curl uniformity” in Table 1 was evaluated by the following procedure. That is, a fiber bundle (hot-rolled yarn), which is a single fiber strength of 120 fibers of bible fiber, is cut into a fixed length, and this is cut into diameters.
20mmのアルミ製筒に巻き付け乍ら両端を固定した後、アルミ製筒ごと 90°Cの空気 循環式オーブンに投入して 30分間加熱した。そして、この繊維束を巻き付けたアルミ 筒を温度 23°C、相対湿度 50%の恒温室で 24時間放置した。次に、ステンレス筒か ら繊維束を取り外して、一方の端を固定して吊り下げ、その際、根元部分のカール形 状の山 (谷)部分の角度と、先端部分のカール形状の山 (谷)部分の角度と、を算出 して、先端部分のカール形状の角度を根元部分のカール形状の角度で割った値 (角 度比）でカール均一性の評価を行った。角度比が 1に近いほど角度の差がなぐカー ルが均一にかかって 、ることを表して 、る。 The both ends were fixed by winding around an aluminum cylinder made of 20 mm, and then the whole aluminum cylinder was placed in an air circulating oven at 90 ° C. and heated for 30 minutes. Then, the aluminum cylinder wound with the fiber bundle was left to stand in a temperature-controlled room at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours. Next, remove the fiber bundle from the stainless steel cylinder and fixate and suspend one end, in which case, the angle of the curled valley (valley) of the root and the curled valley of the tip ( The angle of the valley portion was calculated, and the curl uniformity was evaluated by a value (angle ratio) obtained by dividing the angle of the curl shape of the tip portion by the angle of the curl shape of the root portion. The closer the angle ratio is to 1, the more evenly the curls that the difference in the angle becomes, which means that.
[0057] 塩ィ匕ビュル系繊維のカール均一性は、次に示す評価基準 [0057] Curl uniformity of salt-based fibers is evaluated according to the following evaluation criteria
〇：角度比が 0. 85以上で、カールが均一に力かり合格であるもの X：角度比が 0. 85未満で、カールが不均一に力かり不合格であるもの で評価した。 :: The angle ratio is 0.85 or more, and the curl is evenly passed X: Evaluation was made with an angle ratio of less than 0.85 and nonuniform curling failure.
[0058] 表 1における「紡糸性」は、溶融紡糸を行った際の単糸切れ（120本の内の数本が 切れる）が起きた回数で評価した。即ち、塩ィ匕ビュル系繊維のカール均一性は、単糸 切れが起きた回数を 1時間当たりの糸切れ頻度（回数 Z時間）に換算して、次に示す 評価基準  The “spinning property” in Table 1 was evaluated by the number of times single thread breakage (several 120 out of 120) occurred when melt spinning was performed. That is, the curling uniformity of the chloride-based fiber is calculated by converting the number of occurrences of single yarn breakage into the yarn breakage frequency (number of hours Z hours) per hour, and the following evaluation criteria
〇：糸切れ頻度において、 1時間当たり、 0回で生産性の点でより効果が上がったも の  :: In the yarn breakage frequency, productivity improved at 0 times per hour.
△： 2回以下でロングラン製造対象製品として問題がな 、もの  :: no problem as a product for long run production in 2 times or less
X： 3回以上でロングラン製造対象製品として成り立たないもの  X: 3 or more times that can not be manufactured as a long-run product
で評価した。  It evaluated by.
[0059] 実施例 1〜4で得られた塩ィ匕ビュル系繊維においては、そのカール均一性及び紡 糸性は、ともに使用可能レベルであり、 目標とする塩ィ匕ビュル系繊維であった。特に 、実施例 1, 2で得られた塩ィ匕ビュル系繊維においては、そのカール均一性及び紡 糸性は、ともに良好なレベルであった。  In the chloride-type fibers obtained in Examples 1 to 4, the curl uniformity and the spinnability were both usable levels, and were the target chloride-type fibers. . In particular, in the polyvinyl chloride fiber obtained in Examples 1 and 2, the curl uniformity and spinnability were both at good levels.
[0060] 実施例 3, 4で得られた塩ィ匕ビュル系繊維は、実施例 1, 2で得られた塩化ビニル系 繊維に比べて紡糸性に多少難はある力 そのカール均一性は、良好なレベルであつ た。  [0060] The salted boule based fibers obtained in Examples 3 and 4 have a somewhat difficult spinnability compared to the vinyl chloride fibers obtained in Examples 1 and 2, and the curl uniformity is It was at a good level.
[0061] 比較例 1で得られた塩ィ匕ビュル系繊維は、ビニル系共重合体の配合量が少なかつ たので、そのカール均一性は悪かった。  The curling uniformity of the chloride-based fiber obtained in Comparative Example 1 was poor because the blending amount of the vinyl-based copolymer was small.
[0062] 比較例 2で得られた塩ィ匕ビュル系繊維は、ビニル系共重合体の配合量が多力つた ので、その紡糸性が悪かった。 [0062] The salted fibers obtained in Comparative Example 2 had poor spinnability because the compounding amount of the vinyl copolymer was high.
産業上の利用可能性  Industrial applicability
[0063] 本発明の塩ィ匕ビ二ル系榭脂組成物を用いて得られた塩ィ匕ビニル系繊維は、例え ば、ウイッグ、ヘアピース、ブレード、ドールヘアー、エクステンションヘアー等の頭髪 装飾用の人工毛髪用繊維に用いることができる。 The vinyl chloride-based fiber obtained using the vinyl chloride-based resin composition of the present invention is, for example, for hair decoration of wigs, hair pieces, blades, doll hair, extension hair, etc. It can be used for artificial hair fibers of

Claims

請求の範囲 The scope of the claims
[1] (A)塩ィ匕ビュル系榭脂 100質量部、並びに、  [1] (A) 100 parts by mass of salt-based resin, and
(B)芳香族ビニル単量体 (a)と、シアンィ匕ビニル (b)、及び、 （メタ)クリル酸エステル (c)から選択される 1種又は 2種以上のビニル系単量体と、で構成されるビニル系共 重合体 5〜50質量部、  (B) Aromatic vinyl monomer (a) and one or more vinyl monomers selected from cyanide vinyl (b) and (meth) acrylic acid ester (c) 5 to 50 parts by mass of a vinyl copolymer composed of
を含有することを特徴とする塩化ビュル系榭脂組成物。  Chlorinated burial-based resin composition characterized by containing.
[2] 前記芳香族ビュル単量体 (a)力 スチレンであり、前記シアンィ匕ビュル (b)力 ァク リロ-トリルであり、そして、前記 (メタ)クリル酸エステル (c)が、メチルメタアタリレート であることを特徴とする請求項 1に記載の塩ィ匕ビュル系榭脂組成物。 [2] The aromatic boule monomer (a) power styrene, the cyanide bule (b) force acrylol, and the (meth) acrylic ester (c) is methyl meta. The salt-and-bule-based resin composition according to claim 1, which is atarilate.
[3] 前記ビュル系共重合体が、スチレン 70〜90質量％と、アクリロニトリル 30〜10質量[3] The burl-based copolymer comprises 70 to 90% by mass of styrene and 30 to 10% of acrylonitrile.
%と、を重合含有する共重合体であることを特徴とする請求項 1又は 2に記載の塩ィ匕 ビニル系榭脂組成物。 The vinyl chloride resin composition according to claim 1 or 2, which is a copolymer containing a polymer by weight.
[4] 前記ビュル系共重合体が、スチレン 10〜40質量％と、メチルメタリレート 90〜50質 量％と、アクリロニトリル 0〜10質量％とを重合含有する共重合体であることを特徴と する請求項 1又は 2に記載の塩ィ匕ビュル系榭脂組成物。  [4] The boule-based copolymer is a copolymer comprising 10 to 40% by mass of styrene, 90 to 50% by mass of methyl methacrylate, and 0 to 10% by mass of acrylonitrile. The salt-and-boule based resin composition according to claim 1 or 2.
[5] 請求項 1〜4の 、ずれか 1項に記載の塩ィ匕ビ二ル系榭脂組成物からなることを特徴 とする塩ィ匕ビニル系繊維。  [5] A vinyl chloride-based fiber comprising the vinyl chloride-based resin composition according to any one of claims 1 to 4, characterized in that.
[6] 請求項 1〜4のいずれ力 1項に記載の塩化ビュル系榭脂組成物を 170〜190°Cの 温度で溶融紡糸することを特徴とする塩化ビニル系繊維の製造方法。  [6] A method for producing a vinyl chloride-based fiber, comprising melt-spinning the chloride-based resin composition according to any one of claims 1 to 4 at a temperature of 170 to 190 ° C.
[7] 前記溶融紡糸した塩化ビニル系繊維を 90〜120°Cの温度に保持した空気雰囲気 下で 2〜4倍まで延伸した後、この延伸した塩ィ匕ビュル系繊維を 110〜140°Cの温度 に保持した空気雰囲気下で延伸前の 60〜 100%の長さになるまで熱弛緩させること を特徴とする請求項 6に記載の塩化ビニル系繊維の製造方法。  [7] The melt spun vinyl chloride fiber is stretched to 2 to 4 times in an air atmosphere maintained at a temperature of 90 to 120 ° C., and then this stretched salt boule fiber is stretched to 110 to 140 ° C. The method for producing a vinyl chloride-based fiber according to claim 6, characterized in that the film is thermally relaxed to a length of 60 to 100% before drawing in an air atmosphere maintained at a temperature of
[8] 請求項 5に記載の塩化ビニル系繊維を人工毛髪用繊維としたことを特徴とする人 ェ毛髪用繊維。  [8] A fiber for human hair, characterized in that the vinyl chloride fiber according to claim 5 is used as a fiber for artificial hair.
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JP2015094054A (en) * 2013-11-13 2015-05-18 旭化成ケミカルズ株式会社 Fiber and nonwoven fabric
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US20210246294A1 (en) * 2018-03-20 2021-08-12 Denka Company Limited Fiber for artificial hair and hair accessory product
KR20200133758A (en) 2018-03-20 2020-11-30 덴카 주식회사 Artificial hair fibers and hair decoration products
KR20210016546A (en) 2018-06-07 2021-02-16 덴카 주식회사 Artificial hair fibers and hair decoration products
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WO2023021883A1 (en) * 2021-08-20 2023-02-23 デンカ株式会社 Fibers for artificial hair, fiber bundle for artificial hair, and hair decoration product
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WO2023145171A1 (en) * 2022-01-25 2023-08-03 デンカ株式会社 Artificial hair fibers and hairpiece product

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