WO2012046748A1 - Fiber for artificial hair, and hair accessory formed from same - Google Patents

Fiber for artificial hair, and hair accessory formed from same Download PDF

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Publication number
WO2012046748A1
WO2012046748A1 PCT/JP2011/072914 JP2011072914W WO2012046748A1 WO 2012046748 A1 WO2012046748 A1 WO 2012046748A1 JP 2011072914 W JP2011072914 W JP 2011072914W WO 2012046748 A1 WO2012046748 A1 WO 2012046748A1
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WO
WIPO (PCT)
Prior art keywords
fiber
resin
polyvinyl chloride
chloride resin
artificial hair
Prior art date
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PCT/JP2011/072914
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French (fr)
Japanese (ja)
Inventor
友道 橋本
Original Assignee
株式会社カネカ
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Filing date
Publication date
Application filed by 株式会社カネカ filed Critical 株式会社カネカ
Priority to CN201180047221.9A priority Critical patent/CN103124812B/en
Priority to JP2012537724A priority patent/JP5700048B2/en
Priority to EP11830680.2A priority patent/EP2626452A4/en
Priority to KR1020137007673A priority patent/KR101743497B1/en
Priority to US13/878,115 priority patent/US20130298924A1/en
Priority to SG2013025606A priority patent/SG189286A1/en
Publication of WO2012046748A1 publication Critical patent/WO2012046748A1/en
Priority to ZA2013/02535A priority patent/ZA201302535B/en

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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08Monocomponent 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
    • D01F6/10Monocomponent 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
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41GARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
    • A41G5/00Hair pieces, inserts, rolls, pads, or the like; Toupées
    • A41G5/004Hair pieces
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41GARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
    • A41G3/00Wigs
    • A41G3/0083Filaments for making wigs
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/32Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04DTRIMMINGS; RIBBONS, TAPES OR BANDS, NOT OTHERWISE PROVIDED FOR
    • D04D7/00Decorative or ornamental textile articles
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2503/00Domestic or personal
    • D10B2503/08Wigs

Definitions

  • the present invention provides an artificial hair fiber having excellent styling properties and a soft and smooth touch close to human hair, an artificial hair fiber bundle, and a hair ornament, an artificial hair product comprising the same, and the artificial hair fiber and
  • the present invention relates to a polyvinyl chloride resin fiber constituting a fiber bundle for artificial hair.
  • polyvinyl chloride resin fibers There are many materials such as polyvinyl chloride resin fibers, polyester resin fibers, and modacrylic resin fibers that are generally commercially available synthetic fibers for artificial hair.
  • Each of these synthetic fibers has excellent properties derived from the raw materials, and has been used for headdress products in the field of specialty in accordance with the properties of each fiber.
  • products having a value relatively close to that of human hair products have been put on the market by mixing each fiber and using them in one head ornament product, and making use of each excellent characteristic in harmony.
  • polyvinyl chloride resin fibers have a soft touch close to human hair, are easily processed into an arbitrary style, and have little hair entanglement.
  • Polyester resin fibers are strong and have excellent resilience when they are moved with a product on them, and they are highly durable because of their high form stability.
  • Modacrylic resin fibers are lightweight and have a high volume feeling, and have a feature that a natural appearance can be obtained by utilizing surface irregularities.
  • it is difficult to make full use of the properties of each fiber, and synthetic hair headdress products still have a commercial value comparable to human hair products. There is no actual situation.
  • the biggest challenge when using mixed fibers of different materials is that the optimum processing temperature differs depending on the material.
  • it is important to heat at an appropriate temperature when imparting the curl shape Specifically, by imparting a curl shape at an appropriate temperature, the elasticity and shape retention force are improved, thereby improving the pulsation and durability of use as a hair product.
  • the fiber treatment agent becomes familiar with the fiber surface, and a smooth and moisturizing feeling (moisture feel) similar to human hair can be expressed.
  • the temperature for imparting the curled shape is limited to 80 to 90 ° C.
  • the processing temperature is lower than the appropriate temperature of the polyester resin fibers, so it is not possible to make use of the inherent curl strength.
  • the effect of improving the tactile sensation inherent to the fiber treatment agent cannot be fully exhibited.
  • polyvinyl chloride resin fiber has very excellent properties as a fiber for hair, such as soft and smooth touch similar to human hair, curled style, and cost performance. It has been difficult, and the conventional technology has not been able to obtain a satisfactory level of overall quality.
  • Patent Documents 1 and 2 include examples in which a polyester resin fiber and a halogen-containing resin fiber, or a modacrylic resin fiber and a polyvinyl chloride resin fiber are mixed to impart curl at 100 ° C. or higher. Is described. These technologies have succeeded in developing merchandise superior to conventional products by mixing different materials and taking advantage of their characteristics. However, since the performance of the polyvinyl chloride resin fiber was not sufficient, there was still room for improvement from the viewpoint of tactile sensation, and it was not possible to provide merchandise comparable to human hair products.
  • Patent Document 3 describes a method for calculating curling conditions. However, simply reducing the shrinkage rate does not provide a sufficient effect of suppressing the generation of fiber bending, and the fibers become hard at high temperatures. Since the concept of tactile sensation was not taken into account, satisfactory quality could not be obtained as a hair product.
  • Patent Document 4 describes an example of blending a chlorinated polyvinyl chloride resin having a high chlorine content as an attempt to improve the heat resistance of the polyvinyl chloride resin fiber, but only by reducing the shrinkage rate. A satisfactory tactile sensation as a hair product could not be obtained.
  • An object of the present invention is to provide a fiber for artificial hair and an artificial hair product that have excellent styling properties and have a soft and smooth feel close to human hair.
  • the polyvinyl chloride resin fiber has a low softening temperature of the main component polyvinyl chloride resin, if it is processed at a temperature higher than 90 ° C., which exceeds the glass transition temperature, the fiber bends due to shrinkage. , It becomes a feeling of bad touch.
  • This fiber bending occurs on the following principle. First, in the step of imparting a curl shape, a fiber bundle is wound spirally or concentrically on a cylindrical pipe and heated for a predetermined time in a state in which the shape is maintained, and then the brazed shape is stored in the fiber bundle, and then The process is completed by cooling and removing the fiber bundle from the pipe.
  • the fiber having a low shrinkage rate plays a role of a support column and is less likely to bend. It has been found that when the rigidity is high, the shrinkage of the fiber having a large shrinkage rate is suppressed, and the fiber bending becomes difficult to occur. And by applying that principle, the shrinkage stress of polyvinyl chloride resin fibers that tend to bend fibers is reduced, and if necessary, the rigidity is higher than that of polyvinyl chloride resin fibers and the shrinkage is small. By mixing these, the curl shape was successfully imparted without increasing fiber bending even at a temperature higher than the conventional 90 ° C.
  • the effect of increasing the temperature for imparting the curl shape also affects the tactile feel of the fiber treatment agent, and the familiarity between the fiber treatment agent and the fiber surface is improved by heating at a high temperature, particularly when an amino-modified silicone compound is used. It has been discovered that the fiber smoothness and the moisturizing feeling can be amplified compared to the case where the curl shape is imparted at a temperature of °C or lower. Furthermore, since the amino-modified silicone compound has the effect of suppressing the inter-fiber fusion of the polyvinyl chloride resin fibers, it is possible to ensure the flexibility of the fibers that has been lowered at the time of high temperature heating. It has been found that an excellent tactile sensation close to human hair can be obtained.
  • the present invention has the following gist.
  • One of the characteristics of the present invention is a polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 ⁇ N / dtex or less.
  • Another feature of the present invention is a polyvinyl chloride resin fiber for artificial hair having a shrinkage stress at 130 ° C. of 70 ⁇ N / dtex or less.
  • thermoplastic resin fiber comprising 20 to 100% by weight of a polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 ⁇ N / dtex or less and a composition excluding the polyvinyl chloride resin.
  • a fiber bundle for artificial hair containing 0 to 80% by weight.
  • Another feature of the present invention is that 20 to 100% by weight of polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 ⁇ N / dtex or less, Young's modulus of 4 to 9 GPa, and shrinkage at 130 ° C. Is a fiber bundle for artificial hair containing 10 to 80% by weight of thermoplastic resin fibers having a composition excluding polyvinyl chloride resin.
  • the shrinkage rate of the polyvinyl chloride resin fiber at 130 ° C. is not lower than the shrinkage rate of the thermoplastic resin fiber at 130 ° C., and the shrinkage rate of the polyvinyl chloride resin fiber at 130 ° C.
  • the fiber bundle for artificial hair characterized in that the difference between the shrinkage rate and the shrinkage rate of thermoplastic resin fibers at 130 ° C. is 6% or less.
  • Another feature of the present invention is a fiber bundle for artificial hair in which the polyvinyl chloride resin fiber and the thermoplastic resin fiber contain an amino-modified silicone compound.
  • Another feature of the present invention is a fiber bundle for artificial hair in which the polyvinyl chloride resin fiber contains 0.07 to 0.5 omf% of a polyalkylene oxide compound having a weight average molecular weight of 2000 to 25000.
  • Another feature of the present invention is a fiber bundle for artificial hair in which the polyvinyl chloride resin fiber contains 0 to 0.5 omf% of a silicone compound.
  • thermoplastic resin fiber comprising 20 to 100% by weight of a polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 ⁇ N / dtex or less and a composition excluding the polyvinyl chloride resin.
  • the present invention provides an artificial hair fiber and an artificial hair product that are excellent in styling properties and have a soft and smooth feel close to human hair.
  • FIG. 4 is a diagram showing the measurement results of shrinkage stress relating to the polyvinyl chloride resin fibers described in Production Example 1-4 of the present invention, PVC-1 being a conventional product and PVC-2 to PVC-4 being improved products of the present invention.
  • the fiber bundle for artificial hair of the present invention has 20 to 100% by weight of polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 ⁇ N / dtex or less, Young's modulus of 4 to 9 GPa, and shrinkage at 130 ° C. of 10%. It is characterized by comprising 0 to 80% by weight of thermoplastic resin fibers having the following composition excluding polyvinyl chloride resin.
  • the fiber bundle in the present invention refers to an aggregate of two or more single fibers of 20 to 100 dtex, and may be fixed so that the aggregate of single fibers does not collapse or may not be fixed.
  • Synthetic fibers for artificial hair are usually manufactured as continuous fiber bundles of several hundreds of meters, cut into an arbitrary length at the time of product processing, and then commercialized by mixing fibers or imparting a curled shape.
  • the fiber bundle in the present invention is not particularly limited, and unless otherwise specified, for example, refers to a continuous fiber bundle during production, a fiber bundle cut during product processing, a fiber bundle in a hair product, and the like. .
  • the polyvinyl chloride resin fiber used in the present invention is a fiber mainly composed of a polyvinyl chloride resin and has a small shrinkage stress.
  • the shrinkage stress tends to increase when the shrinkage rate is large.
  • a method of performing relaxation heat treatment for a long time at a high temperature of, for example, 110 ° C. or more at the time of fiber production is effective, and the shrinkage stress can be lowered even with the same shrinkage rate.
  • the method of reducing the shrinkage stress is not limited to this and can be used.
  • the shrinkage stress generally has a peak in the vicinity of 130 ° C. as shown in FIG. 1, and a preferable value of the shrinkage stress in the present invention is specifically a shrinkage stress at 130 ° C. of 70 ⁇ N. / Dtex or less is preferable, preferably 50 ⁇ N / dtex or less, and more preferably 40 ⁇ N / dtex or less.
  • the shrinkage stress exceeds 70 ⁇ N / dtex, the effect of the thermoplastic resin fiber that supports the polyvinyl chloride resin fiber and suppresses the shrinkage is not sufficient, so that the polyvinyl chloride resin fiber bends, and the fiber bending does not occur. Occurs and feels worse.
  • the polyvinyl chloride resin fiber used in the present invention can be suitably used as a polyvinyl chloride resin fiber for artificial hair.
  • composition ratio of the polyvinyl chloride resin fiber used in the present invention in the fiber bundle for artificial hair is 20 to 100% by weight, preferably 30 to 75% by weight, and more preferably 40 to 60% by weight. If the composition ratio in the fiber bundle for artificial hair is lower than 20% by weight, the soft tactile and style properties of the polyvinyl chloride resin fiber are insufficient, and satisfactory merchandise cannot be obtained, and the merchantability tends to decrease. is there.
  • polyvinyl chloride resin fiber used in the present invention 0.07 to 0.5 omf% of a polyalkylene oxide compound having a weight average molecular weight of 2000 to 25000 in a fiber bundle state before being processed into a product, and a silicone type A compound in which a compound is supported on the surface of 0 to 0.5 omf% fiber can be preferably used.
  • “Supported on the surface of the fiber” means a state in which a specific compound adheres to the surface layer of the fiber, and excludes components that have penetrated into the fiber and can no longer be removed.
  • ethanol / cyclohexane 50 wt% / 50 wt% is used as a solvent that does not penetrate into the inside of the polyvinyl chloride resin fiber, and the weight of the compound extracted when the fiber is immersed in this solvent is handled as the supported amount. .
  • a polyalkylene oxide compound obtained by addition-polymerizing an alkylene oxide containing ethylene oxide to an organic compound having two active hydrogen groups can be suitably used.
  • the organic compound having two active hydrogen groups include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,6-hexanediol, and aniline.
  • at least one compound can be suitably used.
  • the alkylene oxide containing ethylene oxide include ethylene oxide and alkylene oxides having 3 to 30 carbon atoms.
  • propylene oxide, butylene oxide, styrene oxide, ⁇ -olefin epoxide, or glycidyl ethers can be used.
  • at least one compound can be suitably used.
  • the number of carbon atoms is small, but a copolymer of ethylene oxide and propylene oxide is preferable because it needs fluidity at room temperature in order to obtain an effect of suppressing fusion.
  • the addition polymerization of alkylene oxide can be carried out according to a known method, and may be random type or block type.
  • the molecular weight is preferably 2000 to 25000 in terms of weight average molecular weight, preferably 5000 to 20000, and more preferably 10,000 to 18000. If the weight average molecular weight is less than 2000, the fiber feels harder because it penetrates into the fiber during heating and the effect of suppressing fusion is reduced, and if it is greater than 25000, even if the amount of adhesion is adjusted, the feeling of stickiness is felt. Become. In order to achieve both the tactile sensation and the antistatic effect, polyalkylene oxide compounds having different weight average molecular weights within the above range may be mixed.
  • the supported amount of the polyalkylene oxide compound used in the present invention on the fiber is preferably 0.07 to 0.5 omf%, preferably 0.07 to 0.3 omf%, more preferably 0.1 to 0.2 omf%. .
  • the supported amount with respect to the fiber is less than 0.07, the effect of suppressing fusion is insufficient, the fiber becomes hard, and the combing property and the effect of suppressing static electricity are insufficient.
  • the loading amount on the fiber is more than 0.5 omf%, the feeling of stickiness is felt, and the fiber is excessively converged to reduce the volume feeling.
  • the polyvinyl chloride resin fiber used in the present invention may carry a silicone compound in addition to the polyalkylene oxide compound.
  • a silicone compound having a specific viscosity does not penetrate into the inside of the fiber as in the case of the polyalkylene oxide compound, and can provide a high fusion suppressing effect.
  • the silicone compound is an amino-modified silicone compound, good tactile sensation is obtained by performing heat treatment at a high temperature as described above, and fiber bending does not occur because heating is performed in a tension state particularly in the relaxation heat treatment step. Therefore, heating can be performed at a higher temperature than when the curled shape is imparted, and a higher tactile improvement effect can be obtained.
  • a silicone compound since a silicone compound has a large charging effect, it cannot be used alone as an oil agent, and must be used in combination with a polyalkylene oxide compound.
  • a linear polydimethylsiloxane that is liquid at 23 ° C., or an amino group, an epoxy group, a carboxyl group, a polyether group, or a thiol group is introduced into the side chain of the polydimethylsiloxane to form a molecule.
  • a compound generally referred to as a silicone oil having a methyl group or a hydroxyl group at the end can be preferably used.
  • a plurality of silicone compounds may be mixed on the fiber surface, and silsesquioxane having the above functional group may be mixed within a range that can maintain the stability of the emulsion.
  • silicone oils generally has a molecular weight generally defined by kinematic viscosity.
  • a preferable kinematic viscosity is 500 to 20000 mm 2 / s at 25 ° C., more preferably 1000 to 10,000 mm 2 / s. s. If the kinematic viscosity is lower than 500 mm 2 / s, the amount of penetration into the fiber increases, so that the effect of suppressing fusion is insufficient and the fiber becomes hard, and if it is higher than 20000 mm 2 / s, it adheres uniformly to the fiber surface. This makes it difficult to obtain a sufficient effect of suppressing fusion and improving the tactile sensation.
  • the supported amount of the silicone compound used in the present invention on the fiber is preferably 0 to 0.5 omf%, preferably 0.02 to 0.3 omf%, more preferably 0.05 to 0.2 omf%.
  • the amount supported on the fiber is more than 0.5 omf%, the charging effect is great, and static electricity is generated, causing problems such as entanglement of single fibers during fiber processing.
  • the polyvinyl chloride resin fiber used in the present invention may contain an antistatic agent or a smoothing agent, but it is a mineral that penetrates into the fiber and exhibits a plasticizing effect.
  • the adhesion amount of oil components such as oil and ester oil should be small, and the preferable adhesion amount of the oil component is 0.15 omf% or less, more preferably 0.07 omf% or less.
  • the polyvinyl chloride resin fiber used in the present invention is not particularly limited in the blending and production method, and can be produced using a conventionally known production method. However, the fineness suitable for hair fibers and the cross-sectional shape of the fiber can be used. In order to obtain the above, it is preferable to use a manufacturing method in the same field. One example will be described below.
  • the polyvinyl chloride resin fiber used in the present invention is a fiber mainly composed of a polyvinyl chloride resin, and the polyvinyl chloride resin fiber is used depending on the purpose as long as the quality and spinning stability of the fiber are not impaired.
  • the well-known compounding agent used for a composition can be added. Specifically, for example, heat resistance improvers such as chlorinated vinyl chloride resins and AS resins, metal soap heat stabilizers, stabilizing aids such as ⁇ diketones, phosphites, polyols, plasticizers, UV absorbers, oxidation Inhibitors, antistatic agents, fillers, flame retardants, pigments and the like can be used. In some cases, special compounding agents such as a foaming agent, a crosslinking agent, a tackifier, a conductivity imparting agent, and a fragrance can be used.
  • the polyvinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention is particularly limited to a homopolymer resin that is a homopolymer of a conventionally known vinyl chloride or various conventionally known copolymer resins. is not.
  • copolymer resins include vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl propionate copolymer resins and other vinyl chloride and vinyl ester copolymer resins, vinyl chloride-butyl acrylate copolymer resins, vinyl chloride-2-ethylhexyl acrylate.
  • a preferred vinyl chloride resin is a homopolymer resin which is a homopolymer of vinyl chloride.
  • the content of the comonomer is not particularly limited, and can be determined according to the moldability of the fiber, the properties of the fiber, and the like. However, when the softening temperature of the copolymer resin is low, the heat resistance may be lowered. Therefore, it is preferable to use a mixture with a homopolymer resin that is a homopolymer of vinyl chloride.
  • the viscosity average polymerization degree of the vinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention is preferably 450 or more in order to obtain sufficient strength and heat resistance as the fiber. In order to produce a safe fiber under an appropriate nozzle pressure, the degree of polymerization is preferably 1800 or less. In order to achieve these molding processability and fiber characteristics, when a vinyl chloride homopolymer resin is used, a region having a viscosity average polymerization degree of 650 to 1450 is particularly preferable. When a copolymer is used, the viscosity average degree of polymerization is particularly preferably in the range of 1000 to 1700, depending on the comonomer content.
  • the viscosity average degree of polymerization was calculated according to JIS-K6721 by dissolving 200 mg of resin in 50 ml of nitrobenzene, measuring the specific viscosity of this polymer solution in a constant temperature bath at 30 ° C. using an Ubbelohde viscometer. .
  • the vinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention can be produced by emulsion polymerization, bulk polymerization or suspension polymerization.
  • a polymer produced by suspension polymerization is preferable in consideration of the initial colorability of the fiber.
  • a chlorinated vinyl chloride resin can also be used.
  • a vinyl chloride resin is used as a raw material, which is reacted with chlorine to increase the chlorine content to 58 to 72%. Since the heat resistance of the resin increases by chlorinating and increasing the chlorine content, the use of a chlorinated vinyl chloride resin has the effect of suppressing fiber shrinkage.
  • the viscosity average polymerization degree of the chlorinated vinyl chloride resin is preferably 300 to 1100.
  • the viscosity average polymerization degree is less than 300, the heat shrinkage of the fiber Since the effect of lowering the rate is reduced, the fiber has a slightly higher shrinkage rate.
  • the viscosity average degree of polymerization exceeds 1100, the melt viscosity becomes high, and the nozzle pressure at the time of spinning tends to be high, so that safe operation tends to be difficult.
  • the viscosity average degree of polymerization is from 500 to 900.
  • the chlorine content is less than 58%, the effect of lowering the heat shrinkage rate of the fiber is reduced. Conversely, if the chlorine content exceeds 72%, the melt viscosity tends to be high and stable operation becomes difficult. Absent.
  • the chlorinated vinyl chloride resin is preferably used in combination with a vinyl chloride resin rather than being used alone in terms of yarn breakage during spinning and coloring of the yarn due to heat. It is preferable to mix the chlorinated vinyl chloride resin at a ratio of 0 to 40% by weight with respect to 100 to 60% by weight of the vinyl chloride resin, and further chlorinated vinyl chloride with respect to 90 to 70% by weight of the vinyl chloride resin. It is preferable to mix the resin at a ratio of 10 to 30% by weight. If the chlorinated vinyl chloride resin exceeds 40% by weight, yarn breakage tends to occur during spinning.
  • the stabilizer used for the polyvinyl chloride resin fiber used in the present invention conventionally known stabilizers can be used. Among them, a tin-based heat stabilizer, a Ca—Zn-based heat stabilizer, a hydrotalcite-based heat stabilizer, At least one heat stabilizer selected from an epoxy heat stabilizer and a ⁇ -diketone heat stabilizer is preferred.
  • the heat stabilizer is preferably used in an amount of 0.2 to 5 parts by weight, more preferably 1 to 3 parts by weight. If it is less than 0.2 parts by weight, the effect as a heat stabilizer is poor. Even if it exceeds 5 parts by weight, the thermal stability is not greatly improved, which is economically disadvantageous.
  • the addition of the heat stabilizer prevents the resin from being thermally decomposed during spinning, so that the color tone of the fiber is not lowered and the spinning can be performed stably (long-run spinnability).
  • the long run spinnability is a property that can be stably operated continuously without stopping the spinning process for several days and can produce fibers.
  • Resin composition with low long-run spinnability can be used to replace breaker plates and nozzles within a relatively short period of time after starting operation, for example, when thread breakage starts due to plate-out or the die pressure starts to rise. Need to restart, production efficiency is poor.
  • the decrease in the color tone of the fiber refers to the initial coloration of the fiber during spinning.
  • the tin stabilizers include dimethyltin mercapto, dimethyltin mercaptoide, dibutyltin mercapto, dioctyltin mercapto, dioctyltin mercaptopolymer, dioctyltin mercaptoacetate, etc.
  • examples thereof include maleate tin thermal stabilizers such as maleate, dibutyltin maleate, dioctyltin maleate, and dioctyltin maleate polymer, and laurate tin thermal stabilizers such as dimethyltin laurate, dibutyltin laurate, and dioctyltin laurate.
  • Examples of the Ca—Zn heat stabilizer include zinc stearate, calcium stearate, zinc 12-hydroxystearate, and calcium 12-hydroxystearate.
  • Examples of the hydrotalcite-based heat stabilizer include Alkamizer manufactured by Kyowa Chemical Industry Co., Ltd.
  • Examples of the epoxy heat stabilizer include epoxidized soybean oil and epoxidized linseed oil.
  • Examples of the ⁇ -diketone heat stabilizer include stearoylbenzoylmethane (SBM) and dibenzoylmethane (DBM).
  • lubricants can be used for the polyvinyl chloride resin fibers used in the present invention, and in particular, metal soap lubricants, polyethylene lubricants, higher fatty acid lubricants, ester lubricants, higher alcohol lubricants.
  • the lubricant is effective for controlling the molten state of the composition and the state of adhesion between the composition and a metal surface such as a screw, cylinder or die in the extruder.
  • the lubricant is preferably used in an amount of 0.2 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. More preferably, it is 1 to 4 parts by weight.
  • metal soap lubricant examples include metal soaps such as stearate salts such as Na, Mg, Al, Ca, Ba, laurate salts, palmitate salts, and oleate salts.
  • metal soaps such as stearate salts such as Na, Mg, Al, Ca, Ba, laurate salts, palmitate salts, and oleate salts.
  • higher fatty acid lubricant examples include saturated fatty acids such as stearic acid, palmitic acid, myristic acid, lauric acid and capric acid, unsaturated fatty acids such as oleic acid, and mixtures thereof.
  • higher alcohol lubricants include stearyl alcohol, palmityl alcohol, myristyl alcohol, lauryl alcohol, oleyl alcohol, and the like.
  • ester lubricants include ester lubricants composed of alcohol and fatty acids, pentaerythritol lubricants such as pentaerythritol or monoesters, diesters, triesters, tetraesters, or mixtures thereof of pentaerythritol or dipentaerythritol and higher fatty acids, and montanic acid.
  • pentaerythritol lubricants such as pentaerythritol or monoesters, diesters, triesters, tetraesters, or mixtures thereof of pentaerythritol or dipentaerythritol and higher fatty acids
  • montanic acid wax-based lubricants of esters of stearyl alcohol, palmityl alcohol, myristyl alcohol, lauryl alcohol, oleyl alcohol, and other higher alcohols.
  • polyvinyl chloride resin fibers used in the present invention depending on the purpose, for example, further processing aids, matting agents, fillers, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, etc. Flame retardants, pigments and the like can be used.
  • EVA resin for obtaining a soft touch, such as PES-250 manufactured by Nihon Unicar Co., Ltd., and acrylic resin for further improving the extrusion processability, for example, PA-20 manufactured by Kaneka Corporation may be added.
  • PES-250 manufactured by Nihon Unicar Co., Ltd.
  • acrylic resin for further improving the extrusion processability, for example, PA-20 manufactured by Kaneka Corporation may be added.
  • a known melt spinning method can be used in the fiberizing step.
  • vinyl chloride resin, chlorinated vinyl chloride resin, heat stabilizer and lubricant are mixed at a specified ratio, stirred and mixed with a Henschel mixer, etc., then filled into an extruder, cylinder temperature 150 to 190 ° C., nozzle In the temperature range of 180 ⁇ 15 ° C., the resin is extruded under conditions with good spinnability, melt spinning is performed, and an undrawn yarn is obtained.
  • a conventionally known extruder can be used.
  • a single screw extruder, a different-direction twin screw extruder, a conical twin screw extruder, etc. can be used, but a single screw extruder having a diameter of about 35 to 85 mm ⁇ or a conical extruder having a diameter of about 35 to 50 mm ⁇ is particularly preferable.
  • the hole shape of the nozzle used at this time is a shape that approximates the final cross-sectional shape, but the shape dimension slightly changes depending on the die swell or stretching at the time of spinning. .
  • the shape of the nozzle hole is not particularly limited, and is circular, flat oval, glasses, saddle, star, C, H, T, Y, cross, pentagon, hexagon Type, octagonal type, etc. can be selected. Among these, it is desirable that the rigidity does not increase remarkably, and a flat elliptical shape, a spectacle shape, and a saddle shape are preferable, and a spectacle shape and a saddle shape are more preferable.
  • the extruded filament is heat-treated for about 0.5 to 1.5 seconds in a heated spinning cylinder (under 200-300 ° C atmosphere and good spinnability) provided directly under the nozzle, and the produced undrawn yarn is drawn by a take-up roll. Sent to the process. Next, the undrawn yarn is drawn about 2 to 4 times through a hot air circulation box whose temperature is adjusted to 100 to 130 ° C. between the take-up roll and the drawing roll.
  • the heat treatment temperature is desirably high, preferably 120 to 145 ° C., more preferably 130 to 140 ° C.
  • the heat treatment temperature is lower than 110 ° C.
  • the shrinkage stress at 130 ° C. cannot be sufficiently reduced, so that fiber bending occurs and the commercial property is lowered.
  • the heat treatment temperature is higher than 150 ° C., the polyalkylene oxide compound is supported. However, it becomes difficult to sufficiently suppress the fusion between the fibers, and the tactile sensation becomes hard.
  • the relaxation rate is desirably as low as possible, preferably 10% or less per minute, and more preferably 8% or less per minute. preferable.
  • the relaxation rate exceeds 10% per minute, the strain in the fiber cannot be sufficiently removed, so that fiber bending tends to occur due to fiber contraction, and the tactile sensation deteriorates.
  • the relaxation heat treatment time is preferably 2 to 60 minutes, more preferably 4 to 20 minutes. If the heat treatment time is shorter than 2 minutes, it is difficult to make the shrinkage ratio between the multifilaments uniform. If it is longer than 60 minutes, it is difficult to sufficiently suppress the fusion between fibers even if a polyalkylene oxide compound is supported. Becomes hard.
  • the fiber after the relaxation heat treatment may be further stretched in a range of 0.1 to 4%.
  • a nip roll or a refracted portion may be introduced into the process after the relaxation heat treatment.
  • the fineness of the single fiber constituting the artificial hair fiber of the present invention is preferably 20 to 100 dtex, more preferably 40 to 90 dtex, as in the case of ordinary artificial hair fibers. If it is thinner than 20 dtex, the curl after processing the product becomes weak, and the style is remarkably lowered. On the other hand, if it is thicker than 100 dtex, the rigidity of the fiber becomes high and the tactile sensation becomes hard.
  • thermoplastic resin fiber used in the present invention has a Young's modulus of 4 to 9 GPa, a shrinkage rate at 130 ° C. of 10% or less, a composition excluding polyvinyl chloride resin, and a composition ratio in a fiber bundle for artificial hair. Is 0 to 80% by weight.
  • the thermoplastic resin fiber has a role of preventing the deterioration of the tactile sensation by suppressing the shrinkage of the polyvinyl chloride resin fiber, and is required to have rigidity sufficient to absorb the shrinkage stress.
  • Rigidity can use Young's modulus as an index.
  • the thermoplastic resin fiber in the present invention needs to have a Young's modulus of 4 to 9 GPa, preferably 4.5 to 8 GPa, more preferably 5 to 7 GPa. If the Young's modulus is less than 4 GPa, the effect of suppressing the shrinkage of the polyvinyl chloride resin fibers cannot be sufficiently obtained, and the tactile sensation is deteriorated due to the generation of fiber bending. On the other hand, if the Young's modulus is greater than 9 GPa, the feeling of touch and style are deteriorated because the stiffness of the hair fibers is too strong.
  • thermoplastic resin fiber needs to be softened and not deformed at the curl shape imparting temperature, and a shrinkage rate of 130 ° C. can be used as an index thereof.
  • a shrinkage rate of 130 ° C. can be used as an index thereof.
  • a fiber bundle having a total fineness of 15000 to 25000 dtex by bundling single fibers is used, and an average value of 20 times in total is used.
  • the fluctuation range of the shrinkage rate is large even in the same fiber, it causes fiber bending. Therefore, when fibers having a shrinkage difference of 2% or more from the average shrinkage occupy 30% or more in the same fiber, there is a possibility that good tactile sensation may not be maintained, so that it is preferable not to use them.
  • the thermoplastic resin fiber used in the present invention needs to have a shrinkage rate at 130 ° C. of 10% or less, preferably 4% or less, more preferably 1% or less.
  • a shrinkage rate at 130 ° C. is higher than 10%, the effect of suppressing the shrinkage of the polyvinyl chloride resin fibers cannot be sufficiently obtained, and the tactile sensation is deteriorated due to the generation of fiber bending.
  • the composition ratio of the thermoplastic resin fibers used in the present invention in the fiber bundle for artificial hair is 0 to 80% by weight, preferably 25 to 70% by weight, more preferably 40 to 60% by weight.
  • the composition ratio in the fiber bundle for artificial hair is higher than 80% by weight, the soft tactile feel and style properties of the polyvinyl chloride resin fiber cannot be sufficiently obtained, and the commercial property is lowered.
  • the composition of the thermoplastic resin fiber used in the present invention is not particularly limited as long as it is a thermoplastic resin excluding a polyvinyl chloride resin.
  • a polyvinyl chloride resin fiber for example, it is possible to increase the rigidity by blending an inorganic substance, but since it has a characteristic that the fiber bending when bending occurs as described above, It is difficult to prevent deterioration of tactile sensation.
  • Specific examples of the composition used for the thermoplastic resin fiber include acrylonitrile resin, modacrylic resin, polyolefin resin, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, and polyamide.
  • Examples include imide resins, polyoxymethylene resins, polyether ketone resins, polycarbonate resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, polyferene sulfide fibers, and Teflon (registered trademark) resins. Can be mentioned. Of these, acrylonitrile-based resin, modacrylic resin, polyester-based resin, polyamide-based resin, polycarbonate-based resin, polyethersulfone-based resin, polyphenylene sulfide-based resin, more preferably Modacrylic resins and polyester resins are used. These compositions may be mixed in several kinds, and may be a composite composition fiber having a multilayer structure such as a core-sheath structure.
  • the thermoplastic resin fiber used in the present invention preferably has a LOI value of 25 or more.
  • the product for hair is required to have flame retardancy for its purpose of use, and a certain flame retardancy can be obtained by mixing a large amount of polyvinyl chloride resin fiber having digestive performance.
  • the present invention is characterized by providing a fiber bundle for artificial hair suitable for supporting a combustible amino-modified silicone compound on a fiber bundle, and the fiber bundle for artificial hair has a high level of flame retardancy. It is desirable. For this reason, it is desirable that the thermoplastic resin fiber also has flame retardancy, and the LOI value is used as an index thereof.
  • the LOI value of the thermoplastic resin fiber used in the present invention is preferably 25 or more, more preferably 27 or more. If the LOI value is lower than 25, the fiber bundle cannot have sufficient flame retardancy and may ignite and spread.
  • a means for setting the LOI value to 25 or more there are a method using a flame-retardant resin such as a modacrylic resin or a polyphenylene sulfide resin, and a method of blending various flame retardants into the resin.
  • the flame retardant that can be used for the thermoplastic resin fiber of the present invention is not particularly limited as long as it does not impair the gloss and hue, and specifically, for example, a phosphorus flame retardant, a bromine-containing polymer, a chlorine-containing polymer, and the like can be used. .
  • flame retardant aids such as antimony compounds can be used as needed.
  • thermoplastic resin fibers used in the present invention may be a mixture of a plurality of different fibers as long as they satisfy the Young's modulus, shrinkage rate, and LOI value of the above conditions.
  • the functionality such as the appearance, tactile sensation, and volume sensation of the fiber bundle for artificial hair, it has surface irregularities such as fibers with a low specific gravity and acrylic synthetic fibers described in International Publication No. WO2005 / 082184. A fiber etc. can be used.
  • an amino-modified silicone compound is supported on the fiber bundle surface at 95 to 130 ° C. It is possible to give a curled shape.
  • the amino-modified silicone compound used in the present invention has a role of expressing a smooth and moisturizing feeling similar to human hair. Furthermore, polyvinyl chloride resin fibers using conventional oil agents that do not contain silicone compounds have the problem that when heated at 95 ° C. or higher, fusion occurs between the fibers and the feel of the hair product becomes stiff. The silicone compound has a role of suppressing the fusion.
  • the amino-modified silicone compound used in the present invention is an oily compound that is liquid at 23 ° C. in which an imino group or an amino group is present in the side chain of the linear polydimethylsiloxane, and the amino group is adsorbed on the fiber surface. Adheres to the fiber more efficiently than a dimethyl silicone compound, and reduces the surface energy of the fiber to lower the frictional resistance, thereby obtaining a smooth, moisturizing and moisturizing feeling that is preferred by human hair. I can do it. However, if there are too many amino groups in the silicone compound, the surface tension of the oil will increase and the frictional resistance reduction effect will decrease, and the hydrophilicity will increase and the durability will be reduced because it will flow down from the fiber surface due to sweat or rain.
  • a suitable amine equivalent in the amino-modified silicone compound of the present invention is 1000 to 20000 g / mol, preferably 1250 to 10000 g / mol, more preferably 1500 to 5000 g / mol.
  • the tactile sensation and durability for use are lowered because of too many amine groups, and when the amine equivalent is higher than 20000 g / mol, the amount of adsorption with the fiber is lowered and the tactile sensation is also lowered.
  • the molecular end of the amino-modified silicone compound may be any of a methyl group, a hydroxyl group, and an amino group, and amino-modified silsesquioxane may be added as long as the liquid state can be maintained.
  • the present invention makes it possible to impart a curl shape at 95 to 130 ° C. by combining polyvinyl chloride resin fibers and thermoplastic resin fibers.
  • the amino-modified silicone compound is Adsorption on the fiber surface will be optimized. This further improves the smoothness and drop-off resistance from the fiber surface as compared with the conventional heating at 90 ° C., and improves the tactile sensation and durability of use.
  • the molecular weight of the amino-modified silicone is low, it penetrates into the inside of the fiber and the original modification effect is reduced, so it is necessary to select an optimal molecular weight.
  • silicone oil generally generally has a molecular weight defined by kinematic viscosity, but in the amino-modified silicone compound of the present invention, the preferred kinematic viscosity is 500 to 20000 mm 2 / s at 25 ° C., more preferably 1000 to 10000 mm 2 / s.
  • the kinematic viscosity is lower than 500 mm 2 / s, the amount of penetration into the fiber increases, so the effect of improving the tactile sensation is not sufficient, and when it is higher than 10000 mm 2 / s, it is difficult to uniformly adhere to the fiber surface. Therefore, the tactile sensation improving effect is also reduced.
  • the method of supporting the amino-modified silicone compound used in the present invention on the fiber is not particularly limited.
  • the emulsion is emulsified with water as a solvent, and then the fiber is immersed and the amount remaining in the fiber is adjusted by centrifugal dehydration.
  • a surfactant or the like so that the solid content is 5 to 25%, and neutralize with acetic acid if necessary.
  • an antistatic agent or a smoothing agent may be used in combination.
  • Preferable combination components include nonionic surfactants that have a smoothing effect and an antistatic effect and also function as an emulsifying surfactant.
  • the amount of the amino-modified silicone compound used in the present invention supported on the fiber is preferably 0.05 to 0.8 omf%, preferably 0.1 to 0.6 omf%, more preferably 0.2 to 0.4 omf%.
  • the supported amount to the fiber is less than 0.05 omf%, the effect of improving the tactile sensation is small, and when it is more than 0.8 omf%, the fiber is excessively converged and the volume feeling is lowered to reduce the merchantability. To do.
  • the fiber bundle for artificial hair of the present invention is characterized by imparting a curl shape at 95 to 130 ° C., and the shrinkage rate of the polyvinyl chloride resin fiber at the temperature is not lower than the shrinkage rate of the thermoplastic resin fiber. And the difference in shrinkage between the polyvinyl chloride resin fiber and the thermoplastic resin fiber is 6% or less.
  • the method for imparting the curl shape is not particularly limited.
  • the fiber bundle is wound spirally or concentrically on a cylindrical pipe, and is heated by heating at a predetermined temperature for a predetermined time while maintaining the shape.
  • the attached shape is stored in the fiber bundle, and then a method of cooling and removing the fiber bundle from the pipe can be used.
  • the diameter of the pipe at this time can be arbitrarily selected according to the product style, but in the present invention, the thermoplastic resin fibers are in close contact with the polyvinyl chloride resin fibers to form a plurality of fulcrums, and at these fulcrums, polyvinyl chloride is used. By supporting the resin fiber, the effect of suppressing shrinkage is expressed.
  • the temperature for imparting the curled shape When the temperature for imparting the curled shape is increased, the effect of improving the style properties and the effect of improving the feel of amino-modified silicone are amplified. On the other hand, if the temperature is excessively increased, the polyvinyl chloride resin fibers are fused by heat. And feel harder. For this reason, it is necessary to set the temperature in the range of 95 to 130 ° C. in view of the balance between the two, and a preferable temperature is 100 to 120 ° C., more preferably 105 to 115 ° C. When the curl-shaped imparting temperature is lower than 95 ° C., the effect of improving the tactile sensation is not sufficient, and the style is worse than the polyvinyl chloride resin fiber alone because it is lower than the minimum processing temperature of the thermoplastic resin fiber.
  • the polyvinyl chloride resin fiber greatly exceeds the softening temperature, so it becomes difficult to suppress the fusion between the fibers only with the fiber treatment agent, and the tactile sensation becomes hard. Productivity is reduced.
  • the difference between the shrinkage ratio of the polyvinyl chloride resin fiber and the shrinkage ratio of the thermoplastic resin fiber at the curling temperature needs to be 6% or less, preferably 4% or less, more preferably 3% or less.
  • thermoplastic resin fibers may be composed of fibers having a plurality of compositions, but the fibers having any composition must satisfy the above shrinkage relationship.
  • Example 1 Shrinkage Before each fiber was mixed, or single fibers of one material were selected and bundled from the mixed fiber bundle, and a fiber bundle having a total fineness of 18000 ⁇ 3000 dtex was produced.
  • the fiber bundle is cut to a length of 40 cm, marked at a position of 5 cm from both ends, with only one end fixed, heated at a predetermined temperature for 30 minutes under drying conditions, and cooled at room temperature. went.
  • the length between the markings of the fiber bundle after cooling was measured, and the shrinkage was determined from the ratio to the original length of 30 cm. This measurement was performed 20 times in total, and the average value was taken as the shrinkage rate of the sample. Since the sample may be shorter than 40 cm in an actual hair product, the length between the markings can be shortened according to the length that can be sampled.
  • Example 5 LOI (limit oxygen index) A filament of 16 cm / 0.25 g was weighed, the ends were lightly collected with double-sided tape, and sandwiched and twisted with a suspender. When the twist was sufficiently applied, the middle of the sample was folded in two and the two were twisted together. The ends were fastened with cellophane tape so that the total length was 7 cm. Pre-drying was performed at 105 ° C. for 60 minutes, and further drying was performed for 30 minutes or more with a desiccator. The dried sample was adjusted to a predetermined oxygen concentration, and after 40 seconds, it was ignited from the top with an igniter throttled to 8 to 12 mm, and the igniter was released after ignition. The oxygen concentration that burned 5 cm or more or continued burning for 3 minutes or more was examined, and the test was repeated three times under the same conditions to obtain the critical oxygen index.
  • the extruded filament was heat-treated for about 0.5 to 1.5 seconds in a heated spinning cylinder (under 200 to 400 ° C. atmosphere and good spinnability) provided immediately below the nozzle, and spun by a first take-up roll.
  • a nonionic surfactant polyethylene oxide / polypropylene oxide copolymer, molecular weight of about 800
  • cationic surfactant ammonium sulfate compound, molecular weight of about 800
  • ester oil olein
  • An oil agent consisting of oleyl acid (molecular weight: about 500) was attached so as to be 0.5 omf% with respect to the fiber.
  • the components of the oil agent include nonionic surfactant (polyethylene oxide / polypropylene oxide copolymer, molecular weight of about 800), cationic surfactant (ammonium sulfate compound, molecular weight of about 800): ester oil (oleyl oleate: A polyvinyl chloride fiber PVC-5 was produced in the same manner as in Production Example 3 except that the molecular weight was about 500) and the amount of oil attached was 0.5 omf%.
  • nonionic surfactant polyethylene oxide / polypropylene oxide copolymer, molecular weight of about 800
  • cationic surfactant ammonium sulfate compound, molecular weight of about 800
  • ester oil oleyl oleate: A polyvinyl chloride fiber PVC-5 was produced in the same manner as in Production Example 3 except that the molecular weight was about 500) and the amount of oil attached was 0.5 omf%.
  • TPR-1 An acrylic copolymer resin obtained by copolymerizing 50% acrylonitrile, 49% vinyl chloride, and 1% sodium styrenesulfonate was dissolved in acetone to prepare a 29% spinning dope.
  • This spinning stock solution was spun into a 20% aqueous acetone solution at 20 ° C. using a dumbbell shaped cross-section nozzle under a nozzle draft of 1.6, and the resulting fiber was desolvated in a water washing bath at 50 ° C. and 1.
  • the film was stretched 5 times, then dried dry at 130 ° C., then stretched 2.5 times at 125 ° C., and further subjected to relaxation heat treatment at 150 ° C. dry heat.
  • the single fiber fineness of the acrylic fiber thus obtained was 47 dtex.
  • the cross-sectional shape was substantially a horseshoe shape.
  • TPR-2 100 parts by weight of polyethylene terephthalate (manufactured by Mitsubishi Chemical Corporation, BK-2180), brominated flame retardant (manufactured by Sakamoto Pharmaceutical Co., Ltd., SR-T20000), antimony compound (manufactured by Nippon Seiko Co., Ltd., SA-A) ) Is dried to a water content of 100 ppm or less, and then 2 parts of polyester pellets for coloring PESM6100 BLACK (manufactured by Dainichi Seika Kogyo Co., Ltd., carbon black content 30%) are added, dry blended, and supplied to a twin screw extruder. After melt-kneading at 280 ° C.
  • the molten polymer is discharged from the spinneret and cooled in a water bath at a water temperature of 50 ° C. set at a position 30 mm below the base, at a speed of 100 m / min.
  • the unwound yarn was obtained by winding.
  • the obtained unstretched yarn is stretched in a warm water bath at 80 ° C.
  • Examples 1 to 14, Comparative Examples 1 to 6) Polyvinyl chloride fibers (PVC-1 to 6) prepared in Production Examples 1 to 8 and thermoplastic resin fibers (TPR-1 and 2) are mixed at the ratio shown in Table 2 to hack and artificial hair fibers It was a bunch.
  • amino-modified silicone oil by Toray Dow Corning Co., Ltd., BY16203, kinematic viscosity 2000 mm 2 / S, functional group equivalent 1900 g / mol
  • polyethylene oxide / polypropylene oxide copolymer having a molecular weight of 10,000
  • pure water by weight
  • the mixture was mixed at a ratio of 0.5: 0.5: 9, stirred with a homogenizer to make an emulsion, and then neutralized by adding acetic acid to prepare a fiber treatment agent.
  • the fiber bundles of Examples 1 to 5, 7 to 13 and Comparative Examples 2, 4, and 6 are immersed in this fiber treatment agent for 5 minutes, and then a centrifugal dehydrator is used so that the supported amount on the fiber surface is 0.4 omf%. After removing the excess fiber treating agent, the fiber bundle was divided into two fiber bundles so that each would have 1.2 million dtex. Similarly, the fiber bundle that did not carry the fiber treatment agent was divided into two fiber bundles so that each would be 1.2 million dtex. Next, one fiber bundle was cut into a length of 35 cm, and 5 cm at both ends were bound with a string, followed by heating at the temperature shown in Table 2 for 1 hour, and the number of fiber bends of the contracted fiber bundle was measured.
  • the remaining fiber bundle is sewed with a wig sewing machine to make a mino hair having a test length of 25 cm, wound on a pipe having a diameter of 35 mm, and heat-set for 1 hour at the temperature shown in Table 2 with a convection dryer.
  • This curled mino hair is sewn on the net in 10 steps at 1 cm intervals to produce a product sample, and merchantability (smoothness, softness, moisturizing / moisturizing, elasticity / curl shape stability, volume) was evaluated. The results are shown in Table 2.
  • the artificial hair fiber of the present invention has excellent tactile sensation and styling properties, and has a quality that greatly exceeds that of conventional products by combining with a particularly rigid fiber, application of a silicone oil agent, application of high-temperature curl, and the like. It was confirmed that it was obtained.

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Abstract

The present invention pertains to a polyvinyl chloride resin fiber having a contraction stress of 70 µN/dtex or less at 130°C. It is possible to obtain an artificial hair product and fiber for artificial hair having a texture similar to human hair and exerting excellent styling properties by processing a fiber bundle for artificial hair containing 20 to 100 weight % of the aforementioned polyvinyl chlorine resin fiber and 0 to 80 weight % of a thermoplastic resin fiber which has a Young's modulus of 4 to 9 GPa and a contraction rate of 10% or less at 130°C and which comprises a composition excluding the polyvinyl chlorine resin.

Description

人工毛髪用繊維及びそれからなる頭髪装飾品Artificial hair fibers and hair ornaments comprising the same
 本発明は、スタイリング性に優れ、人毛に近い柔らかく滑らかな触感を有する人工毛髪用繊維、人工毛髪用繊維束、及び、それからなる頭髪装飾品、人工毛髪製品、さらには前記人口毛髪用繊維及び人工毛髪用繊維束を構成するポリ塩化ビニル系樹脂繊維に関するものである。 The present invention provides an artificial hair fiber having excellent styling properties and a soft and smooth touch close to human hair, an artificial hair fiber bundle, and a hair ornament, an artificial hair product comprising the same, and the artificial hair fiber and The present invention relates to a polyvinyl chloride resin fiber constituting a fiber bundle for artificial hair.
 一般に市販されている人工毛髪用の合成繊維としては、ポリ塩化ビニル系樹脂繊維、ポリエステル系樹脂繊維、モダアクリル系樹脂繊維など、多くの素材が存在する。これらの合成繊維はそれぞれが素材由来の優れた特性を有しており、各繊維の特性に応じて得意とする分野の頭飾製品に使用されてきた。さらに近年では各繊維を混ぜ合わせて一つの頭飾製品に使用し、各々の優れた特性を調和させて活かすことで、人毛品に比較的近い価値を有した商品も上市されてきている。例えばポリ塩化ビニル系樹脂繊維は人毛に近い柔らかな触感を有し、任意のスタイルに加工し易く毛の絡みも少ない。またポリエステル系樹脂繊維はコシが強く商品を装着して動いたときの弾力感に優れ、形態安定性が高いために使用耐久性に優れる。またモダアクリル系樹脂繊維は軽量でボリューム感が高く、表面凹凸を生かして自然な外観が得られる、などの特徴を有する。しかし一方で、素材の異なる繊維を混ぜ合わせて使用する場合には、各繊維の特性を充分に活かし切ることが難しく、合成繊維の頭飾製品では依然として人毛品に匹敵する商品価値を得られていないのが実状である。 There are many materials such as polyvinyl chloride resin fibers, polyester resin fibers, and modacrylic resin fibers that are generally commercially available synthetic fibers for artificial hair. Each of these synthetic fibers has excellent properties derived from the raw materials, and has been used for headdress products in the field of specialty in accordance with the properties of each fiber. Furthermore, in recent years, products having a value relatively close to that of human hair products have been put on the market by mixing each fiber and using them in one head ornament product, and making use of each excellent characteristic in harmony. For example, polyvinyl chloride resin fibers have a soft touch close to human hair, are easily processed into an arbitrary style, and have little hair entanglement. Polyester resin fibers are strong and have excellent resilience when they are moved with a product on them, and they are highly durable because of their high form stability. Modacrylic resin fibers are lightweight and have a high volume feeling, and have a feature that a natural appearance can be obtained by utilizing surface irregularities. However, on the other hand, when mixing fibers of different materials, it is difficult to make full use of the properties of each fiber, and synthetic hair headdress products still have a commercial value comparable to human hair products. There is no actual situation.
 素材の異なる繊維を混ぜ合わせて使用する際の最大の課題は、素材によって最適な加工温度が異なることにある。頭飾製品で商品価値を高めるためには、外観、触感、スタイリング性の3つの品質を何れも損なわずに向上させる必要があるが、これには各繊維の構成比率や繊維処理剤の選定に加えて、カール形状を付与する際に適正な温度で加熱することが重要となる。具体的には、適正な温度でカール形状を付与することによって、弾力性や形状保持力が向上し、これによって頭髪商品としての脈動感や使用耐久性を向上させることが出来る。さらに特定の繊維処理剤では、高温の熱を加えることによって繊維表面に繊維処理剤が馴染み、人毛に似た滑らかで保湿感(モイスチャー触感)を発現させることが可能となる。しかし一方で素材の最適温度から過度に高い温度で加熱すると、繊維間で融着が発生して柔軟性が失われ、熱収縮で繊維に屈曲が生じることでガサツキ気味の悪触感となる。また過度に低い温度で加熱すると充分に形状が保持出来なくなり、スタイリング性が低下することとなるが、相対的に高い温度で生じる課題の方が商品性の低下度が大きいため、素材の異なる繊維を混ぜ合わせる際には、耐熱性の最も低い素材の適正加工温度に合わせてカールを付与することが一般的である。 The biggest challenge when using mixed fibers of different materials is that the optimum processing temperature differs depending on the material. In order to increase the commercial value of headdress products, it is necessary to improve the appearance, tactile sensation, and styling quality without sacrificing all of them, but in addition to selecting the composition ratio of each fiber and the fiber treatment agent Thus, it is important to heat at an appropriate temperature when imparting the curl shape. Specifically, by imparting a curl shape at an appropriate temperature, the elasticity and shape retention force are improved, thereby improving the pulsation and durability of use as a hair product. Furthermore, in a specific fiber treatment agent, by applying high-temperature heat, the fiber treatment agent becomes familiar with the fiber surface, and a smooth and moisturizing feeling (moisture feel) similar to human hair can be expressed. However, on the other hand, when heated at an excessively high temperature from the optimum temperature of the material, fusion occurs between the fibers, the flexibility is lost, and the fibers are bent due to thermal contraction, resulting in a gritty feel. In addition, when heated at an excessively low temperature, the shape cannot be retained sufficiently, and the styling property will be lowered. In general, curling is performed in accordance with an appropriate processing temperature of a material having the lowest heat resistance.
 そして特にポリ塩化ビニル系樹脂は耐熱性が低く、温度の上昇に伴う品質の低下が顕著であるために、カール形状を付与する温度は80~90℃に限定されていた。このため特にポリエステル系樹脂繊維などの高耐熱繊維を混合した場合には、ポリエステル系樹脂繊維の適正温度よりも加工温度が低いために、本来持っているカールの強さを活かすことが出来ない状況となっており、加えて繊維処理剤が本来有している触感の改良効果も充分には発現出来ない状態となっていた。しかしポリ塩化ビニル系樹脂繊維は、人毛に似たソフトで滑らかな触感、カール形状のスタイル性、そしてコストパフォーマンスなど、毛髪用繊維として非常に優れた特性を有するために同分野では外すことが困難な存在となっており、従来の技術では総合的な品質において充分に満足するレベルを得ることは出来ていなかった。 In particular, since the polyvinyl chloride resin has low heat resistance, and the deterioration of the quality due to the increase in temperature is remarkable, the temperature for imparting the curled shape is limited to 80 to 90 ° C. For this reason, especially when high heat-resistant fibers such as polyester resin fibers are mixed, the processing temperature is lower than the appropriate temperature of the polyester resin fibers, so it is not possible to make use of the inherent curl strength. In addition, the effect of improving the tactile sensation inherent to the fiber treatment agent cannot be fully exhibited. However, polyvinyl chloride resin fiber has very excellent properties as a fiber for hair, such as soft and smooth touch similar to human hair, curled style, and cost performance. It has been difficult, and the conventional technology has not been able to obtain a satisfactory level of overall quality.
 具体的には、例えば、特許文献1および2には、ポリエステル系樹脂繊維とハロゲン含有樹脂繊維、またはモダアクリル系樹脂繊維とポリ塩化ビニル系樹脂繊維を混ぜ合わせて100℃以上でカールを付与する例が記載されている。これらの技術は、異なる素材を混ぜ合わせて、その特性を生かすことによって、従来品よりも優れた商品性の発現に成功した。しかし、ポリ塩化ビニル系樹脂繊維の性能が十分ではなかったため、触感の観点ではまだ改良の余地があり、人毛品に匹敵する商品性を提供するまでには至っていなかった。 Specifically, for example, Patent Documents 1 and 2 include examples in which a polyester resin fiber and a halogen-containing resin fiber, or a modacrylic resin fiber and a polyvinyl chloride resin fiber are mixed to impart curl at 100 ° C. or higher. Is described. These technologies have succeeded in developing merchandise superior to conventional products by mixing different materials and taking advantage of their characteristics. However, since the performance of the polyvinyl chloride resin fiber was not sufficient, there was still room for improvement from the viewpoint of tactile sensation, and it was not possible to provide merchandise comparable to human hair products.
 さらに前述の課題を解決することを目的に、ポリ塩化ビニル系樹脂繊維に関する幾つかの試みが行われているが、まだ充分な効果を得るには至っていない。 Furthermore, several attempts have been made regarding polyvinyl chloride resin fibers for the purpose of solving the above-mentioned problems, but sufficient effects have not yet been obtained.
 例えば特許文献3では、カールの付与条件の計算法が記されているが、単純に収縮率を低くするだけでは繊維屈曲の生成を抑える効果が充分ではなく、また高温条件では繊維が硬くなるなど、触感の概念が考慮されていないために毛髪用商品としては満足な品質を得ることが出来なかった。 For example, Patent Document 3 describes a method for calculating curling conditions. However, simply reducing the shrinkage rate does not provide a sufficient effect of suppressing the generation of fiber bending, and the fibers become hard at high temperatures. Since the concept of tactile sensation was not taken into account, satisfactory quality could not be obtained as a hair product.
 また特許文献4では、ポリ塩化ビニル系樹脂繊維の耐熱性を向上させる試みとして、高塩素含有率の塩素化ポリ塩化ビニル樹脂を配合する例が記載されているが、収縮率を低減するだけでは毛髪用商品として満足な触感を得ることは出来なかった。 Patent Document 4 describes an example of blending a chlorinated polyvinyl chloride resin having a high chlorine content as an attempt to improve the heat resistance of the polyvinyl chloride resin fiber, but only by reducing the shrinkage rate. A satisfactory tactile sensation as a hair product could not be obtained.
 そして何れの特許文献も、繊維処理剤の効果を充分に得るための検討はされておらず、頭髪製品に求められる滑らかで保湿感のある触感が満足するレベルには至っていなかった。 None of the patent literatures have been studied for sufficiently obtaining the effect of the fiber treatment agent, and have not reached a level that satisfies the smooth and moisturizing feel required for hair products.
特開2002-227019号公報JP 2002-227019 A WO2005/082184号公報WO2005 / 082184 特開2003-293213号公報JP 2003-293213 A 特許第4491414号公報Japanese Patent No. 4491414
 本発明は、スタイリング性に優れ、人毛に近い柔らかく滑らかな触感を有する人工毛髪用繊維及び人工毛髪製品を提供することを目的とする。 An object of the present invention is to provide a fiber for artificial hair and an artificial hair product that have excellent styling properties and have a soft and smooth feel close to human hair.
 本発明者らは、前記課題を解決するために鋭意検討を重ねた結果、ポリ塩化ビニル系樹脂繊維に収縮応力を低減させる改良を施した上で、必要に応じて耐熱性と剛性に優れる繊維を混ぜ合わせて、カール形状付与温度と収縮率、および繊維処理剤を選定して加工することで、前記の課題を解決した頭飾製品を作製出来ることを見出し、本発明を完成するに至った。以下に、本発明の原理について説明する。 As a result of intensive studies to solve the above problems, the present inventors have made improvements in reducing the shrinkage stress to the polyvinyl chloride resin fiber and, if necessary, a fiber excellent in heat resistance and rigidity. It was found that a head decoration product that solves the above problems can be produced by selecting and processing the curl shape imparting temperature and shrinkage rate, and the fiber treatment agent, thereby completing the present invention. The principle of the present invention will be described below.
 ポリ塩化ビニル系樹脂繊維は、前述のように主成分とするポリ塩化ビニル系樹脂の軟化温度が低いために、ガラス転移温度を超える90℃より高い温度で加工すると、収縮による繊維屈曲を生じて、ガサツキ気味の悪触感となる。この繊維屈曲は以下の原理で発生する。まずカール形状を付与する工程では、円筒形状のパイプに螺旋または同心円状に繊維束を捲き付け、その形態を保持した状態で所定時間加熱を行うことで捲き付け形状が繊維束に記憶され、その後冷却してパイプから繊維束を外すことで工程を完了する。この際に収縮差が大きい繊維が混合されていると、収縮の小さい繊維を収縮の大きい繊維が引っ張ることによって収縮率の小さい繊維に撓みが生じ、温度が高い場合にはその撓みが繊維屈曲となって触感悪化の原因となっていた。そして人間の触感では屈曲の角度が170°未満になるとガサツキ感を感じることを見出した。さらに、ポリ塩化ビニル系樹脂繊維は、モダアクリル系樹脂繊維やポリエステル系樹脂繊維など他の繊維に対して、170°未満の角度の繊維屈曲が発生し易く、加えて繊維間の融着で柔軟性が失われるために、触感の悪化度が極めて大きいことを見出した。 As described above, since the polyvinyl chloride resin fiber has a low softening temperature of the main component polyvinyl chloride resin, if it is processed at a temperature higher than 90 ° C., which exceeds the glass transition temperature, the fiber bends due to shrinkage. , It becomes a feeling of bad touch. This fiber bending occurs on the following principle. First, in the step of imparting a curl shape, a fiber bundle is wound spirally or concentrically on a cylindrical pipe and heated for a predetermined time in a state in which the shape is maintained, and then the brazed shape is stored in the fiber bundle, and then The process is completed by cooling and removing the fiber bundle from the pipe. At this time, if fibers with a large shrinkage difference are mixed, the fibers with a small shrinkage are pulled by the fibers with a small shrinkage by pulling the fibers with a small shrinkage, and when the temperature is high, the deflection is a fiber bending. It became the cause of the tactile deterioration. And in human tactile sensation, it has been found that when the angle of bending is less than 170 °, a feeling of roughness is felt. In addition, polyvinyl chloride resin fibers tend to bend at angles of less than 170 ° relative to other fibers such as modacrylic resin fibers and polyester resin fibers, and in addition, they are flexible by fusion between fibers. It has been found that the degree of deterioration of the tactile sensation is extremely large.
 そして発明者らが検討を重ねた結果、収縮率の高い繊維の収縮応力が小さい場合には、収縮率の低い繊維が支柱の役割を担って撓みが生じ難くなり、さらに収縮率の低い繊維の剛性が高い場合には収縮率の大きい繊維の収縮が抑制されて、繊維屈曲が発生し難くなることを見出した。そしてその原理を応用して、繊維屈曲の発生し易いポリ塩化ビニル系樹脂繊維の収縮応力を低減させ、必要に応じてポリ塩化ビニル系樹脂繊維よりも剛性が高く収縮の小さい例えばポリエステル系樹脂繊維を混合することにより、従来の90℃より高い温度でも繊維屈曲を増加させることなくカール形状を付与することに成功した。 As a result of repeated investigations by the inventors, when the shrinkage stress of the fiber having a high shrinkage rate is small, the fiber having a low shrinkage rate plays a role of a support column and is less likely to bend. It has been found that when the rigidity is high, the shrinkage of the fiber having a large shrinkage rate is suppressed, and the fiber bending becomes difficult to occur. And by applying that principle, the shrinkage stress of polyvinyl chloride resin fibers that tend to bend fibers is reduced, and if necessary, the rigidity is higher than that of polyvinyl chloride resin fibers and the shrinkage is small. By mixing these, the curl shape was successfully imparted without increasing fiber bending even at a temperature higher than the conventional 90 ° C.
 またカール形状の付与温度を上げる効果は繊維処理剤の触感にも影響し、高温で加熱することで繊維処理剤と繊維表面の馴染みが向上し、特にアミノ変性シリコーン化合物を用いた場合には90℃以下でカール形状を付与した場合と比較して、繊維の滑らかさや保湿感の増幅効果が得られることを発見した。さらにアミノ変性シリコーン化合物はポリ塩化ビニル系樹脂繊維の繊維間融着を抑制する効果が得られることから、従来高温加熱時には低下していた繊維の柔軟性も確保することが可能となり、総合的に人毛に近い優れた触感を得られることを見出した。 Further, the effect of increasing the temperature for imparting the curl shape also affects the tactile feel of the fiber treatment agent, and the familiarity between the fiber treatment agent and the fiber surface is improved by heating at a high temperature, particularly when an amino-modified silicone compound is used. It has been discovered that the fiber smoothness and the moisturizing feeling can be amplified compared to the case where the curl shape is imparted at a temperature of ℃ or lower. Furthermore, since the amino-modified silicone compound has the effect of suppressing the inter-fiber fusion of the polyvinyl chloride resin fibers, it is possible to ensure the flexibility of the fibers that has been lowered at the time of high temperature heating. It has been found that an excellent tactile sensation close to human hair can be obtained.
 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.
 本発明の特徴の一つは、130℃における収縮応力が70μN/dtex以下であるポリ塩化ビニル系樹脂繊維である。 One of the characteristics of the present invention is a polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less.
 本発明の別の特徴の一つは、130℃における収縮応力が70μN/dtex以下である人工毛髪用ポリ塩化ビニル系樹脂繊維である。 Another feature of the present invention is a polyvinyl chloride resin fiber for artificial hair having a shrinkage stress at 130 ° C. of 70 μN / dtex or less.
 本発明の別の特徴の一つは、130℃における収縮応力が70μN/dtex以下であるポリ塩化ビニル系樹脂繊維20~100重量%と、ポリ塩化ビニル系樹脂を除く組成からなる熱可塑性樹脂繊維0~80重量%を含む人工毛髪用繊維束である。 Another feature of the present invention is that a thermoplastic resin fiber comprising 20 to 100% by weight of a polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less and a composition excluding the polyvinyl chloride resin. A fiber bundle for artificial hair containing 0 to 80% by weight.
 本発明の別の特徴の一つは、130℃における収縮応力が70μN/dtex以下であるポリ塩化ビニル系樹脂繊維20~100重量%と、ヤング率が4~9GPaであり、130℃における収縮率が10%以下であり、ポリ塩化ビニル系樹脂を除く組成からなる熱可塑性樹脂繊維0~80重量%を含む人工毛髪用繊維束である。 Another feature of the present invention is that 20 to 100% by weight of polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less, Young's modulus of 4 to 9 GPa, and shrinkage at 130 ° C. Is a fiber bundle for artificial hair containing 10 to 80% by weight of thermoplastic resin fibers having a composition excluding polyvinyl chloride resin.
 本発明の別の特徴の一つは、ポリ塩化ビニル系樹脂繊維の130℃における収縮率が、熱可塑性樹脂繊維の130℃における収縮率より低くなく、ポリ塩化ビニル系樹脂繊維の130℃における収縮率と、熱可塑性樹脂繊維の130℃における収縮率の差が6%以下であることを特徴とする人工毛髪用繊維束である。 Another feature of the present invention is that the shrinkage rate of the polyvinyl chloride resin fiber at 130 ° C. is not lower than the shrinkage rate of the thermoplastic resin fiber at 130 ° C., and the shrinkage rate of the polyvinyl chloride resin fiber at 130 ° C. The fiber bundle for artificial hair, characterized in that the difference between the shrinkage rate and the shrinkage rate of thermoplastic resin fibers at 130 ° C. is 6% or less.
 本発明の別の特徴の一つは、ポリ塩化ビニル系樹脂繊維及び熱可塑性樹脂繊維がアミノ変性シリコーン化合物を含む人工毛髪用繊維束である。 Another feature of the present invention is a fiber bundle for artificial hair in which the polyvinyl chloride resin fiber and the thermoplastic resin fiber contain an amino-modified silicone compound.
 本発明の別の特徴の一つは、ポリ塩化ビニル系樹脂繊維が重量平均分子量2000~25000のポリアルキレンオキシド系化合物を0.07~0.5omf%含む人工毛髪用繊維束である。 Another feature of the present invention is a fiber bundle for artificial hair in which the polyvinyl chloride resin fiber contains 0.07 to 0.5 omf% of a polyalkylene oxide compound having a weight average molecular weight of 2000 to 25000.
 本発明の別の特徴の一つは、ポリ塩化ビニル系樹脂繊維がシリコーン系化合物を0~0.5omf%含む人工毛髪用繊維束である。 Another feature of the present invention is a fiber bundle for artificial hair in which the polyvinyl chloride resin fiber contains 0 to 0.5 omf% of a silicone compound.
 本発明の別の特徴の一つは、130℃における収縮応力が70μN/dtex以下であるポリ塩化ビニル系樹脂繊維20~100重量%と、ポリ塩化ビニル系樹脂を除く組成からなる熱可塑性樹脂繊維0~80重量%を含む人工毛髪用繊維束を加工して得られる人工毛髪製品である。 Another feature of the present invention is that a thermoplastic resin fiber comprising 20 to 100% by weight of a polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less and a composition excluding the polyvinyl chloride resin. An artificial hair product obtained by processing a fiber bundle for artificial hair containing 0 to 80% by weight.
 本発明は、スタイリング性に優れ、人毛に近い柔らかく滑らかな触感を有する人工毛髪用繊維及び人工毛髪製品が得られる。 The present invention provides an artificial hair fiber and an artificial hair product that are excellent in styling properties and have a soft and smooth feel close to human hair.
本発明の製造例1-4に記載のポリ塩化ビニル系樹脂繊維に係る収縮応力の測定結果を示す図で、PVC-1が従来品、PVC-2~4が本発明の改良品を示す。FIG. 4 is a diagram showing the measurement results of shrinkage stress relating to the polyvinyl chloride resin fibers described in Production Example 1-4 of the present invention, PVC-1 being a conventional product and PVC-2 to PVC-4 being improved products of the present invention.
 以下に、本発明の詳細を説明する。 Details of the present invention will be described below.
 本発明の人工毛髪用繊維束は、130℃における収縮応力が70μN/dtex以下であるポリ塩化ビニル系樹脂繊維20~100重量%、ヤング率が4~9GPaであり130℃の収縮率が10%以下でありポリ塩化ビニル系樹脂を除く組成からなる熱可塑性樹脂繊維0~80重量%からなることを特徴とする。 The fiber bundle for artificial hair of the present invention has 20 to 100% by weight of polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less, Young's modulus of 4 to 9 GPa, and shrinkage at 130 ° C. of 10%. It is characterized by comprising 0 to 80% by weight of thermoplastic resin fibers having the following composition excluding polyvinyl chloride resin.
 本発明における繊維束とは、1本20~100dtexの単繊維を2本以上集合させたものを指し、単繊維の集合が崩れないように固定してもよく、また固定されていなくてもよい。人工毛髪用の合成繊維は、通常は数百mの連続した繊維束として製造され、商品加工時に任意の長さに切断し、繊維の混合やカール形状の付与などを行って製品化されるが、本発明における繊維束とは特に限定されず、特に指定がない場合には、たとえば、製造時の連続した繊維束、商品加工時に切断した繊維束、毛髪用製品内の繊維束、などを指す。 The fiber bundle in the present invention refers to an aggregate of two or more single fibers of 20 to 100 dtex, and may be fixed so that the aggregate of single fibers does not collapse or may not be fixed. . Synthetic fibers for artificial hair are usually manufactured as continuous fiber bundles of several hundreds of meters, cut into an arbitrary length at the time of product processing, and then commercialized by mixing fibers or imparting a curled shape. The fiber bundle in the present invention is not particularly limited, and unless otherwise specified, for example, refers to a continuous fiber bundle during production, a fiber bundle cut during product processing, a fiber bundle in a hair product, and the like. .
 本発明に用いるポリ塩化ビニル系樹脂繊維は、ポリ塩化ビニル系樹脂を主成分とする繊維であって、収縮応力が小さいことを特徴とする。一般に収縮応力は収縮率が大きいと高くなる傾向にあるが、潜在的な収縮歪があっても収縮時に発生する応力を小さくすることは可能であり、これによって繊維屈曲の発生を抑えることができる。収縮応力を低減させるには繊維製造時に例えば110℃以上の高温で長時間の緩和熱処理を行う方法が有効で、同じ収縮率であっても収縮応力を下げることができる。しかし、収縮応力を低減させる方法はこれに限らず使用できる。ポリ塩化ビニル系樹脂繊維において収縮応力は、一般的に図1のように130℃付近にピークを有し、本発明における収縮応力の好ましい値は、具体的には、130℃における収縮応力が70μN/dtex以下がよく、好ましくは50μN/dtex以下、さらに好ましくは40μN/dtex以下がよい。収縮応力が70μN/dtexを超えると、ポリ塩化ビニル系樹脂繊維を支えて収縮を抑制する熱可塑性樹脂繊維の効果が充分では無くなるために、ポリ塩化ビニル系樹脂繊維に撓みが生じ、繊維屈曲が発生して触感が悪化する。 The polyvinyl chloride resin fiber used in the present invention is a fiber mainly composed of a polyvinyl chloride resin and has a small shrinkage stress. In general, the shrinkage stress tends to increase when the shrinkage rate is large. However, even if there is a potential shrinkage strain, it is possible to reduce the stress generated at the time of shrinkage, thereby suppressing the occurrence of fiber bending. . In order to reduce the shrinkage stress, a method of performing relaxation heat treatment for a long time at a high temperature of, for example, 110 ° C. or more at the time of fiber production is effective, and the shrinkage stress can be lowered even with the same shrinkage rate. However, the method of reducing the shrinkage stress is not limited to this and can be used. In the polyvinyl chloride resin fiber, the shrinkage stress generally has a peak in the vicinity of 130 ° C. as shown in FIG. 1, and a preferable value of the shrinkage stress in the present invention is specifically a shrinkage stress at 130 ° C. of 70 μN. / Dtex or less is preferable, preferably 50 μN / dtex or less, and more preferably 40 μN / dtex or less. When the shrinkage stress exceeds 70 μN / dtex, the effect of the thermoplastic resin fiber that supports the polyvinyl chloride resin fiber and suppresses the shrinkage is not sufficient, so that the polyvinyl chloride resin fiber bends, and the fiber bending does not occur. Occurs and feels worse.
 本発明に用いるポリ塩化ビニル系樹脂繊維は、人工毛髪用ポリ塩化ビニル系樹脂繊維として好適に用いることができる。 The polyvinyl chloride resin fiber used in the present invention can be suitably used as a polyvinyl chloride resin fiber for artificial hair.
 本発明に用いるポリ塩化ビニル系樹脂繊維の、人工毛髪用繊維束における構成比率は20~100重量%、好ましくは30~75重量%、さらに好ましく40~60重量%である。人工毛髪用繊維束における構成比率が20重量%より低いと、ポリ塩化ビニル系樹脂繊維の有する柔軟な触感やスタイル性が不足して満足な商品性が得られず、商品性が低下する傾向にある。 The composition ratio of the polyvinyl chloride resin fiber used in the present invention in the fiber bundle for artificial hair is 20 to 100% by weight, preferably 30 to 75% by weight, and more preferably 40 to 60% by weight. If the composition ratio in the fiber bundle for artificial hair is lower than 20% by weight, the soft tactile and style properties of the polyvinyl chloride resin fiber are insufficient, and satisfactory merchandise cannot be obtained, and the merchantability tends to decrease. is there.
 また本発明に用いるポリ塩化ビニル系樹脂繊維として、商品に加工する前の繊維束の状態において、重量平均分子量2000~25000のポリアルキレンオキシド系化合物を0.07~0.5omf%、およびシリコーン系化合物を0~0.5omf%繊維の表面に担持したものを好適に使用することができる。 Further, as the polyvinyl chloride resin fiber used in the present invention, 0.07 to 0.5 omf% of a polyalkylene oxide compound having a weight average molecular weight of 2000 to 25000 in a fiber bundle state before being processed into a product, and a silicone type A compound in which a compound is supported on the surface of 0 to 0.5 omf% fiber can be preferably used.
 繊維の表面に担持するとは、特定の化合物が繊維の表面層に付着している状態を指し、繊維内部に浸透して除去出来なくなった成分に関しては対象外とする。本発明においては、ポリ塩化ビニル系樹脂繊維の内部まで浸透しない溶剤としてエタノール/シクロヘキサン=50wt%/50wt%を用い、この溶剤に繊維を浸漬した際に抽出される化合物の重量を担持量として扱う。 “Supported on the surface of the fiber” means a state in which a specific compound adheres to the surface layer of the fiber, and excludes components that have penetrated into the fiber and can no longer be removed. In the present invention, ethanol / cyclohexane = 50 wt% / 50 wt% is used as a solvent that does not penetrate into the inside of the polyvinyl chloride resin fiber, and the weight of the compound extracted when the fiber is immersed in this solvent is handled as the supported amount. .
 前述した繊維の収縮応力を低減させる方法として、緩和熱処理の温度を高くした場合、従来の毛髪用ポリ塩化ビニル系樹脂繊維では繊維間で融着が発生して、素材が有する人毛に近いソフトな触感を得られなくなる問題があった。これは通常融着を抑制する目的で使用される工程油剤の性能が充分でないために発生する。ポリ塩化ビニル系樹脂繊維では、工程油剤として、非イオン系の界面活性剤、カチオン系の界面活性剤、エステル油などの油成分、などからなる混合エマルジョンが使用されてきたが、これらの油剤成分は何れも重量平均分子量が1500未満の低分子成分であった。これは高分子量の成分を用いた場合には、ベトツキ気味の触感となり、商品加工時に別の油剤を乗せ換える場合も充分に洗浄することが難しいために、最終商品においても満足な触感を得られなく問題があったからである。しかし発明者らが検討を重ねた結果、重量平均分子量1500未満の繊維処理剤成分は、塩化ビニル系樹脂繊維の表面に担持させた状態で100℃以上で加熱すると、繊維内部に徐々に浸透して、繊維表面層の残存量が大きく低下することで融着抑制効果が低減し、さらに繊維内部に浸透した油成分が可塑化効果を発現することで、繊維間融着の促進や収縮応力の増加を招くことを発見した。そこで検討を重ねた結果、重量平均分子量2000~25000のポリアルキレンオキシド系化合物を工程油剤として用いた場合には、油剤が繊維内部に浸透することはなく、120℃以上の高温で保持しても充分な融着抑制効果を発現できることを見出した。さらに同油剤は、付着量を調整することで触感のベトツキ感が改良され、少ない付着量でも櫛通り性や静電気抑制効果が良好であった。 As a method of reducing the shrinkage stress of the fibers described above, when the temperature of the relaxation heat treatment is increased, the conventional polyvinyl chloride resin fibers for hair cause fusion between the fibers, and the softness close to human hair that the material has There was a problem that it was impossible to get a good touch. This usually occurs because the performance of the process oil used for the purpose of suppressing fusion is not sufficient. In polyvinyl chloride resin fibers, mixed emulsions composed of nonionic surfactants, cationic surfactants, oil components such as ester oils, etc. have been used as process oils. Were low molecular weight components having a weight average molecular weight of less than 1500. When high molecular weight components are used, the feel becomes sticky and it is difficult to wash thoroughly even when changing another oil during product processing, so that a satisfactory feel can be obtained even in the final product. It was because there was a problem. However, as a result of repeated studies by the inventors, a fiber treatment agent component having a weight average molecular weight of less than 1500 is gradually penetrated into the fiber when heated at 100 ° C. or higher while being supported on the surface of a vinyl chloride resin fiber. As a result, the residual amount of the fiber surface layer is greatly reduced, so that the effect of suppressing fusion is reduced, and further, the oil component that has penetrated into the inside of the fiber exhibits a plasticizing effect. I found that it caused an increase. As a result of repeated studies, when a polyalkylene oxide compound having a weight average molecular weight of 2000 to 25000 is used as a process oil, the oil does not penetrate into the fiber and can be maintained at a high temperature of 120 ° C. or higher. It has been found that a sufficient fusion suppression effect can be expressed. Furthermore, the oil agent improved the stickiness of the tactile sensation by adjusting the adhesion amount, and the combing property and the static electricity suppressing effect were good even with a small adhesion amount.
 本発明に用いるポリアルキレンオキシド系化合物として、活性水素基を2個有する有機化合物にエチレンオキシドを含有するアルキレンオキシドを付加重合せしめたポリアルキレンオキシド化合物を好適に用いることができる。活性水素基を2個有する有機化合物としては、例えばエチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、1,6-ヘキサンジオール、アニリン等が例示できる。これらの中から少なくとも1以上の化合物を好適に用いることができる。エチレンオキシドを含有するアルキレンオキシドとしては、エチレンオキシドおよび炭素数3~30のアルキレンオキシドであり、例えばプロピレンオキシド、ブチレンオキシド、スチレンオキシド、α-オレフィンエポキシド又はグリシジルエーテル類を用いることができる。これらの中から少なくとも1以上の化合物を好適に用いることができる。この中で触感の観点では炭素数は少ない方が好ましいが、融着抑制効果を得るには室温で流動性を有することが必要となることから、エチレンオキシドとプロピレンオキシドの共重合体が好ましい。またアルキレンオキシドの付加重合は公知の方法に従って行うことができ、ランダムタイプでもブロックタイプでもよい。また分子量は重量平均分子量で2000~25000がよく、好ましくは5000~20000、さらに好ましくは10000~18000である。重量平均分子量が2000より小さいと、加熱時に繊維内部に浸透して融着抑制効果が低減するために繊維の触感が硬くなり、25000より大きいと付着量を調整してもベトツキ気味の悪触感となる。また触感と帯電防止効果を両立させるために、前述の範囲で異なる重量平均分子量のポリアルキレンオキシド化合物を混合してもよい。 As the polyalkylene oxide compound used in the present invention, a polyalkylene oxide compound obtained by addition-polymerizing an alkylene oxide containing ethylene oxide to an organic compound having two active hydrogen groups can be suitably used. Examples of the organic compound having two active hydrogen groups include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,6-hexanediol, and aniline. Among these, at least one compound can be suitably used. Examples of the alkylene oxide containing ethylene oxide include ethylene oxide and alkylene oxides having 3 to 30 carbon atoms. For example, propylene oxide, butylene oxide, styrene oxide, α-olefin epoxide, or glycidyl ethers can be used. Among these, at least one compound can be suitably used. Among these, from the viewpoint of tactile sensation, it is preferable that the number of carbon atoms is small, but a copolymer of ethylene oxide and propylene oxide is preferable because it needs fluidity at room temperature in order to obtain an effect of suppressing fusion. The addition polymerization of alkylene oxide can be carried out according to a known method, and may be random type or block type. The molecular weight is preferably 2000 to 25000 in terms of weight average molecular weight, preferably 5000 to 20000, and more preferably 10,000 to 18000. If the weight average molecular weight is less than 2000, the fiber feels harder because it penetrates into the fiber during heating and the effect of suppressing fusion is reduced, and if it is greater than 25000, even if the amount of adhesion is adjusted, the feeling of stickiness is felt. Become. In order to achieve both the tactile sensation and the antistatic effect, polyalkylene oxide compounds having different weight average molecular weights within the above range may be mixed.
 本発明に用いるポリアルキレンオキシド系化合物の繊維に対する担持量は0.07~0.5omf%がよく、好ましくは0.07~0.3omf%、さらに好ましくは0.1~0.2omf%である。繊維に対する担持量が0.07より少ない場合には、融着抑制効果が不足するために繊維が硬くなり、また櫛通り性や静電気抑制効果が不十分となる。また繊維に対する担持量が0.5omf%より多いとベトツキ気味の悪触感となり、また繊維が過度に収束してボリューム感が低減する。 The supported amount of the polyalkylene oxide compound used in the present invention on the fiber is preferably 0.07 to 0.5 omf%, preferably 0.07 to 0.3 omf%, more preferably 0.1 to 0.2 omf%. . When the supported amount with respect to the fiber is less than 0.07, the effect of suppressing fusion is insufficient, the fiber becomes hard, and the combing property and the effect of suppressing static electricity are insufficient. On the other hand, when the loading amount on the fiber is more than 0.5 omf%, the feeling of stickiness is felt, and the fiber is excessively converged to reduce the volume feeling.
 本発明に用いるポリ塩化ビニル系樹脂繊維には、ポリアルキレンオキシド系化合物に加えてシリコーン系化合物を担持させてもよい。特定の粘度を有するシリコーン系化合物は、ポリアルキレンオキシド系化合物と同様に繊維内部に浸透することがなく、かつ高い融着抑制効果を得られる。さらにシリコーン系化合物がアミノ変性シリコーン系化合物の場合、前述のように高温で熱処理を行うことで良好な触感が得られ、特に緩和熱処理工程では張力のある状態で加熱するために繊維屈曲が生成しないことから、カール形状付与時よりも高い温度で加熱が可能であり、より高い触感の改良効果が得られる。但しシリコーン系化合物は帯電効果が大きいために、単独で油剤として使用することは出来ず、ポリアルキレンオキシド系化合物と併用して用いる必要がある。 The polyvinyl chloride resin fiber used in the present invention may carry a silicone compound in addition to the polyalkylene oxide compound. A silicone compound having a specific viscosity does not penetrate into the inside of the fiber as in the case of the polyalkylene oxide compound, and can provide a high fusion suppressing effect. Furthermore, when the silicone compound is an amino-modified silicone compound, good tactile sensation is obtained by performing heat treatment at a high temperature as described above, and fiber bending does not occur because heating is performed in a tension state particularly in the relaxation heat treatment step. Therefore, heating can be performed at a higher temperature than when the curled shape is imparted, and a higher tactile improvement effect can be obtained. However, since a silicone compound has a large charging effect, it cannot be used alone as an oil agent, and must be used in combination with a polyalkylene oxide compound.
 本発明に用いるシリコーン系化合物として、23℃で液体の直鎖状ポリジメチルシロキサン、あるいは同ポリジメチルシロキサンにアミノ基、エポキシ基、カルボキシル基、ポリエーテル基、チオール基を側鎖に導入させ、分子の末端はメチル基、あるいは水酸基とした、一般にシリコーンオイルと称される化合物を好適に用いることができる。また繊維表面には複数のシリコーン化合物を混合してもよく、エマルジョンの安定性を保てる範囲で上記官能基を有するシルセスキオキサンを混合してもよい。この中で好ましくは、ポリジメチルシロキサン、アミノ基変性ジメチルシロキサン、エポキシ変性ジメチルシロキサンであり、さらに好ましくはアミノ変性ジメチルシロキサンとジメチルシロキサンである。アミノ変性ジメチルシロキサンは他のシリコーン化合物よりも比較的低温で繊維表面との馴染みが良くなり良好な触感を得ることができ、これに任意の割合でジメチルシロキサンを加えることによって、より滑らかな触感を得ることができる。またシリコーン化合物の中でシリコーンオイルは一般的に分子量を動粘度で規定する場合が多いが、本発明において好ましい動粘度は25℃において500~20000mm2/sで、さらに好ましくは1000~10000mm2/sである。動粘度が500mm2/sより低いと繊維内部に浸透する量が多くなるために、融着抑制効果が不足して繊維が硬くなり、20000mm2/sよりも高いと繊維表面に均一に付着させることが難しくなり、融着抑制効果と触感改良効果を充分に得ることが出来なくなる。 As a silicone compound used in the present invention, a linear polydimethylsiloxane that is liquid at 23 ° C., or an amino group, an epoxy group, a carboxyl group, a polyether group, or a thiol group is introduced into the side chain of the polydimethylsiloxane to form a molecule. A compound generally referred to as a silicone oil having a methyl group or a hydroxyl group at the end can be preferably used. Further, a plurality of silicone compounds may be mixed on the fiber surface, and silsesquioxane having the above functional group may be mixed within a range that can maintain the stability of the emulsion. Among these, polydimethylsiloxane, amino group-modified dimethylsiloxane, and epoxy-modified dimethylsiloxane are preferable, and amino-modified dimethylsiloxane and dimethylsiloxane are more preferable. Amino-modified dimethylsiloxane has a better feel to the fiber surface at a relatively low temperature than other silicone compounds, and can provide a good tactile feel. By adding dimethylsiloxane in any proportion, a smoother tactile feel can be obtained. Obtainable. Among silicone compounds, silicone oil generally has a molecular weight generally defined by kinematic viscosity. In the present invention, a preferable kinematic viscosity is 500 to 20000 mm 2 / s at 25 ° C., more preferably 1000 to 10,000 mm 2 / s. s. If the kinematic viscosity is lower than 500 mm 2 / s, the amount of penetration into the fiber increases, so that the effect of suppressing fusion is insufficient and the fiber becomes hard, and if it is higher than 20000 mm 2 / s, it adheres uniformly to the fiber surface. This makes it difficult to obtain a sufficient effect of suppressing fusion and improving the tactile sensation.
 本発明に用いるシリコーン化合物の繊維に対する担持量は0~0.5omf%がよく、好ましくは0.02~0.3omf%、さらに好ましくは0.05~0.2omf%である。繊維に対する担持量が0.5omf%よりも多い場合には、帯電効果が大きいために静電気が発生して繊維の加工時に単繊維が絡むなどの問題が出る。 The supported amount of the silicone compound used in the present invention on the fiber is preferably 0 to 0.5 omf%, preferably 0.02 to 0.3 omf%, more preferably 0.05 to 0.2 omf%. When the amount supported on the fiber is more than 0.5 omf%, the charging effect is great, and static electricity is generated, causing problems such as entanglement of single fibers during fiber processing.
 また本発明に用いるポリ塩化ビニル系樹脂繊維は、ポリアルキレンオキシド系化合物とシリコーン系化合物以外にも帯電防止剤や平滑剤を加えてもよいが、繊維に浸透して可塑化効果を発現する鉱物油やエステル油などの油成分の付着量は少ない方がよく、油成分の好ましい付着量は0.15omf%以下、さらに好ましくは0.07omf%以下である。 In addition to the polyalkylene oxide compound and the silicone compound, the polyvinyl chloride resin fiber used in the present invention may contain an antistatic agent or a smoothing agent, but it is a mineral that penetrates into the fiber and exhibits a plasticizing effect. The adhesion amount of oil components such as oil and ester oil should be small, and the preferable adhesion amount of the oil component is 0.15 omf% or less, more preferably 0.07 omf% or less.
 本発明に用いるポリ塩化ビニル系樹脂繊維は、配合や製造方法においては、特に限定されず従来公知の製造方法を用いて作製することが出来るが、毛髪用繊維に適した繊度や繊維の断面形状を得るために、同分野の製造方法を用いることが好ましい。以下にその一例を説明する。 The polyvinyl chloride resin fiber used in the present invention is not particularly limited in the blending and production method, and can be produced using a conventionally known production method. However, the fineness suitable for hair fibers and the cross-sectional shape of the fiber can be used. In order to obtain the above, it is preferable to use a manufacturing method in the same field. One example will be described below.
 本発明に用いるポリ塩化ビニル系樹脂繊維は、ポリ塩化ビニル系樹脂を主成分する繊維であって、繊維の透明性等の品質や紡糸安定性を損なわない限りで、目的に応じて塩化ビニル系組成物に使用される公知の配合剤を加えることが出来る。具体的には例えば、塩素化塩化ビニル樹脂やAS樹脂等の耐熱性向上剤、金属石鹸系熱安定剤、βジケトンやホスファイト、ポリオール等の安定化助剤、可塑剤、紫外線吸収剤、酸化防止剤、帯電防止剤、充填剤、難燃剤、顔料等を使用する事ができる。また場合によっては発泡剤、架橋剤、粘着性付与剤、導電性付与剤、香料等特殊な配合剤を使用する事もできる。 The polyvinyl chloride resin fiber used in the present invention is a fiber mainly composed of a polyvinyl chloride resin, and the polyvinyl chloride resin fiber is used depending on the purpose as long as the quality and spinning stability of the fiber are not impaired. The well-known compounding agent used for a composition can be added. Specifically, for example, heat resistance improvers such as chlorinated vinyl chloride resins and AS resins, metal soap heat stabilizers, stabilizing aids such as β diketones, phosphites, polyols, plasticizers, UV absorbers, oxidation Inhibitors, antistatic agents, fillers, flame retardants, pigments and the like can be used. In some cases, special compounding agents such as a foaming agent, a crosslinking agent, a tackifier, a conductivity imparting agent, and a fragrance can be used.
 本発明に用いるポリ塩化ビニル系樹脂繊維に使用するポリ塩化ビニル系樹脂は、従来公知の塩化ビニルの単独重合物であるホモポリマー樹脂、または従来公知の各種のコポリマー樹脂など、特に限定されるものではない。コポリマー樹脂としては、塩化ビニル-酢酸ビニルコポリマー樹脂、塩化ビニル-プロピオン酸ビニルコポリマー樹脂などの塩化ビニルとビニルエステル類とのコポリマー樹脂、塩化ビニル-アクリル酸ブチルコポリマー樹脂、塩化ビニル-アクリル酸2エチルヘキシルコポリマー樹脂などの塩化ビニルとアクリル酸エステル類とのコポリマー樹脂、塩化ビニル-エチレンコポリマー樹脂、塩化ビニル-プロピレンコポリマー樹脂などの塩化ビニルとオレフィン類とのコポリマー樹脂、塩化ビニル-アクリロニトリルコポリマー樹脂などが代表的に例示される。好ましい塩化ビニル系樹脂は、塩化ビニルの単独重合物であるホモポリマー樹脂があげられる。該コポリマー樹脂において、コモノマーの含有量は特に限定されず、繊維への成型加工性、繊維の特性などに応じて決めることができる。ただし、コポリマー樹脂の軟化温度が低い場合には、耐熱性の低下する原因となるため、塩化ビニルの単独重合物であるホモポリマー樹脂と混合して用いることが好ましい。 The polyvinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention is particularly limited to a homopolymer resin that is a homopolymer of a conventionally known vinyl chloride or various conventionally known copolymer resins. is not. Examples of copolymer resins include vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl propionate copolymer resins and other vinyl chloride and vinyl ester copolymer resins, vinyl chloride-butyl acrylate copolymer resins, vinyl chloride-2-ethylhexyl acrylate. Representative examples include copolymer resins of vinyl chloride and acrylates such as copolymer resins, vinyl chloride-ethylene copolymer resins, vinyl chloride and olefins such as vinyl chloride-propylene copolymer resins, and vinyl chloride-acrylonitrile copolymer resins. Illustratively. A preferred vinyl chloride resin is a homopolymer resin which is a homopolymer of vinyl chloride. In the copolymer resin, the content of the comonomer is not particularly limited, and can be determined according to the moldability of the fiber, the properties of the fiber, and the like. However, when the softening temperature of the copolymer resin is low, the heat resistance may be lowered. Therefore, it is preferable to use a mixture with a homopolymer resin that is a homopolymer of vinyl chloride.
 本発明に用いるポリ塩化ビニル系樹脂繊維に使用する塩化ビニル系樹脂の粘度平均重合度は、繊維としての十分な強度、耐熱性を得るためには、450以上が好ましい。また適切なノズル圧力の下で、安全な繊維の製造を行うには、重合度は1800以下が好ましい。これら成型加工性と繊維特性を達成するために、塩化ビニルのホモポリマー樹脂を使用する場合は、粘度平均重合度が650~1450の領域が特に好ましい。コポリマーを使用する場合は、コモノマーの含有量にも依存するが、粘度平均重合度は、1000~1700の領域が特に好ましい。なお、前記粘度平均重合度は、樹脂200mgをニトロベンゼン50mlに溶解させ、このポリマー溶液を30℃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。 The viscosity average polymerization degree of the vinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention is preferably 450 or more in order to obtain sufficient strength and heat resistance as the fiber. In order to produce a safe fiber under an appropriate nozzle pressure, the degree of polymerization is preferably 1800 or less. In order to achieve these molding processability and fiber characteristics, when a vinyl chloride homopolymer resin is used, a region having a viscosity average polymerization degree of 650 to 1450 is particularly preferable. When a copolymer is used, the viscosity average degree of polymerization is particularly preferably in the range of 1000 to 1700, depending on the comonomer content. The viscosity average degree of polymerization was calculated according to JIS-K6721 by dissolving 200 mg of resin in 50 ml of nitrobenzene, measuring the specific viscosity of this polymer solution in a constant temperature bath at 30 ° C. using an Ubbelohde viscometer. .
 本発明に用いるポリ塩化ビニル系樹脂繊維に使用する塩化ビニル系樹脂は、乳化重合、塊状重合または懸濁重合などによって製造することができる。繊維の初期着色性などを勘案して、懸濁重合によって製造した重合体が好ましい。 The vinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention can be produced by emulsion polymerization, bulk polymerization or suspension polymerization. A polymer produced by suspension polymerization is preferable in consideration of the initial colorability of the fiber.
 本発明に用いるポリ塩化ビニル系樹脂繊維に使用する塩化ビニル系樹脂として、塩素化塩化ビニル系樹脂を使用することもできる。塩素化塩化ビニル系樹脂は、塩化ビニル系樹脂を原料とし、これに塩素を反応せしめ、塩素含有量を58~72%に高めたものを使用する。塩素化して塩素含有量が増えることにより、樹脂の耐熱性が上がるので、塩素化塩化ビニル系樹脂を使用することで、繊維の収縮を抑える効果がある。塩素化塩化ビニル系樹脂の粘度平均重合度(原料塩化ビニル系樹脂の粘度平均重合度)は、300~1100であることが好ましく、該粘度平均重合度が300未満であると、繊維の熱収縮率を低下せしめる効果が小さくなるので収縮率のやや高い繊維となる。逆に、該粘度平均重合度が1100を超えると、溶融粘度が高くなり、紡糸時のノズル圧力が高くなるため安全操業が困難になる傾向がある。特に好ましくは、粘度平均重合度は500~900のものが良い。また前記塩素含有率については58%未満であると繊維の熱収縮率を低下せしめる効果が小さくなり、逆に72%を超えると、溶融粘度が高くなって安定操業が困難となる傾向があり好ましくない。 As the vinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention, a chlorinated vinyl chloride resin can also be used. As the chlorinated vinyl chloride resin, a vinyl chloride resin is used as a raw material, which is reacted with chlorine to increase the chlorine content to 58 to 72%. Since the heat resistance of the resin increases by chlorinating and increasing the chlorine content, the use of a chlorinated vinyl chloride resin has the effect of suppressing fiber shrinkage. The viscosity average polymerization degree of the chlorinated vinyl chloride resin (viscosity average polymerization degree of the raw vinyl chloride resin) is preferably 300 to 1100. If the viscosity average polymerization degree is less than 300, the heat shrinkage of the fiber Since the effect of lowering the rate is reduced, the fiber has a slightly higher shrinkage rate. On the other hand, when the viscosity average degree of polymerization exceeds 1100, the melt viscosity becomes high, and the nozzle pressure at the time of spinning tends to be high, so that safe operation tends to be difficult. Particularly preferably, the viscosity average degree of polymerization is from 500 to 900. Further, if the chlorine content is less than 58%, the effect of lowering the heat shrinkage rate of the fiber is reduced. Conversely, if the chlorine content exceeds 72%, the melt viscosity tends to be high and stable operation becomes difficult. Absent.
 塩素化塩化ビニル系樹脂は、紡糸時の糸切れ、熱による糸の着色の点で、単独で使用するよりも、塩化ビニル樹脂と混合して使用するのが好ましい。塩化ビニル樹脂100~60重量%に対して、塩素化塩化ビニル系樹脂0~40重量%の比率で混合するのが好ましく、さらには塩化ビニル樹脂90~70重量%に対して、塩素化塩化ビニル系樹脂10~30重量%の比率で混合することが好ましい。塩素化塩化ビニル系樹脂が40重量%を超えると、紡糸時に糸切れが起こりやすくなる。 The chlorinated vinyl chloride resin is preferably used in combination with a vinyl chloride resin rather than being used alone in terms of yarn breakage during spinning and coloring of the yarn due to heat. It is preferable to mix the chlorinated vinyl chloride resin at a ratio of 0 to 40% by weight with respect to 100 to 60% by weight of the vinyl chloride resin, and further chlorinated vinyl chloride with respect to 90 to 70% by weight of the vinyl chloride resin. It is preferable to mix the resin at a ratio of 10 to 30% by weight. If the chlorinated vinyl chloride resin exceeds 40% by weight, yarn breakage tends to occur during spinning.
 本発明に用いるポリ塩化ビニル系樹脂繊維に使用する安定剤としては、従来公知のものが使用できるが、中でも錫系熱安定剤、Ca-Zn系熱安定剤、ハイドロタルサイト系熱安定剤、エポキシ系熱安定剤、β-ジケトン系熱安定剤から選択される少なくとも1種の熱安定剤が好ましい。熱安定剤は0.2~5重量部使用するのが好ましく、さらに好ましくは1~3重量部である。0.2重量部未満では、熱安定剤としての効果が乏しい。5重量部を超えても、熱安定性が大きく改善されず、経済的に不利である。 As the stabilizer used for the polyvinyl chloride resin fiber used in the present invention, conventionally known stabilizers can be used. Among them, a tin-based heat stabilizer, a Ca—Zn-based heat stabilizer, a hydrotalcite-based heat stabilizer, At least one heat stabilizer selected from an epoxy heat stabilizer and a β-diketone heat stabilizer is preferred. The heat stabilizer is preferably used in an amount of 0.2 to 5 parts by weight, more preferably 1 to 3 parts by weight. If it is less than 0.2 parts by weight, the effect as a heat stabilizer is poor. Even if it exceeds 5 parts by weight, the thermal stability is not greatly improved, which is economically disadvantageous.
 前記熱安定剤の添加により、紡糸時に樹脂の熱分解が防止されるため、繊維の色調が低下せず、安定して紡糸することができる(ロングラン紡糸性)などの効果を示す。前記ロングラン紡糸性とは、数日間にわたって紡糸工程を止めることなく安定して連続運転でき、繊維を生産できる性質のことである。ロングラン紡糸性が低い樹脂組成物は、運転開始後、比較的短時間のうちに、例えばプレートアウトなどで糸切れが起こり始めたり、ダイ圧が上昇し始めたりして、ブレーカプレートやノズルを交換、再スタートする必要があり、生産効率が悪い。前記繊維の色調の低下とは、紡糸時における繊維の初期着色のことである。 The addition of the heat stabilizer prevents the resin from being thermally decomposed during spinning, so that the color tone of the fiber is not lowered and the spinning can be performed stably (long-run spinnability). The long run spinnability is a property that can be stably operated continuously without stopping the spinning process for several days and can produce fibers. Resin composition with low long-run spinnability can be used to replace breaker plates and nozzles within a relatively short period of time after starting operation, for example, when thread breakage starts due to plate-out or the die pressure starts to rise. Need to restart, production efficiency is poor. The decrease in the color tone of the fiber refers to the initial coloration of the fiber during spinning.
 熱安定剤の中で、錫系安定剤としては、ジメチル錫メルカプト、ジメチル錫メルカプタイド、ジブチル錫メルカプト、ジオクチル錫メルカプト、ジオクチル錫メルカプトポリマー、ジオクチル錫メルカプトアセテートなどのメルカプト錫系熱安定剤、ジメチル錫マレエート、ジブチル錫マレエート、ジオクチル錫マレエート、ジオクチル錫マレエートポリマーなどのマレエート錫系熱安定剤、ジメチル錫ラウレート、ジブチル錫ラウレート、ジオクチル錫ラウレートなどのラウレート錫系熱安定剤を例示できる。Ca-Zn系熱安定剤としては、ステアリン酸亜鉛、ステアリン酸カルシウム、12-ヒドロキシステアリン酸亜鉛、12-ヒドロキシステアリン酸カルシウムなどを例示できる。ハイドロタルサイト系熱安定剤としては、例えば協和化学工業株式会社製のアルカマイザーなどがあげられる。エポキシ系熱安定剤としては、例えば、エポキシ化大豆油、エポキシ化アマニ油などがあげられる。βジケトン系熱安定剤としては、例えば、ステアロイルベンゾイルメタン(SBM)、ジベンゾイルメタン(DBM)などがあげられる。 Among the thermal stabilizers, the tin stabilizers include dimethyltin mercapto, dimethyltin mercaptoide, dibutyltin mercapto, dioctyltin mercapto, dioctyltin mercaptopolymer, dioctyltin mercaptoacetate, etc. Examples thereof include maleate tin thermal stabilizers such as maleate, dibutyltin maleate, dioctyltin maleate, and dioctyltin maleate polymer, and laurate tin thermal stabilizers such as dimethyltin laurate, dibutyltin laurate, and dioctyltin laurate. Examples of the Ca—Zn heat stabilizer include zinc stearate, calcium stearate, zinc 12-hydroxystearate, and calcium 12-hydroxystearate. Examples of the hydrotalcite-based heat stabilizer include Alkamizer manufactured by Kyowa Chemical Industry Co., Ltd. Examples of the epoxy heat stabilizer include epoxidized soybean oil and epoxidized linseed oil. Examples of the β-diketone heat stabilizer include stearoylbenzoylmethane (SBM) and dibenzoylmethane (DBM).
 本発明に用いるポリ塩化ビニル系樹脂繊維に使用する滑剤は、従来公知のものを用いることができるが、特に金属石鹸系滑剤、ポリエチレン系滑剤、高級脂肪酸系滑剤、エステル系滑剤、高級アルコール系滑剤からなる群から選択される少なくとも1種が好ましい。該滑剤は、組成物の溶融状態、ならびに組成物と押出し機内の、スクリュー、シリンダー、ダイスなどの金属面との接着状態を制御するために有効である。滑剤は塩化ビニル系樹脂100重量部に対して、0.2~5重量部使用するのが好ましい。さらに好ましくは1~4重量部である。0.2重量部未満になると、紡糸時にダイ圧上昇、吐出量低下により生産効率が低下し、更には糸切れやノズル圧力の上昇などが起こりやすくなり、安定生産が困難になる。5重量部を越えると、吐出量低下、糸切れ多発などにより、0.2重量部未満時と同様に安定生産が困難になり、また透明感のある繊維が得られない傾向にあり好ましくない。 Conventionally known lubricants can be used for the polyvinyl chloride resin fibers used in the present invention, and in particular, metal soap lubricants, polyethylene lubricants, higher fatty acid lubricants, ester lubricants, higher alcohol lubricants. At least one selected from the group consisting of The lubricant is effective for controlling the molten state of the composition and the state of adhesion between the composition and a metal surface such as a screw, cylinder or die in the extruder. The lubricant is preferably used in an amount of 0.2 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. More preferably, it is 1 to 4 parts by weight. When the amount is less than 0.2 parts by weight, production efficiency is lowered due to an increase in die pressure and a decrease in discharge amount during spinning, and further, yarn breakage and an increase in nozzle pressure are likely to occur, and stable production becomes difficult. Exceeding 5 parts by weight is not preferable because stable production becomes difficult as in the case of less than 0.2 parts by weight due to a decrease in discharge amount, frequent yarn breakage, and the like, and a transparent fiber tends to be not obtained.
 金属石鹸系滑剤としては、例えば、Na、Mg、Al、Ca、Baなどのステアレート塩、ラウレート塩、パルミテート塩、オレエート塩などの金属石鹸が例示される。高級脂肪酸系滑剤としては、例えば、ステアリン酸、パルミチン酸、ミリスチン酸、ラウリン酸、カプリン酸などの飽和脂肪酸、オレイン酸などの不飽和脂肪酸、またはこれらの混合物などが例示される。高級アルコール系滑剤としては、ステアリルアルコール、パルミチルアルコール、ミリスチルアルコール、ラウリルアルコール、オレイルアルコールなどが例示される。エステル系滑剤としては、アルコールと脂肪酸からなるエステル系滑剤やペンタエリスリトールまたはジペンタエリスリトールと高級脂肪酸とのモノエステル、ジエステル、トリエステル、テトラエステル、またはこれらの混合物などのペンタエリスリトール系滑剤やモンタン酸とステアリルアルコール、パルミチルアルコール、ミリスチルアルコール、ラウリルアルコール、オレイルアルコールなどの高級アルコールとのエステル類のモンタン酸ワックス系滑剤が例示される。 Examples of the metal soap lubricant include metal soaps such as stearate salts such as Na, Mg, Al, Ca, Ba, laurate salts, palmitate salts, and oleate salts. Examples of the higher fatty acid lubricant include saturated fatty acids such as stearic acid, palmitic acid, myristic acid, lauric acid and capric acid, unsaturated fatty acids such as oleic acid, and mixtures thereof. Examples of higher alcohol lubricants include stearyl alcohol, palmityl alcohol, myristyl alcohol, lauryl alcohol, oleyl alcohol, and the like. Examples of ester lubricants include ester lubricants composed of alcohol and fatty acids, pentaerythritol lubricants such as pentaerythritol or monoesters, diesters, triesters, tetraesters, or mixtures thereof of pentaerythritol or dipentaerythritol and higher fatty acids, and montanic acid. Examples thereof include montanic acid wax-based lubricants of esters of stearyl alcohol, palmityl alcohol, myristyl alcohol, lauryl alcohol, oleyl alcohol, and other higher alcohols.
 本発明に用いるポリ塩化ビニル系樹脂繊維を製造する際には、目的に応じてさらに、例えば、加工助剤、艶消し剤、充填剤、可塑剤、紫外線吸収剤、酸化防止剤、帯電防止剤、難燃剤、顔料などを使用することができる。 When producing the polyvinyl chloride resin fibers used in the present invention, depending on the purpose, for example, further processing aids, matting agents, fillers, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, etc. Flame retardants, pigments and the like can be used.
 これらの中でも、柔軟な触感を得るためのエチレン-酢酸ビニル系(EVA)樹脂、例えば日本ユニカー(株)製のPES-250など、また押し出し加工性をさらに改善するためのアクリル系樹脂、例えば、(株)カネカ製のPA-20などを添加しても良い。 Among these, ethylene-vinyl acetate (EVA) resin for obtaining a soft touch, such as PES-250 manufactured by Nihon Unicar Co., Ltd., and acrylic resin for further improving the extrusion processability, for example, PA-20 manufactured by Kaneka Corporation may be added.
 本発明に用いるポリ塩化ビニル系樹脂繊維は、繊維化工程においては公知の溶融紡糸法を用いることができる。例えば、塩化ビニル系樹脂、塩素化塩化ビニル系樹脂、熱安定剤、滑剤を所定の割合で混合し、ヘンシェルミキサーなどで攪拌混合した後、押出し機に充填し、シリンダー温度150~190℃、ノズル温度180±15℃の範囲で、紡糸性の良い条件で樹脂を押出し、溶融紡糸を行い、未延伸糸を得る。 For the polyvinyl chloride resin fiber used in the present invention, a known melt spinning method can be used in the fiberizing step. For example, vinyl chloride resin, chlorinated vinyl chloride resin, heat stabilizer and lubricant are mixed at a specified ratio, stirred and mixed with a Henschel mixer, etc., then filled into an extruder, cylinder temperature 150 to 190 ° C., nozzle In the temperature range of 180 ± 15 ° C., the resin is extruded under conditions with good spinnability, melt spinning is performed, and an undrawn yarn is obtained.
 また、前記未延伸糸を紡糸にする際には、従来公知の押出し機を使用できる。例えば単軸押出し機、異方向2軸押出し機、コニカル2軸押出し機などを使用できるが、特に好ましくは、口径が35~85mmφ程度の単軸押出し機または口径が35~50mmφ程度のコニカル押出し機を使用するのが良い。この際使用するノズルの孔形状は、最終断面形状に近似した形とするが、紡糸時のダイスウェルや延伸などによって形状寸法は微妙に変化するため、それらを考慮して調整したものを使用する。ノズル孔形状は特に限定されず、円型、扁平楕円型、眼鏡型、繭型、星型、C字型、H字型、T字型、Y字型、十字型、5角型、6角型、8角型などが選択できる。この中で剛性が著しく増加しないことが望ましく、好ましくは扁平楕円型、眼鏡型、繭型、更に好ましくは眼鏡型、繭型がよい。 Further, when spinning the undrawn yarn, a conventionally known extruder can be used. For example, a single screw extruder, a different-direction twin screw extruder, a conical twin screw extruder, etc. can be used, but a single screw extruder having a diameter of about 35 to 85 mmφ or a conical extruder having a diameter of about 35 to 50 mmφ is particularly preferable. Good to use. The hole shape of the nozzle used at this time is a shape that approximates the final cross-sectional shape, but the shape dimension slightly changes depending on the die swell or stretching at the time of spinning. . The shape of the nozzle hole is not particularly limited, and is circular, flat oval, glasses, saddle, star, C, H, T, Y, cross, pentagon, hexagon Type, octagonal type, etc. can be selected. Among these, it is desirable that the rigidity does not increase remarkably, and a flat elliptical shape, a spectacle shape, and a saddle shape are preferable, and a spectacle shape and a saddle shape are more preferable.
 押し出されたフィラメントをノズル直下に設けた加熱紡糸筒内(200~300℃雰囲気で紡糸性の良い条件)で約0.5~1.5秒熱処理し、生成した未延伸糸は引き取りロールによって延伸工程に送られる。次に、引き取りロールと延伸ロールとの間で未延伸糸を100~130℃に温度調整した熱風循環箱を通して約2~4倍に延伸する。 The extruded filament is heat-treated for about 0.5 to 1.5 seconds in a heated spinning cylinder (under 200-300 ° C atmosphere and good spinnability) provided directly under the nozzle, and the produced undrawn yarn is drawn by a take-up roll. Sent to the process. Next, the undrawn yarn is drawn about 2 to 4 times through a hot air circulation box whose temperature is adjusted to 100 to 130 ° C. between the take-up roll and the drawing roll.
 次に110~150℃に温度調整した熱風循環箱の中に設置した2対の円錐形ロール間を引き回し、連続的に20~50%程度の緩和処理を実施し、マルチフィラメントを巻き取ることで本発明の繊維が製造される。この際に収縮応力を低減させるために、熱処理温度は高いことが望ましく、好ましくは120~145℃、さらに好ましくは130~140℃がよい。熱処理温度が110℃より低いと、130℃における収縮応力を充分に低減することが出来なくなるために、繊維屈曲が生じて商品性が低下し、150℃より高いとポリアルキレンオキシド化合物を担持させても繊維間の融着を充分に抑制することが難しくなり触感が硬くなる。 Next, by pulling between two pairs of conical rolls installed in a hot air circulation box whose temperature is adjusted to 110 to 150 ° C, a relaxation treatment of about 20 to 50% is continuously performed, and the multifilament is wound up. The fiber of the present invention is produced. At this time, in order to reduce the shrinkage stress, the heat treatment temperature is desirably high, preferably 120 to 145 ° C., more preferably 130 to 140 ° C. When the heat treatment temperature is lower than 110 ° C., the shrinkage stress at 130 ° C. cannot be sufficiently reduced, so that fiber bending occurs and the commercial property is lowered. When the heat treatment temperature is higher than 150 ° C., the polyalkylene oxide compound is supported. However, it becomes difficult to sufficiently suppress the fusion between the fibers, and the tactile sensation becomes hard.
 また分子内の歪を低減するために緩和速度は極力遅くすることが望ましく、好ましくは1分あたり緩和率10%以下にすることが好ましく、さらには1分あたり緩和率8%以下とすることが好ましい。緩和速度が1分あたり緩和率10%を超えると、繊維内の歪を充分に除去することが出来なくなるために、繊維収縮で繊維屈曲が生成しやすくなり、触感が悪化する。さらに緩和熱処理時間は2~60分が好ましく、さらには4~20分が好ましい。熱処理時間が2分より短いとマルチフィラメント間の収縮率を揃えることが難しくなり、60分より長いとポリアルキレンオキシド化合物を担持させても繊維間の融着を充分に抑制することが難しくなり触感が硬くなる。 In order to reduce intramolecular strain, the relaxation rate is desirably as low as possible, preferably 10% or less per minute, and more preferably 8% or less per minute. preferable. When the relaxation rate exceeds 10% per minute, the strain in the fiber cannot be sufficiently removed, so that fiber bending tends to occur due to fiber contraction, and the tactile sensation deteriorates. Further, the relaxation heat treatment time is preferably 2 to 60 minutes, more preferably 4 to 20 minutes. If the heat treatment time is shorter than 2 minutes, it is difficult to make the shrinkage ratio between the multifilaments uniform. If it is longer than 60 minutes, it is difficult to sufficiently suppress the fusion between fibers even if a polyalkylene oxide compound is supported. Becomes hard.
 また収縮率を調整するために、緩和熱処理後の繊維にさらに0.1~4%の範囲で延伸を加えてもよい。さらに軽度の繊維間融着を解すために、緩和熱処理後に工程内にニップロールや屈折箇所を導入しても良い。 Further, in order to adjust the shrinkage rate, the fiber after the relaxation heat treatment may be further stretched in a range of 0.1 to 4%. Further, in order to release mild interfiber fusion, a nip roll or a refracted portion may be introduced into the process after the relaxation heat treatment.
 本発明の人工毛髪用繊維を構成する単繊維の繊度は、通常の人工毛髪用繊維と同様に20~100dtexであることが好ましく、40~90dtexであることがさらに好ましい。20dtexより細いと商品加工後のカールが弱くなり、スタイル性が著しく低下する。また100dtexより太い場合には、繊維の剛性が高くなり触感が硬くなる。 The fineness of the single fiber constituting the artificial hair fiber of the present invention is preferably 20 to 100 dtex, more preferably 40 to 90 dtex, as in the case of ordinary artificial hair fibers. If it is thinner than 20 dtex, the curl after processing the product becomes weak, and the style is remarkably lowered. On the other hand, if it is thicker than 100 dtex, the rigidity of the fiber becomes high and the tactile sensation becomes hard.
 本発明に用いる熱可塑性樹脂繊維は、ヤング率が4~9GPaであり、130℃の収縮率が10%以下であり、ポリ塩化ビニル系樹脂を除く組成からなり、人工毛髪用繊維束における構成比率が0~80重量%であることを特徴とする。 The thermoplastic resin fiber used in the present invention has a Young's modulus of 4 to 9 GPa, a shrinkage rate at 130 ° C. of 10% or less, a composition excluding polyvinyl chloride resin, and a composition ratio in a fiber bundle for artificial hair. Is 0 to 80% by weight.
 熱可塑性樹脂繊維は、本発明においてポリ塩化ビニル系樹脂繊維の収縮を抑えて触感の悪化を防ぐ役割を持ち、収縮応力を吸収できるだけの剛性を有する必要がある。剛性はヤング率を指標とすることができる。本発明における熱可塑性樹脂繊維は、ヤング率が4~9GPaである必要があり、好ましくは4.5~8GPa、さらに好ましくは5~7GPaである。ヤング率が4GPaより小さいと、ポリ塩化ビニル系樹脂繊維の収縮を抑制する効果が充分に得られず、繊維屈曲生成によって触感が悪化する。またヤング率が9GPaより大きいと、毛髪用繊維としてコシ感が強すぎるために触感やスタイル性が悪化する。 In the present invention, the thermoplastic resin fiber has a role of preventing the deterioration of the tactile sensation by suppressing the shrinkage of the polyvinyl chloride resin fiber, and is required to have rigidity sufficient to absorb the shrinkage stress. Rigidity can use Young's modulus as an index. The thermoplastic resin fiber in the present invention needs to have a Young's modulus of 4 to 9 GPa, preferably 4.5 to 8 GPa, more preferably 5 to 7 GPa. If the Young's modulus is less than 4 GPa, the effect of suppressing the shrinkage of the polyvinyl chloride resin fibers cannot be sufficiently obtained, and the tactile sensation is deteriorated due to the generation of fiber bending. On the other hand, if the Young's modulus is greater than 9 GPa, the feeling of touch and style are deteriorated because the stiffness of the hair fibers is too strong.
 また熱可塑性樹脂繊維は、カール形状付与温度で軟化して変形しないことが必要であり、その指標として130℃の収縮率を用いることが出来る。なお本発明における収縮率の測定には単繊維を束ねて総繊度15000~25000dtexとした繊維束を用い、合計20回の平均値を用いることとする。この際に同じ繊維内でも収縮率の変動幅が大きい場合には、繊維屈曲生成の原因となる。したがって、平均収縮率から2%以上収縮差のある繊維が同じ繊維内で30%以上を占める場合には、良好な触感を保てなくなる恐れがあるため、使用しないことが好ましい。本発明に用いる熱可塑性樹脂繊維は130℃の収縮率が10%以下である必要があり、好ましくは4%以下、さらに好ましくは1%以下である。130℃の収縮率が10%より高いと、ポリ塩化ビニル系樹脂繊維の収縮を抑制する効果が充分に得られず、繊維屈曲生成によって触感が悪化する。 Also, the thermoplastic resin fiber needs to be softened and not deformed at the curl shape imparting temperature, and a shrinkage rate of 130 ° C. can be used as an index thereof. In the measurement of the shrinkage rate in the present invention, a fiber bundle having a total fineness of 15000 to 25000 dtex by bundling single fibers is used, and an average value of 20 times in total is used. At this time, if the fluctuation range of the shrinkage rate is large even in the same fiber, it causes fiber bending. Therefore, when fibers having a shrinkage difference of 2% or more from the average shrinkage occupy 30% or more in the same fiber, there is a possibility that good tactile sensation may not be maintained, so that it is preferable not to use them. The thermoplastic resin fiber used in the present invention needs to have a shrinkage rate at 130 ° C. of 10% or less, preferably 4% or less, more preferably 1% or less. When the shrinkage rate at 130 ° C. is higher than 10%, the effect of suppressing the shrinkage of the polyvinyl chloride resin fibers cannot be sufficiently obtained, and the tactile sensation is deteriorated due to the generation of fiber bending.
 本発明に用いる熱可塑性樹脂繊維の、人工毛髪用繊維束における構成比率は0~80重量%、好ましくは25~70重量%、さらに好ましくは40~60重量%である。人工毛髪用繊維束における構成比率が80重量%より高いと、ポリ塩化ビニル系樹脂繊維の有する柔軟な触感やスタイル性を充分に得ることが出来ず、商品性が低下する。 The composition ratio of the thermoplastic resin fibers used in the present invention in the fiber bundle for artificial hair is 0 to 80% by weight, preferably 25 to 70% by weight, more preferably 40 to 60% by weight. When the composition ratio in the fiber bundle for artificial hair is higher than 80% by weight, the soft tactile feel and style properties of the polyvinyl chloride resin fiber cannot be sufficiently obtained, and the commercial property is lowered.
 本発明に用いる熱可塑性樹脂繊維は、ポリ塩化ビニル系樹脂を除く熱可塑性樹脂であれば、組成は特に限定されない。ポリ塩化ビニル系樹脂繊維の場合には、例えば無機物を配合することで剛性を上げることは可能であるが、前述のように撓みが生じた際の繊維屈曲がシャープになる特性を持つことから、触感の悪化を防ぐことは困難である。熱可塑性樹脂繊維に使用される組成としては、具体的には、例えば、アクリロニトリル系樹脂、モダアクリル系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリエーテルイミド系樹脂、ポリアミドイミド系樹脂、ポリオキシメチレン系樹脂、ポリエーテルケトン系樹脂、ポリカーボネート系樹脂、ポリサルフォン系樹脂、ポリエーテルサルフォン系樹脂、ポリフェニレンエーテル系樹脂、ポリフェレンスルフィド系繊維、テフロン(登録商標)樹脂などが挙げられる。この中で毛髪用繊維として違和感なく混ぜられる観点から、好ましくはアクリロニトリル系樹脂、モダアクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリカーボネート系樹脂、ポリエーテルサルフォン系樹脂、ポリフェニレンスルフィド系樹脂、さらに好ましくはモダアクリル系樹脂、ポリエステル系樹脂が用いられる。またこれらの組成は数種類を混ぜ合わせてもよく、さらには芯鞘構造などの多層構造を有する複合組成の繊維としてもよい。 The composition of the thermoplastic resin fiber used in the present invention is not particularly limited as long as it is a thermoplastic resin excluding a polyvinyl chloride resin. In the case of a polyvinyl chloride resin fiber, for example, it is possible to increase the rigidity by blending an inorganic substance, but since it has a characteristic that the fiber bending when bending occurs as described above, It is difficult to prevent deterioration of tactile sensation. Specific examples of the composition used for the thermoplastic resin fiber include acrylonitrile resin, modacrylic resin, polyolefin resin, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, and polyamide. Examples include imide resins, polyoxymethylene resins, polyether ketone resins, polycarbonate resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, polyferene sulfide fibers, and Teflon (registered trademark) resins. Can be mentioned. Of these, acrylonitrile-based resin, modacrylic resin, polyester-based resin, polyamide-based resin, polycarbonate-based resin, polyethersulfone-based resin, polyphenylene sulfide-based resin, more preferably Modacrylic resins and polyester resins are used. These compositions may be mixed in several kinds, and may be a composite composition fiber having a multilayer structure such as a core-sheath structure.
 本発明に用いる熱可塑性樹脂繊維は、LOI値が25以上であることが好ましい。毛髪用製品はその使用目的から難燃性が要求され、消化性能を有するポリ塩化ビニル系樹脂繊維を多く混ぜることで一定の難燃性は得られる。本発明は可燃性のアミノ変性シリコーン化合物を繊維束に担持させるのに適した人工毛髪用繊維束を提供することを特徴としており、人工毛髪用繊維束が高いレベルの難燃性を有していることが望ましい。このため熱可塑性樹脂繊維も繊維自身に難燃性能を有していることが望ましく、その指標としてLOI値が用いられる。 The thermoplastic resin fiber used in the present invention preferably has a LOI value of 25 or more. The product for hair is required to have flame retardancy for its purpose of use, and a certain flame retardancy can be obtained by mixing a large amount of polyvinyl chloride resin fiber having digestive performance. The present invention is characterized by providing a fiber bundle for artificial hair suitable for supporting a combustible amino-modified silicone compound on a fiber bundle, and the fiber bundle for artificial hair has a high level of flame retardancy. It is desirable. For this reason, it is desirable that the thermoplastic resin fiber also has flame retardancy, and the LOI value is used as an index thereof.
 本発明に用いる熱可塑性樹脂繊維のLOI値は25以上が好ましく、さらに好ましくは27以上である。LOI値が25より低いと、繊維束として充分な難燃性を有することができず、着火して延焼する可能性がある。LOI値を25以上とする手段としては、モダアクリル系樹脂やポリフェニレンスルフィド系樹脂などの難燃性の樹脂を用いる方法、ならびに各種の難燃剤を樹脂に配合する方法がある。本発明の熱可塑性樹脂繊維に使用できる難燃剤は光沢と色相を損なわない範囲であれば特に限定されないが、具体的には例えば、リン系難燃剤、臭素含有ポリマー、塩素含有ポリマーなどが使用できる。また必要に応じてアンチモン化合物などの難燃助剤も適宜使用することが出来る。 The LOI value of the thermoplastic resin fiber used in the present invention is preferably 25 or more, more preferably 27 or more. If the LOI value is lower than 25, the fiber bundle cannot have sufficient flame retardancy and may ignite and spread. As a means for setting the LOI value to 25 or more, there are a method using a flame-retardant resin such as a modacrylic resin or a polyphenylene sulfide resin, and a method of blending various flame retardants into the resin. The flame retardant that can be used for the thermoplastic resin fiber of the present invention is not particularly limited as long as it does not impair the gloss and hue, and specifically, for example, a phosphorus flame retardant, a bromine-containing polymer, a chlorine-containing polymer, and the like can be used. . In addition, flame retardant aids such as antimony compounds can be used as needed.
 また本発明に用いる熱可塑性樹脂繊維は、前記条件のヤング率、収縮率、LOI値を満たす繊維であれば、複数の異なる繊維を混ぜ合わせてもよい。例えば、人工毛髪用繊維束の外観や触感、ボリューム感などの機能性を向上させる目的で、比重の軽い繊維や国際公開公報WO2005/082184号明細書記載のアクリル合成繊維のように表面凹凸を有する繊維などを用いることが出来る。 The thermoplastic resin fibers used in the present invention may be a mixture of a plurality of different fibers as long as they satisfy the Young's modulus, shrinkage rate, and LOI value of the above conditions. For example, for the purpose of improving the functionality, such as the appearance, tactile sensation, and volume sensation of the fiber bundle for artificial hair, it has surface irregularities such as fibers with a low specific gravity and acrylic synthetic fibers described in International Publication No. WO2005 / 082184. A fiber etc. can be used.
 本発明では、ポリ塩化ビニル系樹脂繊維と熱可塑性樹脂繊維を混ぜ合わせた繊維束を毛髪用商品に加工する際に、アミノ変性シリコーン化合物を繊維束表面に担持させることにより、95~130℃でカール形状を付与することを可能とする。 In the present invention, when a fiber bundle in which polyvinyl chloride resin fibers and thermoplastic resin fibers are mixed is processed into a hair product, an amino-modified silicone compound is supported on the fiber bundle surface at 95 to 130 ° C. It is possible to give a curled shape.
 本発明に用いるアミノ変性シリコーン化合物は、人毛に似た滑らかで保湿感を発現させる役割をもつ。さらにシリコーン化合物を含まない従来の油剤を用いたポリ塩化ビニル系樹脂繊維は、95℃以上で加熱すると繊維間で融着が発生して毛髪用製品の触感の硬くなる課題があるが、アミノ変性シリコーン化合物はその融着を抑制させる役割をもつ。 The amino-modified silicone compound used in the present invention has a role of expressing a smooth and moisturizing feeling similar to human hair. Furthermore, polyvinyl chloride resin fibers using conventional oil agents that do not contain silicone compounds have the problem that when heated at 95 ° C. or higher, fusion occurs between the fibers and the feel of the hair product becomes stiff. The silicone compound has a role of suppressing the fusion.
 本発明に用いるアミノ変性シリコーン化合物は、直鎖状ポリジメチルシロキサンの側鎖にイミノ基またはアミノ基が存在する23℃で液体のオイル状化合物で、アミノ基が繊維表面に吸着することで通常のジメチルシリコーン化合物よりも繊維に効率よく単分子膜的に付着し、繊維の表面エネルギーを低減化して摩擦抵抗を下げることで、人毛で好まれる滑らかで保湿感を有する良好なモイスチャー触感を得ることが出来る。但しシリコーン化合物のアミノ基が多すぎると、オイルの表面張力が増加して摩擦抵抗低減効果が減少し、親水性が増加して汗や雨などで繊維表面から流れ落ちることから使用耐久性が低下するため、最適なアミノ基量を選択する必要がある。本発明のアミノ変性シリコーン化合物における適切なアミン当量は1000~20000g/molで、好ましくは1250~10000g/mol、さらに好ましくは1500~5000g/molである。アミン当量が1000g/molより低いと、アミン基が多すぎるために触感や使用耐久性が低下し、アミン当量が20000g/molより高いと繊維との吸着量が低下してやはり触感が低下する。またアミノ変性シリコーン化合物の分子末端は、メチル基、水酸基、アミノ基の何れでも問題はなく、液状を保てる範囲でアミノ変性のシルセスキオキサンを加えてもよい。 The amino-modified silicone compound used in the present invention is an oily compound that is liquid at 23 ° C. in which an imino group or an amino group is present in the side chain of the linear polydimethylsiloxane, and the amino group is adsorbed on the fiber surface. Adheres to the fiber more efficiently than a dimethyl silicone compound, and reduces the surface energy of the fiber to lower the frictional resistance, thereby obtaining a smooth, moisturizing and moisturizing feeling that is preferred by human hair. I can do it. However, if there are too many amino groups in the silicone compound, the surface tension of the oil will increase and the frictional resistance reduction effect will decrease, and the hydrophilicity will increase and the durability will be reduced because it will flow down from the fiber surface due to sweat or rain. Therefore, it is necessary to select an optimal amino group amount. A suitable amine equivalent in the amino-modified silicone compound of the present invention is 1000 to 20000 g / mol, preferably 1250 to 10000 g / mol, more preferably 1500 to 5000 g / mol. When the amine equivalent is lower than 1000 g / mol, the tactile sensation and durability for use are lowered because of too many amine groups, and when the amine equivalent is higher than 20000 g / mol, the amount of adsorption with the fiber is lowered and the tactile sensation is also lowered. The molecular end of the amino-modified silicone compound may be any of a methyl group, a hydroxyl group, and an amino group, and amino-modified silsesquioxane may be added as long as the liquid state can be maintained.
 本発明は、ポリ塩化ビニル系樹脂繊維と熱可塑性樹脂繊維を組み合わせることで、95~130℃でカール形状を付与することを可能とし、このように高温で加熱することによってアミノ変性シリコーン化合物は、繊維表面への吸着が最適化されることになる。これによって従来の90℃加熱時と比較して、さらに滑らかさと繊維表面からの耐脱落性が改良され、触感と使用耐久性が向上することとなる。但しアミノ変性シリコーンの分子量が低い場合には、繊維内部に浸透して本来の改質効果が低減されることとなるため、最適な分子量を選択する必要がある。シリコーン化合物の中でシリコーンオイルは一般的に分子量を動粘度で規定する場合が多いが、本発明のアミノ変性シリコーン化合物において、好ましい動粘度は25℃において500~20000mm2/sで、さらに好ましくは1000~10000mm2/sである。動粘度が500mm2/sより低いと繊維内部に浸透する量が多くなるために触感の改良効果が充分ではなくなり、10000mm2/sよりも高いと繊維表面に均一に付着させることが難しくなることから、やはり触感の改良効果が低下する。 The present invention makes it possible to impart a curl shape at 95 to 130 ° C. by combining polyvinyl chloride resin fibers and thermoplastic resin fibers. By heating at such a high temperature, the amino-modified silicone compound is Adsorption on the fiber surface will be optimized. This further improves the smoothness and drop-off resistance from the fiber surface as compared with the conventional heating at 90 ° C., and improves the tactile sensation and durability of use. However, when the molecular weight of the amino-modified silicone is low, it penetrates into the inside of the fiber and the original modification effect is reduced, so it is necessary to select an optimal molecular weight. Among silicone compounds, silicone oil generally generally has a molecular weight defined by kinematic viscosity, but in the amino-modified silicone compound of the present invention, the preferred kinematic viscosity is 500 to 20000 mm 2 / s at 25 ° C., more preferably 1000 to 10000 mm 2 / s. When the kinematic viscosity is lower than 500 mm 2 / s, the amount of penetration into the fiber increases, so the effect of improving the tactile sensation is not sufficient, and when it is higher than 10000 mm 2 / s, it is difficult to uniformly adhere to the fiber surface. Therefore, the tactile sensation improving effect is also reduced.
 本発明に用いるアミノ変性シリコーン化合物を繊維に担持させる方法は特に限定されないが、例えば、水を溶媒とする乳化エマルジョンとしてから、繊維を浸漬させ、遠心脱水にて繊維への残存量を調整することで繊維表面に担持させる方法などがある。水を溶媒のとする乳化エマルジョンとする際には、界面活性剤などを用いて固形分濃度が5~25%なるように乳化し、必要に応じて酢酸などで中和を行ってから使用する。この際、帯電防止剤や平滑剤を併用してもよい。好ましい併用成分としては、平滑効果や帯電防止効果を有し、エマルジョン化の界面活性剤としても機能する非イオン性界面活性剤があげられる。 The method of supporting the amino-modified silicone compound used in the present invention on the fiber is not particularly limited. For example, the emulsion is emulsified with water as a solvent, and then the fiber is immersed and the amount remaining in the fiber is adjusted by centrifugal dehydration. There is a method of carrying on the fiber surface. When preparing an emulsified emulsion using water as a solvent, use a surfactant or the like so that the solid content is 5 to 25%, and neutralize with acetic acid if necessary. . At this time, an antistatic agent or a smoothing agent may be used in combination. Preferable combination components include nonionic surfactants that have a smoothing effect and an antistatic effect and also function as an emulsifying surfactant.
 また繊維をアミノ変性シリコーン化合物のエマルジョンに浸漬する前に、ポリ塩化ビニル系樹脂繊維、熱可塑性樹脂繊維の繊維表面に付着している余分な繊維処理剤を除くため、界面活性剤を用いて洗浄を行ってもよい。 Before dipping the fiber in the emulsion of amino-modified silicone compound, use a surfactant to remove the excess fiber treatment agent adhering to the fiber surface of the polyvinyl chloride resin fiber and thermoplastic resin fiber. May be performed.
 本発明に用いるアミノ変性シリコーン化合物の繊維に対する担持量は0.05~0.8omf%がよく、好ましくは0.1~0.6omf%、さらに好ましくは0.2~0.4omf%である。繊維に対する担持量が0.05omf%よりも少ない場合には、触感の改良効果が小さく、0.8omf%よりも多い場合には繊維が過度に収束してボリューム感が低下して商品性が低下する。 The amount of the amino-modified silicone compound used in the present invention supported on the fiber is preferably 0.05 to 0.8 omf%, preferably 0.1 to 0.6 omf%, more preferably 0.2 to 0.4 omf%. When the supported amount to the fiber is less than 0.05 omf%, the effect of improving the tactile sensation is small, and when it is more than 0.8 omf%, the fiber is excessively converged and the volume feeling is lowered to reduce the merchantability. To do.
 本発明の人工毛髪用繊維束は、95~130℃でカール形状を付与することを特徴とし、該温度におけるポリ塩化ビニル系樹脂繊維の収縮率が熱可塑性樹脂繊維の収縮率より低くない関係にあり、かつポリ塩化ビニル系樹脂繊維と熱可塑性樹脂繊維の収縮率の差が6%以下であることを特徴とする。 The fiber bundle for artificial hair of the present invention is characterized by imparting a curl shape at 95 to 130 ° C., and the shrinkage rate of the polyvinyl chloride resin fiber at the temperature is not lower than the shrinkage rate of the thermoplastic resin fiber. And the difference in shrinkage between the polyvinyl chloride resin fiber and the thermoplastic resin fiber is 6% or less.
 カール形状を付与する方法は、特に限定されないが、例えば、円筒形状のパイプに螺旋または同心円状に繊維束を捲き付け、その形態を保持した状態で所定温度において所定時間の加熱を行うことで捲き付け形状が繊維束に記憶され、その後冷却してパイプから繊維束を外す方法などを用いることが出来る。このときのパイプの口径は商品スタイルによって任意に選択することが出来るが、本発明では熱可塑性樹脂繊維がポリ塩化ビニル系樹脂繊維に密着することで複数の支点をつくり、該支点でポリ塩化ビニル系樹脂繊維を支えることで、収縮を抑制する効果を発現する。このため各繊維が密着するようにパイプに対して繊維束を圧着する必要があり、その方法としては、繊維束の片末端をパイプに固定した状態で張力を保ちながらパイプに捲き付ける方法や、敷き紙を使ってパイプに捲き付ける方法などを用いることが出来る。また円形のカール形状以外にも、真っ直ぐなストレート系のスタイルにも適用出来るが、その場合には繊維を密着させるために両端を縛るか、全体を板で挟み込むなどの方法を用いる必要がある。 The method for imparting the curl shape is not particularly limited. For example, the fiber bundle is wound spirally or concentrically on a cylindrical pipe, and is heated by heating at a predetermined temperature for a predetermined time while maintaining the shape. The attached shape is stored in the fiber bundle, and then a method of cooling and removing the fiber bundle from the pipe can be used. The diameter of the pipe at this time can be arbitrarily selected according to the product style, but in the present invention, the thermoplastic resin fibers are in close contact with the polyvinyl chloride resin fibers to form a plurality of fulcrums, and at these fulcrums, polyvinyl chloride is used. By supporting the resin fiber, the effect of suppressing shrinkage is expressed. For this reason, it is necessary to pressure-bond the fiber bundle against the pipe so that each fiber is in close contact, and as a method, a method of squeezing the pipe while maintaining the tension with one end of the fiber bundle fixed to the pipe, You can use a method of spreading it on a pipe using laying paper. In addition to the circular curled shape, it can also be applied to straight straight styles, but in that case, it is necessary to use a method such as binding both ends or sandwiching the whole with a plate in order to bring the fibers into close contact.
 カール形状を付与する温度は、高温にするとスタイル性の改良効果やアミノ変性シリコーンの触感改良効果が増幅されるが、一方で過度に温度を高くするとポリ塩化ビニル系樹脂繊維が熱で融着して触感が硬くなる。このため双方のバランスをみて95~130℃の範囲で温度を設定する必要があり、好ましい温度としては100℃~120℃、さらは105℃~115℃とすることが好ましい。カール形状の付与温度が95℃よりも低いと、触感の改良効果が充分でなく、かつ熱可塑性樹脂繊維の最低加工温度よりも低いためにポリ塩化ビニル系樹脂繊維単独よりもスタイル性の悪化する場合がある。またカール形状の付与温度が130℃よりも高いと、ポリ塩化ビニル系樹脂繊維が軟化温度を大きく超えるために繊維間の融着を繊維処理剤だけで抑えることが難しくなり、触感が硬くなって商品性が低下する。 When the temperature for imparting the curled shape is increased, the effect of improving the style properties and the effect of improving the feel of amino-modified silicone are amplified. On the other hand, if the temperature is excessively increased, the polyvinyl chloride resin fibers are fused by heat. And feel harder. For this reason, it is necessary to set the temperature in the range of 95 to 130 ° C. in view of the balance between the two, and a preferable temperature is 100 to 120 ° C., more preferably 105 to 115 ° C. When the curl-shaped imparting temperature is lower than 95 ° C., the effect of improving the tactile sensation is not sufficient, and the style is worse than the polyvinyl chloride resin fiber alone because it is lower than the minimum processing temperature of the thermoplastic resin fiber. There is a case. Also, when the curl-shaped imparting temperature is higher than 130 ° C., the polyvinyl chloride resin fiber greatly exceeds the softening temperature, so it becomes difficult to suppress the fusion between the fibers only with the fiber treatment agent, and the tactile sensation becomes hard. Productivity is reduced.
 また該温度範囲内であっても、ポリ塩化ビニル系樹脂繊維と熱可塑性樹脂繊維の収縮差が大きいと、熱可塑性樹脂繊維が撓んで繊維間の圧着力が低下することで、ポリ塩化ビニル系樹脂繊維に繊維屈曲が生じて触感が悪化する。このためカール付与温度におけるポリ塩化ビニル系樹脂繊維の収縮率と熱可塑性樹脂繊維の収縮率の差は6%以下である必要があり、好ましくは4%以下、さらに好ましくは3%以下がよい。ポリ塩化ビニル系樹脂繊維と熱可塑性樹脂繊維の収縮差が6%を超えると、熱可塑性樹脂繊維が撓んで繊維間の圧着力が低下し、ポリ塩化ビニル系樹脂繊維に繊維屈曲が生じて触感が悪化する。また熱可塑性樹脂繊維は複数の組成の繊維から構成されていてもよいが、何れの組成の繊維も上記収縮率の関係を満たす必要がある。 Even within this temperature range, if the shrinkage difference between the polyvinyl chloride resin fiber and the thermoplastic resin fiber is large, the thermoplastic resin fiber bends and the pressure between the fibers decreases, so that the polyvinyl chloride A fiber bending occurs in the resin fiber and the tactile sensation deteriorates. Therefore, the difference between the shrinkage ratio of the polyvinyl chloride resin fiber and the shrinkage ratio of the thermoplastic resin fiber at the curling temperature needs to be 6% or less, preferably 4% or less, more preferably 3% or less. If the difference in shrinkage between the polyvinyl chloride resin fiber and the thermoplastic resin fiber exceeds 6%, the thermoplastic resin fiber is bent and the crimping force between the fibers is reduced, and the polyvinyl chloride resin fiber is bent and touched. Gets worse. The thermoplastic resin fibers may be composed of fibers having a plurality of compositions, but the fibers having any composition must satisfy the above shrinkage relationship.
 以下に実施例を示して、本発明の具体的な実施態様をより詳細に説明するが、本発明は、この実施例のみに限定されるものではない。 Hereinafter, specific examples of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
 (実験例1)収縮率
 各繊維の混合前、あるいは混合された繊維束から1つの素材の単繊維を選り分けて束ね、総繊度18000±3000dtexの繊維束を作製した。その繊維束を40cmの長さに切断して、両端から5cmの位置にマーキングを行い、片端のみを固定した状態で、所定の温度で30分間乾燥条件下で加熱を行い、室温にて冷却を行った。冷却後の繊維束のマーキング間の長さを測定して元の長さ30cmに対する比率から収縮率を求めた。この測定を合計20回実施し、その平均値を試料の収縮率とした。なお実際の毛髪製品では試料が40cmより短い場合があるため、サンプリング可能な長さに応じてマーキング間の長さは短く出来るものとした。
(Experimental example 1) Shrinkage Before each fiber was mixed, or single fibers of one material were selected and bundled from the mixed fiber bundle, and a fiber bundle having a total fineness of 18000 ± 3000 dtex was produced. The fiber bundle is cut to a length of 40 cm, marked at a position of 5 cm from both ends, with only one end fixed, heated at a predetermined temperature for 30 minutes under drying conditions, and cooled at room temperature. went. The length between the markings of the fiber bundle after cooling was measured, and the shrinkage was determined from the ratio to the original length of 30 cm. This measurement was performed 20 times in total, and the average value was taken as the shrinkage rate of the sample. Since the sample may be shorter than 40 cm in an actual hair product, the length between the markings can be shortened according to the length that can be sampled.
 (実験例2)油剤担持量
 繊維束から繊維を取り出して重量を測定した後に、エタノール/シクロヘキサン=50%/50%の混合溶媒に20分間浸漬させ、混合溶媒から繊維を取り出した後に混合溶媒を120℃で加熱して気化させ、気化しなかった化合物の残分の重量を測定した。その値を元にして次の式で繊維への担持量を求めた。化合物の残重量/(繊維重量-化合物残重量)×100=化合物の繊維表面の担持量(omf%)。
(Experimental example 2) Oil agent carrying amount After taking out the fiber from the fiber bundle and measuring the weight, it was immersed in a mixed solvent of ethanol / cyclohexane = 50% / 50% for 20 minutes, and after removing the fiber from the mixed solvent, the mixed solvent was added. The mixture was heated and vaporized at 120 ° C., and the weight of the remaining compound that was not vaporized was measured. Based on this value, the amount carried on the fiber was determined by the following equation. Compound remaining weight / (fiber weight−compound remaining weight) × 100 = the amount of compound supported on the fiber surface (omf%).
 (実験例3)ヤング率
 A&D(株)社製テンシロン万能試験機(RTC-1210A)を用いて、引張り速度20cm/分の条件で応力-歪み曲線からヤング率の値を求め、N=20の平均値を試料のヤング率とした。
(Experimental example 3) Young's modulus Using a Tensilon universal testing machine (RTC-1210A) manufactured by A & D Co., Ltd., the value of Young's modulus was determined from the stress-strain curve under the condition of a tensile speed of 20 cm / min. The average value was taken as the Young's modulus of the sample.
 (実験例4)収縮応力
 セイコー電子工業(株)製SSC5200H熱分析TMA/SS150Cを用いて、繊維の熱収縮応力を測定した。長さ10mmの単繊維10本をとり、336.2mNの荷重をかけ、昇温速度5℃/分で30~240℃の範囲での収縮応力を測定し、130℃における収縮応力の値を試料の繊維本数10で除して単繊維1本の収縮応力とし、さらに単繊維の繊度で除して単位繊度あたりの収縮応力(μN/dtex)を求めた。
(Experimental example 4) Shrinkage stress The thermal contraction stress of the fiber was measured using SSC5200H thermal analysis TMA / SS150C by Seiko Electronics Industry. Take 10 monofilaments of 10 mm in length, apply a load of 336.2 mN, measure the shrinkage stress in the range of 30-240 ° C at a heating rate of 5 ° C / min, and measure the value of the shrinkage stress at 130 ° C The number of fibers was divided by 10 to obtain the shrinkage stress of one single fiber, and further divided by the fineness of the single fiber to obtain the shrinkage stress (μN / dtex) per unit fineness.
 (実験例5)LOI(限界酸素指数)
 16cm/0.25gのフィラメントを秤量し、端を軽く両面テープでまとめ、懸撚器で挟み撚りをかけた。十分に撚りがかかったら、試料の真中を二つに折り2本を撚り合わせた。端をセロハンテープで留め、全長7cmになるようにした。105℃で60分間前乾燥を行ない、さらにデシケーターで30分以上乾燥した。乾燥したサンプルを所定の酸素濃度に調整し、40秒後8~12mmに絞った点火器で上部より着火し、着火後点火器を離した。5cm以上燃えるか、3分以上燃え続けた酸素濃度を調べ、同じ条件で試験を3回繰り返し、限界酸素指数とした。
(Experimental example 5) LOI (limit oxygen index)
A filament of 16 cm / 0.25 g was weighed, the ends were lightly collected with double-sided tape, and sandwiched and twisted with a suspender. When the twist was sufficiently applied, the middle of the sample was folded in two and the two were twisted together. The ends were fastened with cellophane tape so that the total length was 7 cm. Pre-drying was performed at 105 ° C. for 60 minutes, and further drying was performed for 30 minutes or more with a desiccator. The dried sample was adjusted to a predetermined oxygen concentration, and after 40 seconds, it was ignited from the top with an igniter throttled to 8 to 12 mm, and the igniter was released after ignition. The oxygen concentration that burned 5 cm or more or continued burning for 3 minutes or more was examined, and the test was repeated three times under the same conditions to obtain the critical oxygen index.
 (実験例6)商品性:滑らかさ
 単繊維を抜き出して水平の板上に無荷重下で静置し、その形状をデシタル映像として取り込み、1試料あたり20cm×8本の繊維で角度170°未満の繊維屈曲を数え、1mあたりの繊維屈曲数を求めた。また複数の素材が混合された試料では、各素材の繊維屈曲数を数えた上で、構成比率を乗じて繊維束としての繊維屈曲数を求めた。その繊維屈曲数と合わせて、かつら等の美容評価に従事する一般的技術者の評価を基に以下の5段階で繊維平滑性の判定を行い、3点以上の水準を合格とした。
5点:繊維屈曲数10ケ/m未満:全くガサツキ感を感じない極めて良好な触感
4点:繊維屈曲数10ケ/m以上、20ケ/m未満:ガサツキを感じない良好な触感
3点:繊維屈曲数20ケ/m以上、50ケ/m未満:若干のガサツキを感じるが商品として適用可能なレベルの触感
2点:繊維屈曲数50ケ/m以上、100ケ/m未満:ガサツキを感じるために商品として適用し難いレベルの触感
1点:繊維屈曲数100ケ/m以上:極めてガサツキ感が高く商品に適用出来ないレベルの触感。
(Experimental example 6) Productivity: smoothness A single fiber is extracted and allowed to stand on a horizontal plate under no load, and the shape is captured as a digital image. The angle is less than 170 ° with 20 cm × 8 fibers per sample. The number of fiber bends was counted and the number of fiber bends per meter was determined. Further, in a sample in which a plurality of materials were mixed, after counting the number of fiber bends of each material, the number of fiber bends as a fiber bundle was obtained by multiplying the composition ratio. Together with the number of fiber bends, fiber smoothness was determined in the following five stages based on the evaluation of general engineers engaged in beauty evaluation such as wigs, and a level of 3 or more points was accepted.
5 points: less than 10 bends / m of fiber bending: very good tactile feeling with no feeling of roughness 4 points: More than 10 bends / m of fiber bend, less than 20 points / m: good tactile feeling without feeling of bend 3 points: Fiber bending number of 20 / m or more and less than 50 / m: Feeling slightly gritty, but tactile sensation of a level applicable as a product: 2 points: Fiber bending number of 50 / m or more, less than 100 / m: Feeling gritty Therefore, one point of tactile sensation that is difficult to apply as a product: 100 or more fiber bends / m: A tactile sensation that is extremely rough and cannot be applied to a product.
 (実験例7)商品性:柔らかさ
 人工毛髪用繊維束について、かつら等の美容評価に従事する一般的技術者により、人毛に近い柔らかな触感の再現性を基準に5段階で外観の評価を行い、3点以上の水準を合格とした。
5点:人毛とほぼ同等の柔らかな良好な触感
4点:人毛に近い柔らかな触感
3点:やや硬さ感はあるものの、比較的人毛に近い触感
2点:合成繊維特有の硬さ感がある触感
1点:一部に繊維間の融着が残る明らかに人毛と異なる触感。
(Experimental example 7) Productivity: softness About a fiber bundle for artificial hair, a general engineer engaged in beauty evaluation of wigs and the like evaluates the appearance in five stages based on reproducibility of soft touch close to human hair. And a score of 3 or more was accepted.
5 points: soft and good tactile feeling almost equivalent to human hair 4 points: soft tactile feeling close to human hair 3 points: Although somewhat hard, tactile feel relatively close to human hair 2 points: Hardness peculiar to synthetic fibers Feeling of touch 1 point: Tactile sensation that is clearly different from human hair, in which some interfiber fusion remains.
 (実験例8)商品性:潤い感/保湿感
 人工毛髪用繊維束について、かつら等の美容評価に従事する一般的技術者により、人毛に近い潤い感や保湿感を有するかを基準に5段階で外観の評価を行い、3点以上の水準を合格とした。
5点:潤い感、保湿感の何れも人毛に近いレベルの良好な触感
4点:若干不足気味ではあるものの、潤い感、保湿感の何れも人毛に近いレベルの触感
3点:潤い感、保湿感の何れかが不足気味ではあるものの、比較的人毛に近いレベルの触感
2点:潤い感、保湿感が明らかに人毛に対して劣る触感
1点:潤い感、保湿感が認識出来ない触感。
(Experimental example 8) Productivity: moisturizing / moisturizing feeling A general engineer engaged in beauty evaluation of wigs and the like with respect to a fiber bundle for artificial hair, based on whether it has a moisturizing feeling or moisturizing feeling close to human hair. Appearance was evaluated in stages, and a level of 3 or more was accepted.
5 points: good feeling of moisture and moisturizing feeling close to human hair 4 points: slightly dull, but moisturizing and moisturizing feeling close to human hair 3 points: moist feeling Although one of the moisturizing sensations is inadequate, tactile sensation at a level relatively close to human hair 2 points: moist feeling, moisturizing feeling clearly inferior to human hair 1 point: moist feeling, moisturizing sensation recognized Tactile feeling that can not be done.
 (実験例9)商品性:弾力感/カール形状安定性
 人工毛髪用繊維束について、カール形状付与後に60時間繊維束を吊るし、かつら等の美容評価に従事する一般的技術者により、弾力感とカール形状が長期間の使用でも保持されるかを基準に5段階で安定性の判定を行い、3点以上の水準を合格とした。
5点:試料を動かした際にカールが違和感なく脈動的に跳ね、カール形状も殆ど乱れが無い良好な状態
4点:試料を動かした際に違和感無くカールが跳ね、カール形状も大きな乱れがない状態
3点:試料を動かした際にややカールの跳ねが弱く、ややカール形状に乱れがある状態
2点:試料を動かした際にカールが垂れた状態にあり、カール形状も大きく乱れた状態
1点:60時間の保持のみで動かす前からカールが伸びて大きく乱れた状態。
(Experimental Example 9) Productivity: Elasticity / Curl Shape Stability Regarding a fiber bundle for artificial hair, the fiber bundle is hung for 60 hours after imparting the curl shape, and a general engineer engaged in beauty evaluation such as wigs gives elasticity Based on whether the curl shape is maintained even after long-term use, stability was determined in five stages, and a level of 3 or more points was accepted.
5 points: When the sample is moved, the curl jumps pulsating without any sense of incongruity, and the curl shape is almost undisturbed. State 3 point: When the sample is moved, the curl is slightly weak and the curl shape is somewhat disturbed. 2 point: When the sample is moved, the curl is in a suspended state, and the curl shape is greatly disturbed 1 Point: A state in which the curl is stretched and greatly disturbed before it is moved only by holding for 60 hours.
 (実験例10)商品性:ボリューム感
 人工毛髪用繊維束について、かつら等の美容評価に従事する一般的技術者により、繊維束試料の外観ならびに握り締めた際の反発力を基準に5段階でボリューム感を判定し、3点以上の水準を合格とした。
5点:3点を基準にして同一重量でも外観・反発力共に優れた嵩高性を有する
4点:3点を基準にして同一重量ではやや高い嵩高性を有する
3点:標準レベル
2点:3点を基準にして同一重量ではやや嵩高性が劣る
1点:3点を基準にして同一重量では明らかに嵩高性が劣る。
(Experimental example 10) Productivity: Sense of volume About a fiber bundle for artificial hair, a general engineer engaged in cosmetic evaluation of wigs, etc. has a volume in five stages based on the appearance of the fiber bundle sample and the repulsive force when clasped. The feeling was judged, and a level of 3 or more points was accepted.
5 points: Excellent bulkiness in appearance and repulsion even with the same weight based on 3 points 4 points: Slightly higher bulkiness with the same weight based on 3 points 3 points: Standard level 2 points: 3 Bulkiness is slightly inferior at the same weight based on the point 1 point: Bulkiness is clearly inferior at the same weight based on the 3 points.
 (実験例11)商品性:総合評価
 滑らかさ、柔らかさ、潤い感/保湿感、弾力感/カール形状安定性、ボリューム感の5項目の点数を合算して、21点以上を優良、20~17点を良、16~14点を並、13点以下を劣と判定し、良以上を合格とした。
(Experimental example 11) Productivity: Comprehensive evaluation Smoothness, softness, moisturizing feeling / moisturizing feeling, elasticity feeling / curl shape stability, and a sense of volume are added together, and 21 points or more are excellent. 17 points were judged good, 16-14 points were averaged, 13 points or less were judged as inferior, and good or better were judged as acceptable.
 (製造例1)PVC-1
 ポリ塩化ビニル樹脂S1001(カネカ(株)製)100重量部に対し、塩素化ポリ塩化ビニル樹脂H438(カネカ(株)製)10重量部、安定剤として、協和化学株式会社製のハイドロタルサイト熱安定剤であるアルカマイザー1を1重量部、エステル系滑剤として、理研ビタミン(株)社製EW-100を0.5重量部、ポリエチレンワックス系滑剤として三井化学(株)社製HW400Pを0.5重量部、その他に、β-ジケトンを0.4重量部、カルシウム石鹸・亜鉛石鹸を0.4重量部、エポキシ化大豆油を2重量部添加し、ヘンシェルミキサーで攪拌混合し、コンパウンドを製造した。また色の調整用に黒色系顔料を添加した。40mmφ押し出し機に、孔断面積0.1mm2、孔数120個のノズルを取り付けた。孔形状は繭型形状とした。シリンダー温度140~190℃、ノズル温度180±15℃の範囲で、紡糸性の良い条件で上記コンパウンドを押し出し溶融紡糸した。押し出されたフィラメントをノズル直下に設けた加熱紡糸筒内(200~400℃雰囲気で紡糸性の良い条件)で約0.5~1.5秒熱処理し、第一の引き取りロールによって紡糸した。この第一引き取りロールの直前で、非イオン性界面活性剤(ポリエチレンオキシド/ポリプロピレンオキシド共重合体、分子量約800)、カチオン系界面活性剤(アンモニウムサルフェート系化合物、分子量約800):エステル油(オレイン酸オレイル:分子量約500)からなる油剤を、繊維に対して0.5omf%になるように添付した。次に、第二の延伸ロールとの間で110℃の熱風循環箱を通して約3倍程度に延伸した。さらに110℃に温度調整した箱の中に設置した2対の円錐形ロール間を引き回し、2分間で約35%緩和熱処理を実施し、この中の単繊維が約77~81dtexの繊度になるようにマルチフィラメントを巻き取って、ポリ塩化ビニル系樹脂繊維PVC-1を作製した。
(Production Example 1) PVC-1
10 parts by weight of chlorinated polyvinyl chloride resin H438 (manufactured by Kaneka Corp.) and 100 parts by weight of polyvinyl chloride resin S1001 (manufactured by Kaneka Corp.), hydrotalcite heat manufactured by Kyowa Chemical Co., Ltd. 1 part by weight of Alkamizer 1 as a stabilizer, 0.5 parts by weight of EW-100 manufactured by Riken Vitamin Co., Ltd. as an ester lubricant, and HW400P manufactured by Mitsui Chemicals Co., Ltd. as a polyethylene wax type Add 5 parts by weight, 0.4 parts by weight of β-diketone, 0.4 parts by weight of calcium soap / zinc soap, and 2 parts by weight of epoxidized soybean oil, and stir and mix with a Henschel mixer to produce a compound. did. A black pigment was added for color adjustment. A nozzle having a hole cross-sectional area of 0.1 mm 2 and a hole number of 120 was attached to a 40 mmφ extruder. The hole shape was a saddle shape. The above compound was extruded and melt-spun in the range of a cylinder temperature of 140 to 190 ° C. and a nozzle temperature of 180 ± 15 ° C. under good spinning properties. The extruded filament was heat-treated for about 0.5 to 1.5 seconds in a heated spinning cylinder (under 200 to 400 ° C. atmosphere and good spinnability) provided immediately below the nozzle, and spun by a first take-up roll. Immediately before this first take-up roll, a nonionic surfactant (polyethylene oxide / polypropylene oxide copolymer, molecular weight of about 800), cationic surfactant (ammonium sulfate compound, molecular weight of about 800): ester oil (olein) An oil agent consisting of oleyl acid (molecular weight: about 500) was attached so as to be 0.5 omf% with respect to the fiber. Next, it extended | stretched about 3 times through the 110 degreeC hot-air circulation box between 2nd extending | stretching rolls. Furthermore, it is drawn between two pairs of conical rolls installed in a box whose temperature is adjusted to 110 ° C., and is subjected to a relaxation heat treatment of about 35% in 2 minutes, so that the single fibers therein have a fineness of about 77 to 81 dtex. The multifilament was wound around to prepare polyvinyl chloride resin fiber PVC-1.
 (製造例2)PVC-2
 油剤の構成成分を、分子量10000のポリエチレンオキシド/ポリプロピレンオキシド共重合体とし、油剤添付量を0.2omf%とし、緩和熱処理の温度を130℃とし、緩和速度を4分間で35%緩和とした以外は、製造例1と同様の方法を用いて、ポリ塩化ビニル系繊維PVC-2を作製した。
(Production Example 2) PVC-2
The component of the oil agent is a polyethylene oxide / polypropylene oxide copolymer having a molecular weight of 10,000, the amount of oil agent attached is 0.2 omf%, the temperature of the relaxation heat treatment is 130 ° C., and the relaxation rate is 35% relaxation for 4 minutes. In the same manner as in Production Example 1, a polyvinyl chloride fiber PVC-2 was produced.
 (製造例3)PVC-3
 緩和速度を6分間で37%緩和とした以外は、製造例2と同様の方法を用いて、ポリ塩化ビニル系繊維PVC-3を作製した。
(Production Example 3) PVC-3
A polyvinyl chloride fiber PVC-3 was produced in the same manner as in Production Example 2 except that the relaxation rate was reduced to 37% over 6 minutes.
 (製造例4)PVC-4
 緩和速度を8分間で39%緩和とした以外は、製造例2と同様の方法を用いて、ポリ塩化ビニル系繊維PVC-4を作製した。
(Production Example 4) PVC-4
A polyvinyl chloride fiber PVC-4 was produced in the same manner as in Production Example 2, except that the relaxation rate was reduced to 39% over 8 minutes.
 (製造例5)PVC-5
 油剤の構成成分を、非イオン性界面活性剤(ポリエチレンオキシド/ポリプロピレンオキシド共重合体、分子量約800)、カチオン系界面活性剤(アンモニウムサルフェート系化合物、分子量約800):エステル油(オレイン酸オレイル:分子量約500)とし、油剤添付量を0.5omf%とした以外は、製造例3と同様の方法を用いて、ポリ塩化ビニル系繊維PVC-5を作製した。
(Production Example 5) PVC-5
The components of the oil agent include nonionic surfactant (polyethylene oxide / polypropylene oxide copolymer, molecular weight of about 800), cationic surfactant (ammonium sulfate compound, molecular weight of about 800): ester oil (oleyl oleate: A polyvinyl chloride fiber PVC-5 was produced in the same manner as in Production Example 3 except that the molecular weight was about 500) and the amount of oil attached was 0.5 omf%.
 (製造例6)PVC-6
 油剤の構成成分を、分子量10000のポリエチレンオキシド/ポリプロピレンオキシド共重合体75重量%、動粘度1000mm2/Sのアミノ変性シリコーンオイル25重量%とし、油剤添付量を0.2omf%とした以外は、製造例3と同様の方法を用いて、ポリ塩化ビニル系繊維PVC-6を作製した。
(Production Example 6) PVC-6
The component of the oil was 75% by weight of polyethylene oxide / polypropylene oxide copolymer having a molecular weight of 10,000, 25% by weight of amino-modified silicone oil having a kinematic viscosity of 1000 mm 2 / S, and the amount of oil attached was 0.2 omf%. Using a method similar to that in Production Example 3, polyvinyl chloride fiber PVC-6 was produced.
 (製造例7)TPR-1
 アクリルニトリル50%、塩化ビニル49%、スチレンスルホン酸ソーダ1%を共重合して成るアクリル系共重合体樹脂をアセトンに溶解し、29%の紡糸原液を作製した。亜鈴型異形断面ノズルを用い、ノズルドラフトが1.6となる条件で、この紡糸原液を20℃の20%アセトン水溶液中に紡出し、得られた繊維を水洗浴50℃で脱溶剤及び1.5倍延伸し、次いで130℃で乾熱乾燥後、125℃で2.5倍の乾熱延伸を行い、更に150℃の乾熱で弛緩熱処理を行った。こうして得られたアクリル系繊維の単糸繊度は47dtexであった。又、断面形状は略馬蹄型であった。
(Production Example 7) TPR-1
An acrylic copolymer resin obtained by copolymerizing 50% acrylonitrile, 49% vinyl chloride, and 1% sodium styrenesulfonate was dissolved in acetone to prepare a 29% spinning dope. This spinning stock solution was spun into a 20% aqueous acetone solution at 20 ° C. using a dumbbell shaped cross-section nozzle under a nozzle draft of 1.6, and the resulting fiber was desolvated in a water washing bath at 50 ° C. and 1. The film was stretched 5 times, then dried dry at 130 ° C., then stretched 2.5 times at 125 ° C., and further subjected to relaxation heat treatment at 150 ° C. dry heat. The single fiber fineness of the acrylic fiber thus obtained was 47 dtex. The cross-sectional shape was substantially a horseshoe shape.
 (製造例8)TPR-2
 ポリエチレンテレフタレート(三菱化学(株)製、BK-2180)100重量部、臭素系難燃剤(阪本薬品工業(株)製、SR-T20000)、アンチモン化合物(日本精鉱(株)製、SA-A)を水分量100ppm以下に乾燥した後に着色用ポリエステルペレットPESM6100  BLACK(大日精化工業(株)製、カーボンブラック含有量30%)2部を添加してドライブレンドし、二軸押出機に供給し、280℃で溶融混練し、ペレット化したのちに、水分量100ppm以下に乾燥させた。ついで、溶融紡糸機で280℃で、眼鏡型ノズルを用いて、紡糸口金より溶融ポリマーを吐出し、口金下30mmの位置に設置した水温50℃の水浴中で冷却し、100m/分の速度で巻き取って未延伸糸を得た。得られた未延伸糸を80℃の温水浴中で延伸を行ない、4倍延伸糸とし、200℃に加熱したヒートロールを用いて、100m/分の速度で巻き取り、熱処理を行ない、単繊維繊度が65dtex前後のポリエステル系繊維(マルチフィラメント)を得た。
製造例1~8で得られた繊維の物性を表1に示した。
(Production Example 8) TPR-2
100 parts by weight of polyethylene terephthalate (manufactured by Mitsubishi Chemical Corporation, BK-2180), brominated flame retardant (manufactured by Sakamoto Pharmaceutical Co., Ltd., SR-T20000), antimony compound (manufactured by Nippon Seiko Co., Ltd., SA-A) ) Is dried to a water content of 100 ppm or less, and then 2 parts of polyester pellets for coloring PESM6100 BLACK (manufactured by Dainichi Seika Kogyo Co., Ltd., carbon black content 30%) are added, dry blended, and supplied to a twin screw extruder. After melt-kneading at 280 ° C. and pelletizing, it was dried to a water content of 100 ppm or less. Next, at 280 ° C. with a melt spinning machine, using a spectacle-type nozzle, the molten polymer is discharged from the spinneret and cooled in a water bath at a water temperature of 50 ° C. set at a position 30 mm below the base, at a speed of 100 m / min. The unwound yarn was obtained by winding. The obtained unstretched yarn is stretched in a warm water bath at 80 ° C. to obtain a 4-fold stretched yarn, wound at a speed of 100 m / min using a heat roll heated to 200 ° C., heat treated, and single fiber A polyester fiber (multifilament) having a fineness of around 65 dtex was obtained.
The physical properties of the fibers obtained in Production Examples 1 to 8 are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 (実施例1~14、比較例1~6)
 製造例1~8で作製したポリ塩化ビニル系繊維(PVC-1~6)ならびに熱可塑性樹脂繊維(TPR-1,2)を表2に示す比率で混合してハックリングを行い人工毛髪用繊維束とした。次に、アミノ変性シリコーンオイル(東レ・ダウコーニング(株)製、BY16203、動粘度2000mm2/S、官能基当量1900g/mol)、分子量10000のポリエチレンオキシド/ポリプロピレンオキシド共重合体、純水を重量比で0.5:0.5:9の割合で混合し、ホモジナイザーで攪拌してエマルジョン化させた後に酢酸を加えて中和を行い、繊維処理剤を作製した。この繊維処理剤に実施例1~5、7~13、ならびに比較例2、4、6の繊維束を5分間浸漬させ、繊維表面の担持量が0.4omf%となるように遠心脱水機で過剰な繊維処理剤を取り除いたのち、繊維束を各々120万dtexになるように2つの繊維束に分けた。また繊維処理剤を担持させなかった繊維束も同様に、各々120万dtexになるように2つの繊維束に分けた。次に一方の繊維束を長さ35cmに切断し、両端5cmを紐で括ってから表2記載の温度で1時間加熱を行い、収縮した繊維束の繊維屈曲数を測定した。次に残りの繊維束をかつら用ミシンで縫製して試長25cmのミノ毛を作り、これを直径35mmのパイプに巻いて、対流型乾燥機で表2記載の温度で1時間の熱セットを行い、カール形状を付与した。このカール付与したミノ毛をネットに1cm間隔で10段に縫製して商品見本を作製し、商品性(滑らかさ、柔らかさ、潤い感/保湿感、弾力感/カール形状安定性、ボリューム感)の評価を行った。結果を表2に示した。
(Examples 1 to 14, Comparative Examples 1 to 6)
Polyvinyl chloride fibers (PVC-1 to 6) prepared in Production Examples 1 to 8 and thermoplastic resin fibers (TPR-1 and 2) are mixed at the ratio shown in Table 2 to hack and artificial hair fibers It was a bunch. Next, amino-modified silicone oil (by Toray Dow Corning Co., Ltd., BY16203, kinematic viscosity 2000 mm 2 / S, functional group equivalent 1900 g / mol), polyethylene oxide / polypropylene oxide copolymer having a molecular weight of 10,000, and pure water by weight The mixture was mixed at a ratio of 0.5: 0.5: 9, stirred with a homogenizer to make an emulsion, and then neutralized by adding acetic acid to prepare a fiber treatment agent. The fiber bundles of Examples 1 to 5, 7 to 13 and Comparative Examples 2, 4, and 6 are immersed in this fiber treatment agent for 5 minutes, and then a centrifugal dehydrator is used so that the supported amount on the fiber surface is 0.4 omf%. After removing the excess fiber treating agent, the fiber bundle was divided into two fiber bundles so that each would have 1.2 million dtex. Similarly, the fiber bundle that did not carry the fiber treatment agent was divided into two fiber bundles so that each would be 1.2 million dtex. Next, one fiber bundle was cut into a length of 35 cm, and 5 cm at both ends were bound with a string, followed by heating at the temperature shown in Table 2 for 1 hour, and the number of fiber bends of the contracted fiber bundle was measured. Next, the remaining fiber bundle is sewed with a wig sewing machine to make a mino hair having a test length of 25 cm, wound on a pipe having a diameter of 35 mm, and heat-set for 1 hour at the temperature shown in Table 2 with a convection dryer. To give a curl shape. This curled mino hair is sewn on the net in 10 steps at 1 cm intervals to produce a product sample, and merchantability (smoothness, softness, moisturizing / moisturizing, elasticity / curl shape stability, volume) Was evaluated. The results are shown in Table 2.
 表2から明らかなとおり、本発明の人工毛髪用繊維は、触感とスタイリング性に優れ、特に剛性の高い繊維との組み合わせ、シリコーン油剤の適用、高温カール付与などにより、従来品を大きく上回る品質が得られることを確認した。 As is apparent from Table 2, the artificial hair fiber of the present invention has excellent tactile sensation and styling properties, and has a quality that greatly exceeds that of conventional products by combining with a particularly rigid fiber, application of a silicone oil agent, application of high-temperature curl, and the like. It was confirmed that it was obtained.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 1.従来PVC繊維PVC-1
 2.本発明PVC繊維PVC-2
 3.本発明PVC繊維PVC-3
 4.本発明PVC繊維PVC-4
1. Conventional PVC fiber PVC-1
2. Invention PVC fiber PVC-2
3. Invention PVC fiber PVC-3
4). Invention PVC fiber PVC-4

Claims (16)

  1.  130℃における収縮応力が70μN/dtex以下であるポリ塩化ビニル系樹脂繊維。 A polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less.
  2.  前記130℃における収縮応力が50μN/dtex以下である請求項1に記載のポリ塩化ビニル系樹脂繊維。 The polyvinyl chloride resin fiber according to claim 1, wherein the shrinkage stress at 130 ° C is 50 µN / dtex or less.
  3.  前記130℃における収縮応力が40μN/dtex以下である請求項2に記載のポリ塩化ビニル系樹脂繊維。 The polyvinyl chloride resin fiber according to claim 2, wherein the shrinkage stress at 130 ° C is 40 µN / dtex or less.
  4.  前記ポリ塩化ビニル系樹脂繊維が、塩化ビニルのホモポリマー樹脂、塩化ビニルとビニルエステル類とのコポリマー樹脂、塩化ビニルとアクリル酸エステル類とのコポリマー樹脂、塩化ビニルとオレフィン類とのコポリマー樹脂、及び、塩化ビニル-アクリロニトリルコポリマー樹脂からなる群から選ばれる1以上の樹脂からなる樹脂繊維である請求項1から3のいずれか1項に記載のポリ塩化ビニル系樹脂繊維。 The polyvinyl chloride resin fiber is a homopolymer resin of vinyl chloride, a copolymer resin of vinyl chloride and vinyl esters, a copolymer resin of vinyl chloride and acrylates, a copolymer resin of vinyl chloride and olefins, and The polyvinyl chloride resin fiber according to any one of claims 1 to 3, which is a resin fiber made of one or more resins selected from the group consisting of vinyl chloride-acrylonitrile copolymer resins.
  5.  前記ポリ塩化ビニル系樹脂繊維が人工毛髪用ポリ塩化ビニル系樹脂繊維である請求項1から4のいずれか1項に記載のポリ塩化ビニル系樹脂繊維。 The polyvinyl chloride resin fiber according to any one of claims 1 to 4, wherein the polyvinyl chloride resin fiber is a polyvinyl chloride resin fiber for artificial hair.
  6.  請求項1から5のいずれか1項に記載のポリ塩化ビニル系樹脂繊維20~100重量%と、ポリ塩化ビニル系樹脂を除く組成からなる熱可塑性樹脂繊維0~80重量%を含む人工毛髪用繊維束。 An artificial hair comprising 20 to 100% by weight of the polyvinyl chloride resin fiber according to any one of claims 1 to 5 and 0 to 80% by weight of a thermoplastic resin fiber having a composition excluding the polyvinyl chloride resin. Fiber bundle.
  7.  前記熱可塑性樹脂繊維のヤング率が4~9GPaである請求項6に記載の人工毛髪用繊維束。 The fiber bundle for artificial hair according to claim 6, wherein the Young's modulus of the thermoplastic resin fiber is 4 to 9 GPa.
  8.  前記熱可塑性樹脂繊維の130℃における収縮率が10%以下である請求項6または7に記載の人工毛髪用繊維束。 The fiber bundle for artificial hair according to claim 6 or 7, wherein the shrinkage rate of the thermoplastic resin fiber at 130 ° C is 10% or less.
  9.  前記ポリ塩化ビニル系樹脂繊維の130℃における収縮率が、前記熱可塑性樹脂繊維の130℃における収縮率より低くないことを特徴とする請求項6から8のいずれか1項に記載の人工毛髪用繊維束。 9. The artificial hair according to claim 6, wherein the shrinkage rate of the polyvinyl chloride resin fiber at 130 ° C. is not lower than the shrinkage rate of the thermoplastic resin fiber at 130 ° C. 9. Fiber bundle.
  10.  前記ポリ塩化ビニル系樹脂繊維の130℃における収縮率と、前記熱可塑性樹脂繊維の130℃における収縮率の差が6%以下であることを特徴とする請求項9に記載の人工毛髪用繊維束。 The fiber bundle for artificial hair according to claim 9, wherein the difference between the shrinkage rate of the polyvinyl chloride resin fibers at 130 ° C and the shrinkage rate of the thermoplastic resin fibers at 130 ° C is 6% or less. .
  11.  前記熱可塑性樹脂繊維が、アクリロニトリル系樹脂、モダアクリル系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリエーテルイミド系樹脂、ポリアミドイミド系樹脂、ポリオキシメチレン系樹脂、ポリエーテルケトン系樹脂、ポリカーボネート系樹脂、ポリサルフォン系樹脂、ポリエーテルサルフォン系樹脂、ポリフェニレンエーテル系樹脂、ポリフェレンスルフィド系繊維、および、テフロン(登録商標)樹脂からなる群から選ばれる1以上の樹脂からなる樹脂繊維である請求項6から10のいずれか1項に記載の人工毛髪用繊維束。 The thermoplastic resin fibers are acrylonitrile resin, modacrylic resin, polyolefin resin, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polyamideimide resin, polyoxymethylene resin, polyether. It consists of one or more resins selected from the group consisting of ketone resins, polycarbonate resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, polyferene sulfide fibers, and Teflon (registered trademark) resins. The fiber bundle for artificial hair according to any one of claims 6 to 10, which is a resin fiber.
  12.  前記ポリ塩化ビニル系樹脂繊維及び前記熱可塑性樹脂繊維がアミノ変性シリコーン化合物を含む請求項6から11のいずれか1項に記載の人工毛髪用繊維束。 The fiber bundle for artificial hair according to any one of claims 6 to 11, wherein the polyvinyl chloride resin fiber and the thermoplastic resin fiber contain an amino-modified silicone compound.
  13.  前記ポリ塩化ビニル系樹脂繊維が重量平均分子量2000~25000のポリアルキレンオキシド系化合物を0.07~0.5omf%含む請求項6から12のいずれか1項に記載の人工毛髪用繊維束。 The fiber bundle for artificial hair according to any one of claims 6 to 12, wherein the polyvinyl chloride resin fiber contains 0.07 to 0.5 omf% of a polyalkylene oxide compound having a weight average molecular weight of 2000 to 25000.
  14.  前記ポリ塩化ビニル系樹脂繊維がシリコーン系化合物を0~0.5omf%含む請求項6から13のいずれか1項に記載の人工毛髪用繊維束。 The artificial hair fiber bundle according to any one of claims 6 to 13, wherein the polyvinyl chloride resin fiber contains 0 to 0.5 omf% of a silicone compound.
  15.  請求項6から14のいずれか1項に記載の人工毛髪用繊維束を加工して得られる人工毛髪製品。 An artificial hair product obtained by processing the fiber bundle for artificial hair according to any one of claims 6 to 14.
  16.  前記加工が95~130℃で行われる請求項15に記載の人工毛髪製品。 The artificial hair product according to claim 15, wherein the processing is performed at 95 to 130 ° C.
PCT/JP2011/072914 2010-10-06 2011-10-05 Fiber for artificial hair, and hair accessory formed from same WO2012046748A1 (en)

Priority Applications (7)

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CN201180047221.9A CN103124812B (en) 2010-10-06 2011-10-05 Preparation method of polyvinyl chloride resin
JP2012537724A JP5700048B2 (en) 2010-10-06 2011-10-05 Manufacturing method of polyvinyl chloride resin fiber
EP11830680.2A EP2626452A4 (en) 2010-10-06 2011-10-05 Fiber for artificial hair, and hair accessory formed from same
KR1020137007673A KR101743497B1 (en) 2010-10-06 2011-10-05 Fiber for artificial hair, and hair accessory formed from same
US13/878,115 US20130298924A1 (en) 2010-10-06 2011-10-05 Fiber for artificial hair, and hair accessory formed from same
SG2013025606A SG189286A1 (en) 2010-10-06 2011-10-05 Fiber for artificial hair, and hair accessory formed from same
ZA2013/02535A ZA201302535B (en) 2010-10-06 2013-04-09 Fiber for artificial hair,and hair accessory formed from same

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KR20130138223A (en) 2013-12-18
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SG189286A1 (en) 2013-05-31
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ZA201302535B (en) 2016-08-31
US20130298924A1 (en) 2013-11-14

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