WO2007099858A1 - Vinyl chloride resin fiber and method for producing same - Google Patents

Vinyl chloride resin fiber and method for producing same Download PDF

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Publication number
WO2007099858A1
WO2007099858A1 PCT/JP2007/053314 JP2007053314W WO2007099858A1 WO 2007099858 A1 WO2007099858 A1 WO 2007099858A1 JP 2007053314 W JP2007053314 W JP 2007053314W WO 2007099858 A1 WO2007099858 A1 WO 2007099858A1
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WO
WIPO (PCT)
Prior art keywords
resin
fiber
vinyl
polyester
mass
Prior art date
Application number
PCT/JP2007/053314
Other languages
French (fr)
Japanese (ja)
Inventor
Akira Sakurai
Yukihisa Hoshino
Original Assignee
Denki Kagaku Kogyo Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Denki Kagaku Kogyo Kabushiki Kaisha filed Critical Denki Kagaku Kogyo Kabushiki Kaisha
Priority to CN2007800041870A priority Critical patent/CN101379229B/en
Priority to JP2008502743A priority patent/JP5210856B2/en
Priority to US12/280,688 priority patent/US20100233390A1/en
Publication of WO2007099858A1 publication Critical patent/WO2007099858A1/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
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/10—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polyvinyl chloride or polyvinylidene chloride
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
    • 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

  • Vinyl chloride resin fiber and method for producing the same
  • the present invention relates to a salty-bull type resin fiber that is resistant to heat shrinkage and excellent in heat resistance, and a method for producing the same.
  • salt-bulb resin is excellent in weather resistance, transparency, flame retardancy, chemical resistance, and is inexpensive, so it is used as a typical general-purpose plastic for various applications.
  • the fiber is often used as a fiber for artificial hair such as wigs for human hair because it has strength, elongation, and feel close to those of natural hair.
  • Patent Document 1 Japanese Patent Publication No. 60-18323
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-193329
  • An object of the present invention is to provide a fiber comprising a vinyl chloride resin having excellent heat resistance, which is difficult to heat shrink even at temperatures exceeding 100 ° C, and a method for producing the same. Means for solving the problem
  • the present invention has the following gist.
  • (1) It comprises a melt-spun fiber of a resin composition containing 1 to 300 parts by mass of a polyester-based resin with respect to 100 parts by mass of the salt-and-bulb resin.
  • the salty vinyl resin fiber is a melt-spun fiber of a resin composition containing 1 to 300 parts by mass of a polyester-based resin with respect to 100 parts by mass of the salt-and-bulb resin.
  • the fiber comprising the salty vinyl resin of the present invention comprises 1 to 10 parts of a polyester resin relative to 100 parts by weight of the salty vinyl resin and 100 parts by mass of the salty vinyl resin. It is formed from a resin composition containing 300 parts by mass.
  • the salt-bulb resin used in the present invention may be a resin obtained by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., taking into consideration the initial coloration of the fiber, etc. Thus, it is preferable to use those produced by suspension polymerization.
  • the salt-bulb-based resin is a homopolymer resin of a salt-bulu that is a homopolymer of a conventionally known salt-vinyl, or various conventionally known salt-bulb copolymer resins, It is not particularly limited.
  • a conventionally known copolymer resin can be used.
  • a copolymer resin of a salt-bule and a bull ester such as a salt-bulle monoacetate-bule copolymer resin, a salt-bulle-propionate-bule copolymer resin
  • a typical example is a copolymer resin of a salted bule and olefins such as a propylene copolymer resin; a salt-bulu-acrylonitrile copolymer resin. It is particularly preferable to use homopolymer resin, salt-bulle ethylene copolymer resin, salt-bule acetate bulcopolymer resin, etc., which are homopolymers of salt-bulu.
  • the content of the comonomer is not particularly limited in the above-described salt-bulb copolymer resin.
  • the content of comonomer is preferably 2 to 30% by mass, particularly preferably 2 to 20% by mass.
  • the viscosity-average polymerization degree of the salt-bulb type resin used in the present invention is preferably 600-2500, more preferably 600-1800. If the viscosity average polymerization degree of the salty vinyl resin is less than 600, the melt viscosity is lowered, and the resulting fiber may be easily heat-shrinked. On the other hand, if the viscosity average polymerization degree exceeds 2500, the melt pressure increases and the nozzle pressure increases. It may become difficult to manufacture safely.
  • the viscosity average degree of polymerization was determined by dissolving 200 mg of rosin in 50 ml of nitrobenzene and setting the specific viscosity of this polymer solution in a 30 ° C constant temperature bath! Measured with an Ubbelohde viscometer and calculated according to JIS-K6720-2.
  • the polyester-based resin used in the present invention is an aromatic polyester-based resin such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; , Aliphatic polyester coffins such as polybutylene adipate, polyethylene succinate, polyglycolic acid, poly 3-hydroxypropionate, poly 3-hydroxybutyrate, and the like.
  • the polyester-based resin includes the polyester-based resin copolymer, the polyester-based resin block or graft polymer shown above, and also blends with other resins. Is done. Among them, although not particularly limited, aliphatic polyester resin is preferred, and polylactic acid resin is particularly preferable from the viewpoint of mixing with a salty vinyl resin.
  • the polyester resin in the present invention has a melting point of preferably 100 to 300 ° C, particularly preferably 120 to 250 ° C, most preferably 130 to 200 ° C, and has crystallinity. It is preferable to use. If the melting point of the polyester resin is less than 100 ° C, the resulting fiber may have poor heat resistance. On the other hand, when the melting point exceeds 300 ° C, it may be difficult to mix with the salted vinyl resin.
  • the melting point of the polyester-based resin is the temperature at which the peak of the heat of fusion occurs when a sample is heated at a heating rate of 10 ° CZ in a nitrogen atmosphere using a differential scanning calorimeter (DSC). This is a value calculated according to JISK-7121.
  • the polylactic acid-based rosin in the present invention is not particularly limited! /.
  • the molecular weight of the polylactic acid-based resin used in the present invention is preferably 10,000 to 1,000,000, more preferably 20,000 to the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography. 750,000, particularly preferably 30,000 to 500,000. Weight If the average molecular weight is small, the effect of improving the heat resistance of the obtained fiber is too small, and mixing with the salted bull resin may be difficult.
  • the resin composition for forming the fiber of the present invention 1 to 300 parts by mass, preferably 2 parts of polyester resin is used per 100 parts by mass of vinyl chloride resin and 100 parts by mass of vinyl chloride resin. ⁇ 200 parts by mass, particularly preferably 5 to 150 parts by mass, most preferably 10 to: LOO parts by mass. If the polyester-based resin is less than 1 part by mass, the resulting fiber has poor heat resistance. On the other hand, if the polyester-based resin exceeds 300 parts by mass, the obtained fiber has poor flame retardancy.
  • the fiber composition for fiber formation of the present invention is not limited to the salt-based resin and the polyester-based resin, and is conventionally used for a salt-based resin depending on the purpose.
  • Known additives are mixed. These additives are not particularly limited, but known additives may be blended depending on the purpose. For example, lubricants, heat stabilizers, processing aids, reinforcing agents, UV absorbers, antioxidants, antistatic agents, fillers, flame retardants, pigments, initial color improvers, conductivity enhancers, surface treatment agents, light There are stabilizers and fragrances.
  • a resin composition containing a vinyl chloride resin, a polyester resin, and, if necessary, an additive used in the production of the fiber of the present invention is prepared by using a conventionally known mixer such as a Henschel mixer, a super It can be used as a powder compound formed by mixing using a mixer, a ribbon blender or the like, or as a pellet compound formed by melting and mixing this.
  • a conventionally known mixer such as a Henschel mixer, a super It can be used as a powder compound formed by mixing using a mixer, a ribbon blender or the like, or as a pellet compound formed by melting and mixing this.
  • the powder compound can be produced under conventional conditions known in the art.
  • the pellet composition can be produced in the same manner as ordinary salt vinyl chloride pellets.
  • pellets using a kneader such as a single screw extruder, a different direction twin screw extruder, a conical twin screw extruder, a same direction twin screw extruder, a kneader, a planetary gear single extruder, a roll kneader, etc. It can be a compound.
  • the fiber composition is made into a fibrous undrawn yarn by a conventionally known spinning method.
  • the spinning method is not particularly limited, but the melt spinning method is preferable.
  • a conventionally known extruder can be used for melt spinning.
  • single screw extruder, Different-direction twin screw extruders, co-axial twin screw extruders, etc. can be used, but in particular, a single screw extruder preferably having a diameter of about 35 to 200 mm, or a conical twin screw extruder having a diameter of preferably about 35 to 150 mm Is preferably used.
  • melt spinning can be performed using a conventionally known nozzle.
  • the cross-sectional area of one nozzle hole is more than 3 mm 2, undrawn yarn of fine fineness, or it is necessary to apply an excessive tension to the drawn yarn, sometimes yarn breakage.
  • the shape of the cross-sectional area of the nozzle hole is preferably a circular hollow shape, eyeglass shape, Y shape, or C shape.
  • a multi-type nozzle hole (the number of nozzle holes is preferably 50 to 500, preferably formed by arranging a plurality of nozzle holes having a cross-sectional area of 3 mm 2 or less in one die hole on a die).
  • the number of nozzle arrangements is preferably 1 to 5 rows.
  • the strands are allowed to flow out, and it is preferable to produce undrawn yarns having a single fineness of preferably 300 dtex or less.
  • the pellet compound of the resin composition is melt-spun using, for example, a short screw extruder at a resin temperature of preferably 150 to 200 ° C, more preferably 155 to 195 ° C.
  • a resin temperature of preferably 150 to 200 ° C, more preferably 155 to 195 ° C.
  • An undrawn yarn can be obtained.
  • the undrawn yarn obtained by melt spinning can be subjected to a drawing treatment and heat treatment by a known method to obtain a fiber (drawn yarn) having a fineness of preferably 600 dtex or less.
  • stretching is preferably performed at a stretching ratio of preferably 2 to 20 times in an air atmosphere where the stretching temperature is preferably maintained at a temperature of 30 to 150 ° C.
  • the stretching ratio is preferably 2 to 10 times in an air atmosphere with a stretching temperature of preferably 80 to 140 ° C.
  • the total length of the fiber is preferably 99.8 to 50% before treatment, more preferably 99.8 to 70%.
  • the thermal contraction rate can be lowered by heat relaxation treatment until the length becomes.
  • the thermal relaxation process can be performed in conjunction with the stretching process or can be performed separately.
  • a conventionally known technique related to melt spinning for example, various nozzles It is possible to apply any combination of technologies related to cross-sectional shapes, technologies related to heating cylinders, and technologies related to heat treatment.
  • the undrawn yarn that has been drawn and heat-treated has a single fineness of preferably 1 to 200 dtex, more preferably 5 to 150 dtex, and particularly preferably 10 to 100 dtex.
  • a single fineness preferably 1 to 200 dtex, more preferably 5 to 150 dtex, and particularly preferably 10 to 100 dtex.
  • Decitex is a value obtained by measuring the weight of 20 fibers with a length of 100 cm and multiplying the average weight per fiber by 10,000.
  • the above-described fibers may not be necessarily uniform, and a plurality of fibers having different single filament sizes may be mixed in the spinning process or after spinning. (Blend) can also be used.
  • a step of obtaining an undrawn yarn having an average fineness of 150 decitus (c) a step of drawing the melt-spun fiber to 300% in an air atmosphere of 105 ° C, and (d) the drawing Under air atmosphere 140 ° C to the fibers, the step of thermal relaxation until the entire length of the fiber to shrink to 75% of the length of the pre-treatment, the through sequential, single fineness to obtain a fiber of 65 dtex.
  • Example 2 to: L0 Fibers were obtained in the same manner as in Example 1 using the blending amounts of vinyl chloride-based resin and polyester-based resin shown in Table 1.
  • a fiber was obtained in the same manner as in Example 1, except that the salty-bulb-based resin had a low degree of polymerization and was changed to vinyl chloride resin (TH-700 manufactured by Taiyo PVC Co., Ltd., viscosity average polymerization degree 700). .
  • a fiber was obtained in the same manner as in Example 1 except that the salty-bulb-based resin was changed to a high degree of polymerization and vinyl chloride resin (TH-2000, Taiyo PVC Co., Ltd., viscosity average polymerization degree 2000). .
  • Example 1 with the exception that the salt-bulb-based resin was changed to salt-bule-ethylene copolymer resin (E-1050, Taiyo PVC Co., 98% by weight chloride content, viscosity average polymerization degree 1050). In the same manner, fibers were obtained.
  • E-1050 salt-bule-ethylene copolymer resin
  • Taiyo PVC Co. 98% by weight chloride content, viscosity average polymerization degree 1050
  • Example 1 and Example 1 except that the salty bule-based rosin was changed to salty bule acetate bulle copolymer rosin (Taiyo PVC Co., Ltd. TV 800, butyl chloride content 93 mass%, viscosity average polymerization degree 780) In the same manner, a fiber was obtained.
  • a fiber was obtained in the same manner as in Example 1 except that the polylactic acid-based resin was changed to crystalline polyester resin (Nylon GM-925, Toyobo Co., Ltd., melting point 166 ° C).
  • a fiber was obtained in the same manner as in Example 1, except that the polylactic acid resin was changed to crystalline polyester resin (Nonlon GA-5410 manufactured by Toyobo Co., Ltd., melting point: 117 ° C).
  • a fiber was obtained in the same manner as in Example 1 except that it did not contain polylactic acid-based greaves.
  • Fibers were obtained in the same procedure as in Example 1 using chlorinated salt-bulle fat (HA-24K manufactured by Sekisui Chemical Co., Ltd.) instead of polylactic acid-based fat, using the blending amounts shown in Table 2. .
  • spinnability represents the moldability when melt-spinning the resin composition.
  • spinnability test when 120 fibers were extruded from a spinning mold at the same time, the number of occurrences of yarn breakage of the fibers (several fibrous bodies were interrupted during melt extrusion). The measurement time is 30 minutes and the number of measurements is 3.
  • thermal shrinkage (%) represents the thermal shrinkage rate that occurs when the specimen is heat-treated. Specifically, twelve fiber specimens adjusted to a length of 100 mm were left in a gear oven at 130 ° C for 15 minutes, and the ratio of the specimen lengths before and after leaving (((length before leaving) -Length after standing) Length before leaving Z) Calculated by X100. The numerical value is the average value of 10 out of 12, excluding the maximum and minimum values.
  • the fibers obtained using the greave composition of the present invention are, for example, clothing textile products such as underwear and socks, life-related textile products such as rugs, curtains and towels, especially for hair decoration and artificial hair. It can be suitably used for fibers. It should be noted that the entire contents of the specification, claims, and abstract of the Japanese Patent Application No. 2006-051859 filed on February 28, 2006 are hereby incorporated herein by reference. And that is what we take in.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Artificial Filaments (AREA)

Abstract

Disclosed is a fiber made of a vinyl chloride resin, which is excellent in heat resistance and thus hardly shrinks thermally even at a temperature higher than 100˚C. Specifically disclosed is a fiber obtained by melt-spinning a resin composition containing a vinyl chloride resin and 1-300 parts by mass of a polyester resin per 100 parts by mass of the vinyl chloride resin. The vinyl chloride resin has a viscosity-average polymerization degree of 600-2500. The polyester resin is composed of a polylactic acid resin, and has a melting point of 100-300˚C.

Description

明 細 書  Specification
塩化ビニル系樹脂繊維及びその製造方法  Vinyl chloride resin fiber and method for producing the same
技術分野  Technical field
[0001] 本発明は、熱収縮しにくい耐熱性に優れた塩ィ匕ビュル系榭脂繊維及びその製造 方法に関するものである。  TECHNICAL FIELD [0001] The present invention relates to a salty-bull type resin fiber that is resistant to heat shrinkage and excellent in heat resistance, and a method for producing the same.
背景技術  Background art
[0002] 従来、塩ィ匕ビュル系榭脂は、耐候性、透明性、難燃性、耐薬品性に優れ、安価で あることから典型的な汎用プラスチックとして、様々な用途に利用されている。その繊 維は、強度、伸度、感触などが天然毛髪に近いことから、例えば、頭髪用カツラゃ人 形頭髪などの人工毛髪用繊維として多く使用されている。  [0002] Conventionally, salt-bulb resin is excellent in weather resistance, transparency, flame retardancy, chemical resistance, and is inexpensive, so it is used as a typical general-purpose plastic for various applications. . The fiber is often used as a fiber for artificial hair such as wigs for human hair because it has strength, elongation, and feel close to those of natural hair.
[0003] しかし、更に天然毛髪に近似させるため、様々な繊維二次力卩ェが施される力 この 結果として頭髪用カツラなどの加工工程において、必要以上に熱収縮してしまう課題 がある。これを解決する手段として、塩ィ匕ビュル榭脂と塩素化塩ィ匕ビュル榭脂からな る塩化ビニル系繊維 (特許文献 1参照。）が提案されているが、この方法では多量の 塩素化塩ィ匕ビュル榭脂を添加することが困難であり、十分な効果を得られない場合 かあつた。  However, there is a problem that heat shrinks more than necessary in the processing step of hair wigs and the like as a result of applying various fiber secondary forces to approximate natural hair. As a means to solve this problem, vinyl chloride fiber (see Patent Document 1) consisting of salt-bulb fat and chlorinated salt-bulb fat has been proposed. It was difficult to add salty mulberry oil and it was not possible to obtain a sufficient effect.
[0004] 更に、特定の塩素化塩ィ匕ビュル榭脂を 2種類添加した塩ィ匕ビュル系繊維 (特許文 献 2参照。）が提案されている。この手段により塩素化塩ィ匕ビュル榭脂の添加量を増 カロさせることができ、 100°C程度での熱収縮を抑えることは可能となった。しかし近年 、頭飾用かつらのスタイルの多様化、高度化によって、より高温での加工処理が要求 され、該手段では対応が困難であり、加工特性に劣る場合があった。  [0004] Furthermore, a salty-bull fiber (see Patent Document 2) to which two types of specific chlorinated salt-bully resin are added has been proposed. By this means, it was possible to increase the amount of chlorinated salt / bulb fat added and to suppress heat shrinkage at around 100 ° C. However, in recent years, with the diversification and sophistication of the style of wigs for head ornaments, processing at higher temperatures has been required, and it has been difficult to cope with this means, and the processing characteristics have sometimes been poor.
特許文献 1：特公昭 60— 18323号公報  Patent Document 1: Japanese Patent Publication No. 60-18323
特許文献 2 :特開 2003— 193329号公報  Patent Document 2: Japanese Patent Laid-Open No. 2003-193329
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0005] 本発明の目的は、 100°Cを超える温度でも熱収縮しにく!/ヽ耐熱性の優れた塩化ビ 二ル系榭脂からなる繊維及びその製造方法を提供することにある。 課題を解決するための手段 [0005] An object of the present invention is to provide a fiber comprising a vinyl chloride resin having excellent heat resistance, which is difficult to heat shrink even at temperatures exceeding 100 ° C, and a method for producing the same. Means for solving the problem
[0006] すなわち、本発明は、以下の要旨を有するものである。  That is, the present invention has the following gist.
(1)塩ィ匕ビュル系榭脂、及び該塩ィ匕ビュル系榭脂 100質量部に対しポリエステル系 榭脂を 1〜300質量部含有する榭脂組成物の溶融紡糸繊維からなることを特徴とす る塩ィ匕ビ二ル系榭脂繊維。  (1) It comprises a melt-spun fiber of a resin composition containing 1 to 300 parts by mass of a polyester-based resin with respect to 100 parts by mass of the salt-and-bulb resin. The salty vinyl resin fiber.
(2)塩化ビニル系榭脂の粘度平均重合度が、 600〜2500である、上記（1)に記載 の塩ィ匕ビ二ル系榭脂繊維。  (2) The vinyl chloride resin fiber according to (1) above, wherein the vinyl chloride resin has a viscosity average polymerization degree of 600 to 2500.
(3)ポリエステル系榭脂の融点が 100〜300°Cである、上記（1)又は（2)に記載の塩 化ビュル系榭脂繊維。  (3) The salted bull resin fiber according to (1) or (2) above, wherein the melting point of the polyester resin is 100 to 300 ° C.
(4)ポリエステル系榭脂がポリ乳酸系榭脂である、上記（1)〜（3)の 、ずれかに記載 の塩ィ匕ビ二ル系榭脂繊維。  (4) The salted vinyl resin fiber according to any one of (1) to (3), wherein the polyester resin is a polylactic acid resin.
(5)繊維の単繊度が 1〜200デシテックスである、上記（1)〜（4)のいずれかに記載 の塩ィ匕ビ二ル系榭脂繊維。  (5) The salted vinyl resin fiber according to any one of the above (1) to (4), wherein the single fineness of the fiber is 1 to 200 dtex.
(6)上記（1)〜（5)の 、ずれかに記載の塩ィ匕ビ二ル系榭脂繊維力もなる人工毛髪。 (6) Artificial hair which also has the strength of the salty vinyl resin fiber according to any one of (1) to (5) above.
(7) (a)塩ィ匕ビ二ル系榭脂と、ポリエステル系榭脂と、を含む榭脂組成物を混合する 工程； (7) (a) a step of mixing a resin composition containing a salty vinyl resin and a polyester resin;
(b)前記榭脂組成物を、紡糸金型力も榭脂温度 150〜200°Cで溶融紡糸する工程  (b) A step of melt spinning the resin composition at a resin temperature of 150 to 200 ° C.
(c)前記溶融紡糸した繊維を、延伸処理温度 30〜150°Cの空気雰囲気下で、延 伸倍率 2〜20倍に延伸する工程； (c) stretching the melt-spun fiber at a stretching ratio of 2 to 20 times in an air atmosphere at a stretching temperature of 30 to 150 ° C;
(d)前記延伸した繊維を、 80〜200°Cの温度に保持した空気雰囲気下で、繊維全 長が処理前の 99. 8〜50%の長さになるまで熱弛緩処理する工程；  (d) a step of subjecting the drawn fiber to a thermal relaxation treatment in an air atmosphere maintained at a temperature of 80 to 200 ° C. until the total fiber length is 99.8 to 50% before treatment;
を順次有する塩化ビニル系榭脂繊維の製造方法。  The manufacturing method of the vinyl chloride type | system | group resin fiber which has these one by one.
(8)前記溶融紡糸する工程で用いるノズル孔の 1個の断面積が 3mm2以下である、 上記 (7)に記載の塩ィ匕ビュル系榭脂繊維の製造方法。 (8) The method for producing a salty-bull resin fiber according to (7) above, wherein one nozzle hole used in the melt spinning step has a cross-sectional area of 3 mm 2 or less.
発明の効果  The invention's effect
[0007] 本発明によれば、 100°Cを越える温度でも熱収縮しにく!/、耐熱性に優れ、光沢が 少なぐし力も溶融紡糸時に糸切れの少ないために、頭髪装飾用や人工毛髪用繊維 に好適である塩ィ匕ビュル系榭脂からなる繊維及びその製造方法が提供される。 発明を実施するための最良の形態 [0007] According to the present invention, heat shrinkage does not easily occur even at temperatures exceeding 100 ° C! /, Because of excellent heat resistance, low gloss, and low squeezing force, and less thread breakage during melt spinning. Fiber And a method for producing the same, which is suitable for a fiber comprising a salt-bulb resin. BEST MODE FOR CARRYING OUT THE INVENTION
[0008] 本発明の塩ィ匕ビニル榭脂からなる繊維は、塩ィ匕ビ二ル系榭脂と、該塩ィ匕ビニル系 榭脂 100質量部に対して、ポリエステル系榭脂を 1〜300質量部、を含有する榭脂 組成物から形成される。  [0008] The fiber comprising the salty vinyl resin of the present invention comprises 1 to 10 parts of a polyester resin relative to 100 parts by weight of the salty vinyl resin and 100 parts by mass of the salty vinyl resin. It is formed from a resin composition containing 300 parts by mass.
[0009] 本発明で使用される塩ィ匕ビュル系榭脂は、塊状重合、溶液重合、懸濁重合、乳化 重合等によって得られた榭脂を使用できるが、繊維の初期着色性等を勘案して、懸 濁重合によって製造したものを使用することが好ましい。 [0009] The salt-bulb resin used in the present invention may be a resin obtained by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., taking into consideration the initial coloration of the fiber, etc. Thus, it is preferable to use those produced by suspension polymerization.
塩ィ匕ビュル系榭脂とは、従来公知の塩ィ匕ビニルの単独重合物である塩ィ匕ビュルの ホモポリマー榭脂、又は、従来公知の各種の塩ィ匕ビュルコポリマー榭脂であり、特に 限定されるものではない。  The salt-bulb-based resin is a homopolymer resin of a salt-bulu that is a homopolymer of a conventionally known salt-vinyl, or various conventionally known salt-bulb copolymer resins, It is not particularly limited.
[0010] 上記塩ィ匕ビニル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。例えば、塩ィ匕ビュル一酢酸ビュルコポリマー榭脂、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ュルとビュルエステル類とのコポリマー榭脂[0010] As the above-mentioned salty vinyl copolymer resin, a conventionally known copolymer resin can be used. For example, a copolymer resin of a salt-bule and a bull ester such as a salt-bulle monoacetate-bule copolymer resin, a salt-bulle-propionate-bule copolymer resin
；塩化ビニルーアクリル酸ブチルコポリマー榭脂、塩化ビニルーアクリル酸 2ェチルへ キシルコポリマー榭脂等の塩ィ匕ビュルとアクリル酸エステル類とのコポリマー榭脂；塩 化ビュル エチレンコポリマー榭脂、塩ィ匕ビュル プロピレンコポリマー榭脂等の塩 化ビュルとォレフィン類とのコポリマー榭脂；塩ィ匕ビュル一アクリロニトリルコポリマー 榭脂などが代表的に例示される。特に好ましくは、塩ィ匕ビュ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 ポリマー榭脂等を使用することが好ましい。 ： Vinyl chloride-butyl acrylate copolymer resin, vinyl chloride-acrylic acid 2-ethyl hexyl copolymer resin, etc. salt resin resin and acrylate ester copolymer resin; A typical example is a copolymer resin of a salted bule and olefins such as a propylene copolymer resin; a salt-bulu-acrylonitrile copolymer resin. It is particularly preferable to use homopolymer resin, salt-bulle ethylene copolymer resin, salt-bule acetate bulcopolymer resin, etc., which are homopolymers of salt-bulu.
[0011] 上記塩ィ匕ビュルコポリマー榭脂において、コモノマーの含有量は、特に限定されず[0011] The content of the comonomer is not particularly limited in the above-described salt-bulb copolymer resin.
、成形加工性、糸特性などの要求品質に応じて決めることができる。コモノマーの含 有量は、好ましくは 2〜30質量％であり、特に好ましくは 2〜20質量％である。 It can be determined according to the required quality such as moldability and yarn characteristics. The content of comonomer is preferably 2 to 30% by mass, particularly preferably 2 to 20% by mass.
[0012] 本発明に使用する塩ィ匕ビュル系榭脂の粘度平均重合度は、 600〜2500が好まし ぐ 600〜1800がより好ましい。塩ィ匕ビ二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ため、得られる繊維が熱収縮しやすくなる恐れがある。 一方、粘度平均重合度が 2500を超えると、溶融粘度が高くなるためノズル圧力が高 くなり安全な製造が困難になる恐れがある。尚、粘度平均重合度は、榭脂 200mgを ニトロベンゼン 50mlに溶解させ、このポリマー溶液の比粘度を 30°C恒温槽中にお！ヽ て、ウベローデ型粘度計を用いて測定し、 JIS— K6720— 2により算出した値である。 [0012] The viscosity-average polymerization degree of the salt-bulb type resin used in the present invention is preferably 600-2500, more preferably 600-1800. If the viscosity average polymerization degree of the salty vinyl resin is less than 600, the melt viscosity is lowered, and the resulting fiber may be easily heat-shrinked. On the other hand, if the viscosity average polymerization degree exceeds 2500, the melt pressure increases and the nozzle pressure increases. It may become difficult to manufacture safely. The viscosity average degree of polymerization was determined by dissolving 200 mg of rosin in 50 ml of nitrobenzene and setting the specific viscosity of this polymer solution in a 30 ° C constant temperature bath! Measured with an Ubbelohde viscometer and calculated according to JIS-K6720-2.
[0013] 本発明で使用するポリエステル系榭脂は、ポリエチレンテレフタレート、ポリトリメチ レンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートなどの芳香 族ポリエステル系榭脂；ポリ乳酸、ポリヒドロキシ酪酸、ポリ力プロラタトン、ポリプチレン サクシネート、ポリブチレンアジペート、ポリエチレンサクシネート、ポリグリコール酸、 ポリ 3—ヒドロキシプロピオネート、ポリ 3—ヒドロキシブチレートなどの脂肪族ポリ エステル榭脂などが挙げられる。  [0013] The polyester-based resin used in the present invention is an aromatic polyester-based resin such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; , Aliphatic polyester coffins such as polybutylene adipate, polyethylene succinate, polyglycolic acid, poly 3-hydroxypropionate, poly 3-hydroxybutyrate, and the like.
[0014] また、上記ポリエステル系榭脂には、上記に示したポリエステル系榭脂の共重合体 、ポリエステル系榭脂のブロック若しくはグラフト重合体、更には、他の樹脂とのプレン ド物も包含される。なかでも、特に限定されないが、塩ィ匕ビ二ル系榭脂との混合性の 点で、脂肪族ポリエステル榭脂が好ましぐ特にポリ乳酸系榭脂が好ましい。  [0014] Further, the polyester-based resin includes the polyester-based resin copolymer, the polyester-based resin block or graft polymer shown above, and also blends with other resins. Is done. Among them, although not particularly limited, aliphatic polyester resin is preferred, and polylactic acid resin is particularly preferable from the viewpoint of mixing with a salty vinyl resin.
[0015] 本発明におけるポリエステル系榭脂は、融点が、好ましくは 100〜300°C、特に好 ましくは 120〜250°C、最も好ましくは 130〜200°Cであり、結晶性を有するものを使 用することが好ましい。ポリエステル系榭脂の融点力 100°C未満であると得られる繊 維の耐熱性が劣る場合がある。一方、融点が、 300°Cを超えると塩ィ匕ビ二ル系榭脂と の混合が難しくなる場合がある。  [0015] The polyester resin in the present invention has a melting point of preferably 100 to 300 ° C, particularly preferably 120 to 250 ° C, most preferably 130 to 200 ° C, and has crystallinity. It is preferable to use. If the melting point of the polyester resin is less than 100 ° C, the resulting fiber may have poor heat resistance. On the other hand, when the melting point exceeds 300 ° C, it may be difficult to mix with the salted vinyl resin.
ポリエステル系榭脂の上記融点とは、示差走査型熱量計 (DSC)を用い、試料約 5 mgを窒素中、昇温速度 10°CZ分で昇温させた時の融解熱量のピークとなる温度を 表し、 JISK— 7121により算出した値である。  The melting point of the polyester-based resin is the temperature at which the peak of the heat of fusion occurs when a sample is heated at a heating rate of 10 ° CZ in a nitrogen atmosphere using a differential scanning calorimeter (DSC). This is a value calculated according to JISK-7121.
[0016] 本発明における好ま 、ポリ乳酸系榭脂としては、特に制限されるものではな!/、。  [0016] Preferably, the polylactic acid-based rosin in the present invention is not particularly limited! /.
一般的に、ポリ乳酸系榭脂の光学純度が低いと結晶性が低下し、特に融点が低下 することが知られている。このため、 L体が 70%以上、好ましくは 80%以上、特に好ま しくは 90%以上含まれるものが使用される。  In general, it is known that when the optical purity of the polylactic acid-based resin is low, the crystallinity is lowered, and in particular, the melting point is lowered. For this reason, a substance containing 70% or more of L form, preferably 80% or more, particularly preferably 90% or more is used.
本発明にお 、て用いられるポリ乳酸系榭脂の分子量は、ゲルパーミエーシヨンクロ マトグラフィ一で測定した標準ポリスチレン換算の重量平均分子量として、好ましくは 1万〜 100万、より好ましくは 2万〜 75万、特に好ましくは 3万〜 50万である。重量平 均分子量が小さければ、得られる繊維の耐熱性向上の効果が乏しぐ大きければ塩 化ビュル系榭脂との混合が困難になる場合がある。 In the present invention, the molecular weight of the polylactic acid-based resin used in the present invention is preferably 10,000 to 1,000,000, more preferably 20,000 to the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography. 750,000, particularly preferably 30,000 to 500,000. Weight If the average molecular weight is small, the effect of improving the heat resistance of the obtained fiber is too small, and mixing with the salted bull resin may be difficult.
[0017] 本発明の繊維を形成する榭脂組成物としては、塩化ビニル系榭脂と、塩化ビニル 系榭脂 100質量部に対して、ポリエステル系榭脂を 1〜300質量部、好ましくは 2〜2 00質量部、特に好ましくは 5〜150質量部、最も好ましくは 10〜： LOO質量部含むも のである。ポリエステル系榭脂が 1質量部未満であると、得られる繊維の耐熱性が劣 る。一方、ポリエステル系榭脂が 300質量部を超えると、得られる繊維の難燃性が劣 る。  [0017] As the resin composition for forming the fiber of the present invention, 1 to 300 parts by mass, preferably 2 parts of polyester resin is used per 100 parts by mass of vinyl chloride resin and 100 parts by mass of vinyl chloride resin. ~ 200 parts by mass, particularly preferably 5 to 150 parts by mass, most preferably 10 to: LOO parts by mass. If the polyester-based resin is less than 1 part by mass, the resulting fiber has poor heat resistance. On the other hand, if the polyester-based resin exceeds 300 parts by mass, the obtained fiber has poor flame retardancy.
[0018] 本発明の繊維形成用の榭脂組成物には、塩ィ匕ビ二ル系榭脂とポリエステル系榭脂 以外に、目的に応じて塩ィ匕ビュル系榭脂に使用される従来公知の添加剤が混合さ れる。これらの添加剤は特に限定されないが、目的に応じて公知の添加剤が配合さ れる。例えば、滑剤、熱安定剤、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、香料等がある。  [0018] The fiber composition for fiber formation of the present invention is not limited to the salt-based resin and the polyester-based resin, and is conventionally used for a salt-based resin depending on the purpose. Known additives are mixed. These additives are not particularly limited, but known additives may be blended depending on the purpose. For example, lubricants, heat stabilizers, processing aids, reinforcing agents, UV absorbers, antioxidants, antistatic agents, fillers, flame retardants, pigments, initial color improvers, conductivity enhancers, surface treatment agents, light There are stabilizers and fragrances.
[0019] 次に、本発明の塩ィ匕ビュル系榭脂繊維の製造方法について述べる。  [0019] Next, a method for producing the salty bulle type resin fiber of the present invention will be described.
本発明の繊維の製造に使用する塩化ビニル系榭脂と、ポリエステル系榭脂と、必要 に応じて添加剤とを含んだ榭脂組成物は、従来公知の混合機、例えば、ヘンシェル ミキサー、スーパーミキサー、リボンブレンダ一等を使用して混合してなるパウダーコ ンパウンド、又はこれを溶融混合してなるペレットコンパウンドとして使用することがで きる。  A resin composition containing a vinyl chloride resin, a polyester resin, and, if necessary, an additive used in the production of the fiber of the present invention is prepared by using a conventionally known mixer such as a Henschel mixer, a super It can be used as a powder compound formed by mixing using a mixer, a ribbon blender or the like, or as a pellet compound formed by melting and mixing this.
[0020] パウダーコンパウンドは、従来公知の通常の条件で製造できる。また、ペレットコン ノゥンドは、通常の塩ィ匕ビニル系ペレットの製造と同様にして製造できる。例えば、単 軸押出機、異方向 2軸押出機、コニカル 2軸押出機、同方向 2軸押出機、コニーダー 、プラネタリーギア一押出機、ロール混練り機等の混練り機を使用してペレットコンパ ゥンドとすることができる。  [0020] The powder compound can be produced under conventional conditions known in the art. In addition, the pellet composition can be produced in the same manner as ordinary salt vinyl chloride pellets. For example, pellets using a kneader such as a single screw extruder, a different direction twin screw extruder, a conical twin screw extruder, a same direction twin screw extruder, a kneader, a planetary gear single extruder, a roll kneader, etc. It can be a compound.
[0021] 本発明にお 、て、前記榭脂組成物を繊維状の未延伸糸にするのは、従来公知の 紡糸法によって行われる。紡糸法は特に限定されないが、溶融紡糸法が好ましい。 溶融紡糸をおこなう際には従来公知の押出機を使用できる。例えば、単軸押出機、 異方向 2軸押出機、コ-カル 2軸押出機等を使用できるが、特に口径が好ましくは 35 〜200mm程度の単軸押出機、又は口径が好ましくは 35〜150mm程度のコニカル 2軸押出機を使用することが好ましい。 [0021] In the present invention, the fiber composition is made into a fibrous undrawn yarn by a conventionally known spinning method. The spinning method is not particularly limited, but the melt spinning method is preferable. A conventionally known extruder can be used for melt spinning. For example, single screw extruder, Different-direction twin screw extruders, co-axial twin screw extruders, etc. can be used, but in particular, a single screw extruder preferably having a diameter of about 35 to 200 mm, or a conical twin screw extruder having a diameter of preferably about 35 to 150 mm Is preferably used.
[0022] 本発明においては、従来公知のノズルを用いて溶融紡糸をすることが可能である。 In the present invention, melt spinning can be performed using a conventionally known nozzle.
例えば、 1個のノズル孔の断面積が好ましくは 3mm2以下、より好ましくは lmm2以下 、特に好ましくは 0. 5mm2以下のノズルをダイ (紡糸金型）の先端部に取り付けて溶 融紡糸を行なうのが好ましい。 1個のノズル孔の断面積が 3mm2を超えると、細繊度 の未延伸糸、又は延伸糸とするために過大な張力をかける必要があり、糸切れする 場合がある。ノズル孔の断面積の形状は好ましくは円形の中空形、メガネ形、 Y形、 又は C形である。 For example, is preferably cross-sectional area of one nozzle hole 3 mm 2 or less, more preferably lmm 2 or less, particularly preferably molten spun attached to the tip of the die (spinning die) nozzles 0. 5 mm 2 or less Is preferably performed. When the cross-sectional area of one nozzle hole is more than 3 mm 2, undrawn yarn of fine fineness, or it is necessary to apply an excessive tension to the drawn yarn, sometimes yarn breakage. The shape of the cross-sectional area of the nozzle hole is preferably a circular hollow shape, eyeglass shape, Y shape, or C shape.
[0023] 本発明においては、 1個のノズル孔の断面積が 3mm2以下の複数のノズル孔をダイ に配列してなるマルチタイプのノズル孔（ノズル孔数は、好ましくは 50〜500個、ノズ ル配列数は好ましくは 1〜5列である。）からストランドを流出せしめて、単繊度が好ま しくは 300デシテックス以下の未延伸糸を製造することが好ま 、。 [0023] In the present invention, a multi-type nozzle hole (the number of nozzle holes is preferably 50 to 500, preferably formed by arranging a plurality of nozzle holes having a cross-sectional area of 3 mm 2 or less in one die hole on a die). The number of nozzle arrangements is preferably 1 to 5 rows.) The strands are allowed to flow out, and it is preferable to produce undrawn yarns having a single fineness of preferably 300 dtex or less.
具体的には榭脂組成物のペレットコンパウンド等を、例えば、短軸押出機を使用し て榭脂温度好ましくは 150〜200°C、より好ましくは 155〜195°Cで溶融紡糸するこ とによって未延伸糸を得ることができる。  Specifically, the pellet compound of the resin composition is melt-spun using, for example, a short screw extruder at a resin temperature of preferably 150 to 200 ° C, more preferably 155 to 195 ° C. An undrawn yarn can be obtained.
[0024] 前記溶融紡糸で得られた未延伸糸に公知の方法で延伸処理及び熱処理を施して 、好ましくは 600デシテックス以下の細繊度の繊維 (延伸糸）とすることができる。延伸 処理条件としては、延伸処理温度が好ましくは 30〜150°Cの温度に保持した空気雰 囲気下で、延伸倍率が好ましくは 2〜20倍に延伸することが好ましい。特に、延伸処 理温度が好ましくは 80〜140°Cの空気雰囲気下で、延伸倍率が好ましくは 2〜 10倍 に延伸される。  [0024] The undrawn yarn obtained by melt spinning can be subjected to a drawing treatment and heat treatment by a known method to obtain a fiber (drawn yarn) having a fineness of preferably 600 dtex or less. As stretching conditions, stretching is preferably performed at a stretching ratio of preferably 2 to 20 times in an air atmosphere where the stretching temperature is preferably maintained at a temperature of 30 to 150 ° C. In particular, the stretching ratio is preferably 2 to 10 times in an air atmosphere with a stretching temperature of preferably 80 to 140 ° C.
[0025] さらに、延伸した繊維を好ましくは 80〜200°Cの温度に保持した空気雰囲気下で、 繊維全長が処理前の好ましくは 99. 8〜50%、より好ましくは 99. 8〜70%の長さに なるまで熱弛緩処理することにより、熱収縮率を低下させることができる。該熱弛緩処 理は、延伸処理と連動して実施することもできるし、切り離して実施することもできる。 また、本発明においては、従来公知の溶融紡糸に関わる技術、例えば、各種ノズル 断面形状に関わる技術、加熱筒に関わる技術、熱処理に関わる技術などを、自在に 組み合わせて適用することが可能である。 [0025] Further, in an air atmosphere in which the drawn fiber is preferably maintained at a temperature of 80 to 200 ° C, the total length of the fiber is preferably 99.8 to 50% before treatment, more preferably 99.8 to 70%. The thermal contraction rate can be lowered by heat relaxation treatment until the length becomes. The thermal relaxation process can be performed in conjunction with the stretching process or can be performed separately. Further, in the present invention, a conventionally known technique related to melt spinning, for example, various nozzles It is possible to apply any combination of technologies related to cross-sectional shapes, technologies related to heating cylinders, and technologies related to heat treatment.
[0026] 未延伸糸に延伸処理及び熱処理をした繊維は、その一本の単繊度が、好ましくは 1〜200デシテックス、より好ましくは 5〜150デシテックス、特に好ましくは 10〜100 デシテックスである。ここで、繊維が細くても、太くても天然品から乖離することになり、 自然感が損なわれる。  [0026] The undrawn yarn that has been drawn and heat-treated has a single fineness of preferably 1 to 200 dtex, more preferably 5 to 150 dtex, and particularly preferably 10 to 100 dtex. Here, even if the fiber is thin or thick, it deviates from the natural product, and the natural feeling is lost.
デシテックスとは、長さ 100cmの繊維 20本の重量を測定し、この 1本当たりの平均 重量を 1万倍した値である。  Decitex is a value obtained by measuring the weight of 20 fibers with a length of 100 cm and multiplying the average weight per fiber by 10,000.
本発明にお 、ては特に限定されな 、が、上記の繊維は単繊度が必ずしも均一であ る必要は無ぐ場合によっては、紡糸の過程で又は紡糸後に単繊度が異なる複数の 繊維を混合 (ブレンド）して使用することも可能である。  In the present invention, although not particularly limited, in some cases, the above-described fibers may not be necessarily uniform, and a plurality of fibers having different single filament sizes may be mixed in the spinning process or after spinning. (Blend) can also be used.
実施例  Example
[0027] 以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらに限 定して解釈されるべきではな 、。  [0027] Hereinafter, the present invention will be described in more detail based on examples, but the present invention should not be construed as being limited thereto.
[0028] (実施例 1) [0028] (Example 1)
(a)塩ィ匕ビ二ル系榭脂（大洋塩ビ社製 TH— 1000、粘度平均重合度 1000) 100 質量部とポリ乳酸系榭脂（ュ-チカ社製 テラマック TE— 4000、融点 170°C) 50質 量部、ノ、イド口タルサイト系複合熱安定剤 (日産化学工業社製 CP-410A) 1質量 部、及びエステル系滑剤（理研ビタミン社製 EW- 100) 0. 75質量部を含有する混 合物を、ヘンシェルミキサーを使用し、 100°Cまで攪拌昇温させて榭脂組成物を得る 工程、（b)前記榭脂組成物を、丸形ノズル、ノズル孔断面積 0. 05mm2,及びノズル 孔数 180個の紡糸金型を用いて、 175〜185°Cで制御した 40mm単軸押出機により 、金型温度 190°C及び押し出し量 15kgZ時で溶融紡糸して、平均繊度 150デシテ ッタスの未延伸糸を得る工程、（c)前記溶融紡糸した繊維を 105°Cの空気雰囲気下 で 300%に延伸する工程、そして、（d)前記延伸した繊維に 140°Cの空気雰囲気下 で、繊維の全長が処理前の 75%の長さに収縮するまで熱弛緩処理する工程、を順 次経て、単繊度が 65デシテックスの繊維を得た。 (a) Vinyl chloride-based resin (TH-1000, Taiyo PVC Co., Ltd., viscosity average polymerization degree 1000) 100 parts by mass and polylactic acid-based resin (Nutika Terramac TE-4000, melting point 170 ° C) 50 parts by mass, 1 part by weight of talcite-based composite heat stabilizer (Nissan Chemical Industries CP-410A) and ester lubricant (EW-100 by Riken Vitamin) 0.75 parts by mass A step of heating the mixture containing 100g to 100 ° C using a Henschel mixer to obtain a resin composition, (b) using the round nozzle, nozzle hole cross-sectional area 0 Using a spinning die with 05mm 2 and 180 nozzle holes, melt spinning at a die temperature of 190 ° C and an extrusion amount of 15kgZ by a 40mm single screw extruder controlled at 175 to 185 ° C. A step of obtaining an undrawn yarn having an average fineness of 150 decitus, (c) a step of drawing the melt-spun fiber to 300% in an air atmosphere of 105 ° C, and (d) the drawing Under air atmosphere 140 ° C to the fibers, the step of thermal relaxation until the entire length of the fiber to shrink to 75% of the length of the pre-treatment, the through sequential, single fineness to obtain a fiber of 65 dtex.
[0029] (実施例 2〜： L0) 表 1に示す塩化ビニル系榭脂、ポリエステル系榭脂の配合量を用い、実施例 1と同 様にして、繊維を得た。 [0029] (Example 2 to: L0) Fibers were obtained in the same manner as in Example 1 using the blending amounts of vinyl chloride-based resin and polyester-based resin shown in Table 1.
[0030] (実施例 11)  [Example 11]
塩ィ匕ビュル系榭脂を重合度の低 、塩化ビニル榭脂 (大洋塩ビ社製 TH - 700、 粘度平均重合度 700)に変更した以外は、実施例 1と同様にして、繊維を得た。  A fiber was obtained in the same manner as in Example 1, except that the salty-bulb-based resin had a low degree of polymerization and was changed to vinyl chloride resin (TH-700 manufactured by Taiyo PVC Co., Ltd., viscosity average polymerization degree 700). .
[0031] (実施例 12) [0031] (Example 12)
塩ィ匕ビュル系榭脂を重合度の高 、塩化ビニル榭脂 (大洋塩ビ社製 TH - 2000、 粘度平均重合度 2000)に変更した以外は、実施例 1と同様にして、繊維を得た。  A fiber was obtained in the same manner as in Example 1 except that the salty-bulb-based resin was changed to a high degree of polymerization and vinyl chloride resin (TH-2000, Taiyo PVC Co., Ltd., viscosity average polymerization degree 2000). .
[0032] (実施例 13) [0032] (Example 13)
塩ィ匕ビュル系榭脂を塩ィ匕ビュル—エチレンコポリマー榭脂 (大洋塩ビ社製 E- 10 50、塩化ビュル含有量 98質量％、粘度平均重合度 1050)に変更した以外は、実施 例 1と同様にして、繊維を得た。  Example 1 with the exception that the salt-bulb-based resin was changed to salt-bule-ethylene copolymer resin (E-1050, Taiyo PVC Co., 98% by weight chloride content, viscosity average polymerization degree 1050). In the same manner, fibers were obtained.
[0033] (実施例 14) [Example 14]
塩ィ匕ビュル系榭脂を塩ィ匕ビュル 酢酸ビュルコポリマー榭脂 (大洋塩ビ社製 TV 800、塩化ビュル含有量 93質量％、粘度平均重合度 780)に変更した以外は、実 施例 1と同様にして、繊維を得た。  Example 1 and Example 1 except that the salty bule-based rosin was changed to salty bule acetate bulle copolymer rosin (Taiyo PVC Co., Ltd. TV 800, butyl chloride content 93 mass%, viscosity average polymerization degree 780) In the same manner, a fiber was obtained.
[0034] (実施例 15) [Example 15]
ポリ乳酸系榭脂を結晶性ポリエステル榭脂 (東洋紡績社製 ノ ィロン GM— 925、 融点 166°C)に変更した以外は、実施例 1と同様にして、繊維を得た。  A fiber was obtained in the same manner as in Example 1 except that the polylactic acid-based resin was changed to crystalline polyester resin (Nylon GM-925, Toyobo Co., Ltd., melting point 166 ° C).
[0035] (実施例 16) [Example 16]
ポリ乳酸榭脂を結晶性ポリエステル榭脂 (東洋紡績社製 ノ ィロン GA— 5410、融 点 117°C)に変更した以外は、実施例 1と同様にして、繊維を得た。  A fiber was obtained in the same manner as in Example 1, except that the polylactic acid resin was changed to crystalline polyester resin (Nonlon GA-5410 manufactured by Toyobo Co., Ltd., melting point: 117 ° C).
[0036] (比較例 1) [0036] (Comparative Example 1)
ポリ乳酸系榭脂を含まないとした以外は、実施例 1と同様にして、繊維を得た。  A fiber was obtained in the same manner as in Example 1 except that it did not contain polylactic acid-based greaves.
[0037] (比較例 2、 3) [0037] (Comparative Examples 2 and 3)
ポリ乳酸系榭脂の代わりに塩素化塩ィ匕ビュル榭脂 (積水化学工業社製 HA- 24 K)を表 2に示す配合量を用 、て実施例 1と同様の手順で繊維を得た。  Fibers were obtained in the same procedure as in Example 1 using chlorinated salt-bulle fat (HA-24K manufactured by Sekisui Chemical Co., Ltd.) instead of polylactic acid-based fat, using the blending amounts shown in Table 2. .
[0038] 上記実施例 1〜16及び比較例 1〜3の結果を、それぞれ、表 1及び表 2にまとめて
Figure imgf000010_0001
[0038] The results of Examples 1 to 16 and Comparative Examples 1 to 3 are summarized in Table 1 and Table 2, respectively.
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0002
[0039] [表 2] [0039] [Table 2]
Figure imgf000011_0001
Figure imgf000011_0001
[0040] 表 1にお ヽて「紡糸性」とは、榭脂組成物を溶融紡糸する際の成形性を表したもの である。紡糸性の試験にあっては、紡糸金型から同時に 120本の繊維を押出成形し た際の、該繊維の糸切れ発生回数 (溶融押出中に、数本の繊維状体が途切れる現 象で、測定時間は 30分間、測定回数は 3回である。）を測定したものである。  [0040] In Table 1, "spinnability" represents the moldability when melt-spinning the resin composition. In the spinnability test, when 120 fibers were extruded from a spinning mold at the same time, the number of occurrences of yarn breakage of the fibers (several fibrous bodies were interrupted during melt extrusion). The measurement time is 30 minutes and the number of measurements is 3.)
[0041] 表 1において「熱収縮（％)」とは、試験体を熱処理した際に発生する熱収縮率を表 したものである。具体的には、長さ 100mmに調整した繊維の試験体 12本を、 130°C のギアオーブン中で 15分間放置し、放置前後における試験体の長さの比を、（(放置 前の長さ-放置後の長さ) Z放置前の長さ） X 100により算出したものである。また、 数値は、 12本のうち、最大値、最小値を排除した 10本の平均値である。  [0041] In Table 1, "thermal shrinkage (%)" represents the thermal shrinkage rate that occurs when the specimen is heat-treated. Specifically, twelve fiber specimens adjusted to a length of 100 mm were left in a gear oven at 130 ° C for 15 minutes, and the ratio of the specimen lengths before and after leaving (((length before leaving) -Length after standing) Length before leaving Z) Calculated by X100. The numerical value is the average value of 10 out of 12, excluding the maximum and minimum values.
[0042] 表 1において「光沢」とは、繊維 24000本を束ねて、直射日光の当たる室内と蛍光 灯下において目視判定することにより評価した。評価基準は以下のとおりである。 優良：平滑感があって、光沢が少ないもの  [0042] In Table 1, "gloss" was evaluated by bundling 24,000 fibers and visually judging in a room exposed to direct sunlight and under a fluorescent lamp. The evaluation criteria are as follows. Excellent: Smooth and low gloss
良 ：平滑感が少な!、が、光沢が少な!、もの  Good: Less smoothness, but less gloss!
可 ：凹凸感があって光沢が少ない、または平滑で光沢が少しあるもの  Good: Uneven and less glossy, or smooth and slightly glossy
不良：凹凸が大きい、または光沢が強いもの  Defect: Large unevenness or strong gloss
[0043] 表 1、 2から明らかなように、本発明によれば、熱収縮性に優れ、光沢が少なぐしか も溶融紡糸時に糸切れの少ない繊維力 容易に得られることが分かる。 [0043] As is apparent from Tables 1 and 2, according to the present invention, it can be seen that a fiber force having excellent heat shrinkage and less gloss, and less fiber breakage during melt spinning can be easily obtained.
産業上の利用可能性  Industrial applicability
[0044] 本発明の榭脂組成物を用いて得られた繊維は、例えば肌着、靴下等の服飾繊維 製品、敷物、カーテン、タオル等の生活関連繊維製品、特に、頭髪装飾用や人工毛 髪用繊維に好適に用 、ることができる。 なお、 2006年 2月 28曰〖こ出願された曰本特許出願 2006— 051859号の明細書 、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示と して、取り入れるものである。 [0044] The fibers obtained using the greave composition of the present invention are, for example, clothing textile products such as underwear and socks, life-related textile products such as rugs, curtains and towels, especially for hair decoration and artificial hair. It can be suitably used for fibers. It should be noted that the entire contents of the specification, claims, and abstract of the Japanese Patent Application No. 2006-051859 filed on February 28, 2006 are hereby incorporated herein by reference. And that is what we take in.

Claims

請求の範囲 The scope of the claims
[1] 塩ィ匕ビュル系榭脂、及び該塩ィ匕ビニル系榭脂 100質量部に対しポリエステル系榭 脂を 1〜300質量部含有する榭脂組成物の溶融紡糸繊維からなることを特徴とする 塩ィ匕ビ二ル系榭脂繊維。  [1] It is characterized by comprising a melt-spun fiber of a resin composition containing 1 to 300 parts by mass of a polyester resin with respect to 100 parts by mass of a salty vinyl resin and 100 parts by mass of the vinyl salt vinyl resin. It is a salty vinyl resin fiber.
[2] 塩化ビュル系榭脂の粘度平均重合度が、 600〜2500である、請求項 1に記載の 塩ィ匕ビ二ル系榭脂繊維。 [2] The salted vinyl resin fiber according to claim 1, wherein the viscosity average polymerization degree of the chlorinated mulled resin is 600 to 2500.
[3] ポリエステル系榭脂の融点が 100〜300°Cである、請求項 1又は 2に記載の塩ィ匕ビ[3] The salt vinyl according to claim 1 or 2, wherein the melting point of the polyester-based resin is 100 to 300 ° C.
-ル系榭脂繊維。 -Lead fiber.
[4] ポリエステル系榭脂がポリ乳酸系榭脂である、請求項 1〜3のいずれかに記載の塩 化ビュル系榭脂繊維。  [4] The salted bull resin fiber according to any one of claims 1 to 3, wherein the polyester resin is a polylactic acid resin.
[5] 繊維の単繊度が 1〜200デシテックスである、請求項 1〜4のいずれかに記載の塩 化ビュル系榭脂繊維。  [5] The salted bull-based greaves fiber according to any one of claims 1 to 4, wherein the single fineness of the fiber is 1 to 200 dtex.
[6] 請求項 1〜5のいずれかに記載の塩ィ匕ビ二ル系榭脂繊維力もなる人工毛髪。 [6] An artificial hair having a salty vinyl resin fiber strength according to any one of claims 1 to 5.
[7] (a)塩ィ匕ビ二ル系榭脂と、ポリエステル系榭脂と、を含む榭脂組成物を混合するェ 程； [7] (a) a step of mixing a resin composition containing a salted vinyl resin and a polyester resin;
(b)前記榭脂組成物を、紡糸金型力も榭脂温度 150〜200°Cで溶融紡糸する工程  (b) A step of melt spinning the resin composition at a resin temperature of 150 to 200 ° C.
(c)前記溶融紡糸した繊維を、延伸処理温度 30〜150°Cの空気雰囲気下で、延 伸倍率 2〜20倍に延伸する工程； (c) stretching the melt-spun fiber at a stretching ratio of 2 to 20 times in an air atmosphere at a stretching temperature of 30 to 150 ° C;
(d)前記延伸した繊維を、 80〜200°Cの温度に保持した空気雰囲気下で、繊維全 長が処理前の 99. 8〜50%の長さになるまで熱弛緩処理する工程；  (d) a step of heat-relaxing the drawn fiber in an air atmosphere maintained at a temperature of 80 to 200 ° C. until the total fiber length is 99.8 to 50% before treatment;
を順次有する塩化ビニル系榭脂繊維の製造方法。  The manufacturing method of the vinyl chloride type | system | group resin fiber which has these one by one.
[8] 前記溶融紡糸する工程で用いるノズル孔の 1個の断面積が、 3mm2以下である、請 求項 7に記載の塩化ビュル系榭脂繊維の製造方法。 [8] The method for producing a chlorinated bull-based resin fiber according to claim 7, wherein a cross-sectional area of one nozzle hole used in the melt spinning step is 3 mm 2 or less.
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US20100233390A1 (en) 2010-09-16
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JPWO2007099858A1 (en) 2009-07-16
CN101379229A (en) 2009-03-04
KR20080083643A (en) 2008-09-18

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