WO2016208630A1 - Acrylic copolymer, acrylic fiber for artificial hair and method for manufacturing same - Google Patents

Acrylic copolymer, acrylic fiber for artificial hair and method for manufacturing same Download PDF

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WO2016208630A1
WO2016208630A1 PCT/JP2016/068533 JP2016068533W WO2016208630A1 WO 2016208630 A1 WO2016208630 A1 WO 2016208630A1 JP 2016068533 W JP2016068533 W JP 2016068533W WO 2016208630 A1 WO2016208630 A1 WO 2016208630A1
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acrylic copolymer
sulfonic acid
acrylic
acid group
weight
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PCT/JP2016/068533
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French (fr)
Japanese (ja)
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穴原賢
吉村悟
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株式会社カネカ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile

Definitions

  • the present invention relates to an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride and a sulfonic acid group-containing vinyl monomer, an acrylic fiber for artificial hair composed of an acrylic copolymer, and
  • the present invention relates to a manufacturing method thereof.
  • Acrylic fibers especially acrylic fibers composed of an acrylic copolymer containing vinyl chloride or vinylidene chloride as one of the copolymer components, are artificially used for headdress products such as wigs, hairpieces, and weaving because of their soft touch. It is suitably used as a hair fiber.
  • an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride with a sulfonic acid group-containing vinyl monomer in order to improve transparency during dyeing. It was.
  • Patent Documents 1 to 3 describe acrylic fibers composed of an acrylic copolymer obtained by copolymerizing a halogen-containing vinyl monomer such as acrylonitrile and vinyl chloride, and a sulfonic acid group-containing vinyl monomer. It has been proposed to be used as artificial hair.
  • JP 2002-227018 A Japanese Patent Laid-Open No. 2002-227028 JP2011-252251A
  • an acrylic copolymer having a sulfonic acid group-containing vinyl monomer as a copolymer component is dissolved in an organic solvent such as dimethyl sulfoxide, and the resulting acrylic polymer is obtained when the solution is used as a spinning dope for wet spinning.
  • an organic solvent such as dimethyl sulfoxide
  • the present invention provides an acrylic copolymer capable of obtaining an acrylic fiber having a good combing property, an acrylic fiber for artificial hair having a good combing property, and a method for producing the same. I will provide a.
  • the present invention is an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer, and the acrylic copolymer has a weight average molecular weight of 100. , 000 or less, a sulfur content of 0.35% by weight or more, and in the acrylic copolymer, the diffusion coefficient D of the main chain and the diffusion coefficient D ′ of the sulfonic acid group-containing component measured by the DOSY method The ratio D / D ′ is 1.07 or less, and the present invention relates to an acrylic copolymer.
  • the present invention is also an acrylic fiber for artificial hair comprising an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer,
  • the acrylic copolymer has a weight average molecular weight of 100,000 or less and a sulfur content of 0.35% by weight or more.
  • the main chain diffusion coefficient measured by the DOSY method is used.
  • the present invention relates to an acrylic fiber for artificial hair, wherein the ratio D / D ′ of D and the diffusion coefficient D ′ of the sulfonic acid group-containing component is 1.07 or less.
  • the present invention also relates to a method for producing the acrylic copolymer, wherein polymerization of acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer is continuously performed in a single reaction vessel.
  • the polymerization reaction is started, the sulfonic acid group-containing vinyl monomer is not charged into the reaction vessel at the start of the polymerization reaction.
  • the yield of the acrylic copolymer is 8% by weight or more of the target amount of the acrylic copolymer.
  • the present invention relates to a method for manufacturing coalescence.
  • the present invention also relates to the above-described method for producing an acrylic fiber for artificial hair, wherein the acrylic copolymer is used as one or more organic solvents selected from the group consisting of dimethyl sulfoxide, dimethylacetamide and N, N-dimethylformamide.
  • the present invention relates to a method for producing acrylic fiber for artificial hair, characterized by wet spinning a spinning dope obtained by dissolution.
  • the acrylic copolymer of the present invention By using the acrylic copolymer of the present invention, it is possible to obtain acrylic fiber for artificial hair having good combability.
  • the acrylic fiber for artificial hair of the present invention has good combability.
  • the weight average molecular weight is 100,000 or less
  • the sulfur content is 0.35% by weight or more
  • the main chain diffusion coefficient D measured by the DOSY method.
  • An acrylic copolymer having a ratio D / D ′ of 1.07 or less of the diffusion coefficient D ′ of the sulfonic acid group-containing component can be obtained.
  • acrylic fiber for artificial hair of the present invention by using one or more organic solvents selected from the group consisting of the acrylic polymer and dimethyl sulfoxide, dimethylacetamide and N, N-dimethylformamide, An acrylic fiber for artificial hair with good productivity and good combing property can be obtained.
  • the inventors of the present invention improved the combing property of acrylic fibers composed of an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer.
  • the weight average molecular weight is 100,000 or less
  • the sulfur content is 0.35% by weight or more
  • the main chain diffusion coefficient D and sulfonic acid group content measured by the DOSY method are used.
  • the ratio D / D ′ of the component diffusion coefficient D ′ is set to 1.07 or less, and it has been found that the combing property of the acrylic fiber composed of the acrylic copolymer is improved, leading to the present invention. It was.
  • the weight average molecular weight is 100,000 or less, the sulfur content is 0.35% by weight or more, and the ratio D between the diffusion coefficient D of the main chain and the diffusion coefficient D ′ of the sulfonic acid group-containing component measured by the DOSY method
  • An acrylic copolymer having / D ′ of 1.07 or less is dissolved in an organic solvent such as dimethyl sulfoxide to form a spinning stock solution, and when the spinning stock solution is wet-spun, fibers having a smooth surface are easily formed. The combability of the fiber will be improved.
  • the acrylic copolymer comprises 30 to 70% by weight of acrylonitrile, 25 to 69.5% by weight of vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl based on the total weight of the acrylic copolymer. It is preferable to contain 0.5 to 5% by weight of monomer. That is, the acrylic copolymer contains 30 to 70% by weight of acrylonitrile, 25 to 69.5% by weight of vinyl chloride and / or vinylidene chloride, and 0.5 to 5% by weight of sulfonic acid group-containing vinyl monomer. A total of 100% by weight of the monomer mixture is polymerized.
  • the acrylic copolymer when the acrylonitrile content is 30 to 70% by weight, the heat resistance is improved, and the processing temperature at the curl setting of the acrylic fiber composed of the acrylic copolymer is set. It can be set appropriately.
  • the acrylic copolymer when the content of vinyl chloride and / or vinylidene chloride is 25 to 69.5% by weight, the flame retardancy is good.
  • the acrylic copolymer contains 0.5 to 5% by weight of the sulfonic acid group-containing vinyl monomer, the dyeability is improved, the hydrophilicity is increased, and the void ratio is lowered.
  • the acrylic copolymer preferably contains 1% by weight or more, more preferably 1.5% by weight or more of the sulfonic acid group-containing vinyl monomer with respect to the total weight of the acrylic copolymer.
  • the acrylic copolymer preferably contains 69% by weight or less, more preferably 68.5% by weight or less of vinyl chloride and / or vinylidene chloride based on the total weight of the acrylic copolymer. preferable.
  • the acrylic copolymer preferably contains vinyl chloride.
  • the sulfonic acid group-containing vinyl monomer is not particularly limited, and examples thereof include sulfonic acids such as allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid.
  • sulfonic acids such as allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid.
  • Compounds, metal salts such as sodium salts of these sulfonic acid compounds such as sodium parastyrene sulfonate, and amine salts of these sulfonic acid compounds such as styrene sulfonic acid amine salts can be used.
  • the acrylic copolymer has a weight average molecular weight (Mw) of 100,000 or less.
  • Mw weight average molecular weight
  • the acrylic copolymer preferably has a weight average molecular weight of 60,000 to 100,000 from the viewpoint of increasing the resin concentration of the spinning dope, realizing a dense fiber structure, and achieving both fiber strength. More preferably, it is 70,000 to 100,000.
  • the acrylic copolymer is not particularly limited, but has a number average molecular weight (Mn) of 20,000 to 20,000 from the viewpoint of increasing the resin concentration of the spinning dope, realizing a dense fiber structure, and achieving both fiber strength. It is preferably 50,000, and more preferably 30,000 to 50,000. In the embodiment of the present invention, the weight average molecular weight and number average molecular weight of the acrylic copolymer can be measured by gel permeation chromatography.
  • the acrylic copolymer is not particularly limited, but a molecular weight distribution (Mw / Mn) represented by a ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) from the viewpoint of increasing fiber strength and obtaining fibers having good combability.
  • Mw / Mn molecular weight distribution
  • PDI molecular weight distribution
  • the acrylic copolymer has a sulfur content of 0.35% by weight or more.
  • the sulfur content in the acrylic copolymer is preferably 0.35 to 1.0% by weight, and more preferably 0.4 to 0.6% by weight. In embodiments of the present invention, the sulfur content can be measured as described below.
  • the ratio D / D ′ (hereinafter also simply referred to as “D / D ′”) of the diffusion coefficient D ′ of the main chain measured by the DOSY method and the diffusion coefficient D ′ of the sulfonic acid group-containing component. .) Is 1.07 or less.
  • D / D ′ is preferably 0.4 or more and 1.07 or less, and more preferably 0.6 or more and 1.07 or less.
  • the measurement of the diffusion coefficient by the DOSY method can be performed as described later.
  • the diffusion coefficient of the sulfonic acid group-containing component is preferably 17 to 50 ⁇ m 2 / sec, more preferably 20 to 35 ⁇ m 2 / sec. If the diffusion coefficient of the sulfonic acid group-containing component is too small, the proportion of the sulfonic acid in the sulfonic acid group-containing component is reduced, the hydrophilicity is lowered, and there is a tendency that dense solidification is difficult to obtain during spinning. If the diffusion coefficient of the sulfonic acid group-containing component is too large, the hydrophilicity of the molecular chain becomes excessively high and the sulfonic acid group-containing component may be eluted into the bath during spinning.
  • the weight average molecular weight of the sulfonic acid group-containing component represented by the following formula (1) is preferably 24,000 to 110,000, and preferably 36,000 to 100,000. More preferred. Dense solidification can be realized in the spinning process, and elution of the sulfonic acid group-containing component into the bath can be effectively prevented.
  • Mw ′ is the weight average molecular weight of the sulfonic acid group-containing component
  • Mw is the weight average molecular weight of the acrylic copolymer.
  • Mw ′ (D / D ′) 2 ⁇ Mw (1)
  • the acrylic copolymer can be prepared by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer.
  • the method of copolymerization is not particularly limited, and usual vinyl polymerization methods such as slurry polymerization method, emulsion polymerization method, solution polymerization method and the like can be used.
  • the polymerization is preferably carried out by an emulsion polymerization method, from the stability of the production process, It is preferable to carry out continuously in a single reaction vessel.
  • the weight average molecular weight is 100,000 or less
  • the sulfur content is 0.35% by weight or more
  • D / D ′ is An acrylic copolymer of 1.07 or less
  • the emulsion polymerization can be carried out using an emulsifier in the presence of a water-soluble initiator in the same manner as a general method, except that the sulfonic acid group-containing vinyl monomer is charged into the reaction vessel as described above. it can.
  • the water-soluble initiator is not particularly limited, but it is preferable to use a persulfate that functions as an oxidizing agent.
  • the activation energy is low and the yield can be increased even at low temperatures.
  • the persulfate is preferably added in an amount of 0.1 to 0.4 parts by weight, more preferably 0.2 to 0.3 parts by weight, when the total weight of the monomers is 100 parts by weight.
  • the persulfate examples include, but are not limited to, ammonium persulfate and potassium persulfate.
  • the reducing agent include, but are not limited to, sodium bisulfite, sodium bisulfite, and sulfurous acid.
  • catalyst decomposition accelerators such as iron sulfate and copper sulfate, and chain transfer agents such as t-butyl mercaptan and 2-mercaptoethanol may be used in combination. From the viewpoint of easily obtaining an acrylic copolymer having a desired molecular weight, the catalyst decomposition accelerator is preferably 0.0018 to 0.0039 parts by weight when the total weight of the monomers is 100 parts by weight. .
  • the emulsifier is preferably an anionic surfactant usually used in emulsion polymerization, and examples thereof include, but are not limited to, alkylbenzene sulfonate and alkyl alcohol sulfate.
  • alkyl alcohol sulfate ester salt for example, sodium lauryl sulfate can be used.
  • the polymerization temperature is preferably 40 to 70 ° C., more preferably 45 to 55 ° C. from the viewpoint of productivity and quality of the acrylic copolymer.
  • Raw materials such as monomers, initiators, emulsifiers and water that are continuously added to the reaction tank are accurately added under the control of the metering pump, but the amount of heat removed from the polymerization heat generated in the reaction tank is ensured. Therefore, you may cool beforehand as needed.
  • the latex is discharged from the reaction tank using a metering pump or a flow control valve from the bottom of the reaction tank or from the lower side of the reaction tank so as to maintain the pressure inside the reaction tank and to discharge the same amount of copolymer liquid as the added raw material. Is preferred.
  • the average residence time inside the reaction tank (time obtained by dividing the volume of the reaction tank by the amount of additional raw materials per hour) is usually 0.5 to 10 hours, preferably 1.5 to 3 hours. It is preferable in terms of mechanical stability and quality when the copolymer is a fiber.
  • a polymerization inhibitor, a coagulant, a flame retardant, and a pH adjuster may be added to the discharged acrylic copolymer latex, and unreacted monomers are recovered and post-polymerized. May be. Thereafter, an acrylic copolymer can be obtained through known methods such as coagulation, heat treatment, dehydration, washing with water, and drying.
  • the acrylic fiber for artificial hair is composed of the acrylic copolymer.
  • the weight average molecular weight (Mw), the number average molecular weight (Mn), the sulfur content, the diffusion coefficient of the main chain and the diffusion coefficient of the sulfonic acid group-containing component of the acrylic copolymer constituting the acrylic fiber for artificial hair are described above. It is the same as that of the acrylic copolymer before constituting the prepared fiber, and can be measured in the same manner as in the case of the acrylic copolymer except that the fiber is used as a sample.
  • the acrylic fiber for artificial hair preferably has a surface roughness of 6100 ⁇ m 2 or less, more preferably 6000 ⁇ m 2 or less in the region of 40 ⁇ m length and 80 ⁇ m width on the fiber side surface. More preferably, it is 5900 ⁇ m 2 or less.
  • the surface roughness can be measured and calculated as described later.
  • the acrylic fiber for artificial hair can be produced by wet-spinning a spinning stock solution obtained by dissolving the acrylic copolymer in an organic solvent.
  • the organic solvent is preferably one or more organic solvents selected from the group consisting of dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc) and N, N-dimethylformamide (DMF).
  • the organic solvent is more preferably dimethyl sulfoxide.
  • the spinning dope depends on the composition of the acrylic copolymer, it preferably contains 20-30% by weight of the acrylic copolymer, more preferably the acrylic copolymer, based on the total weight of the spinning dope. Is contained in an amount of 22 to 30% by weight, more preferably 25 to 30% by weight of an acrylic copolymer.
  • the spinning dope may contain a small amount of water from the viewpoint of suppressing void formation.
  • the water content is preferably 1 to 5% by weight, more preferably 2 to 4% by weight, based on the total weight of the spinning dope.
  • the spinning undiluted solution may contain other additives for improving the fiber characteristics, if necessary, as long as the effects of the present invention are not impaired.
  • additives include gloss modifiers such as esters and ethers of cellulose derivatives such as titanium dioxide, silicon dioxide, and cellulose acetate, colorants such as organic pigments, inorganic pigments, and dyes, and improvements in light resistance and heat resistance. Stabilizers and the like.
  • Acrylic fibers are obtained by wet-spinning the spinning dope using a conventional method.
  • the spinning solution is first solidified by discharging through a spinning nozzle or directly into a coagulation bath to coagulate.
  • a coagulation bath for example, an aqueous solution having an organic solvent concentration of 40 to 70% by weight such as dimethyl sulfoxide can be used.
  • the temperature of the coagulation bath can be 5 to 40 ° C. If the concentration of the organic solvent such as dimethyl sulfoxide in the coagulation bath is too low, coagulation is accelerated and the coagulation structure becomes rough and voids tend to form inside the fiber.
  • the fiber (coagulated yarn) is washed with water.
  • the organic solvent is removed by washing with water. Note that the organic solvent used in the spinning dope cannot be completely removed from the fiber and may remain in an extremely small amount.
  • warm water of 30 ° C. or higher or an aqueous solution of an organic solvent having a lower concentration of the organic solvent than the coagulation bath can be used.
  • bath stretching may be performed in a stretching bath before or after the water washing step. As the stretching bath, warm water of 30 ° C. or higher or an aqueous solution of an organic solvent having a lower organic solvent concentration than the coagulation bath can be used.
  • the draw ratio of the bath drawing is not particularly limited, but is preferably 2 to 8 times, more preferably 2 to 7 times, and more preferably 2 to 6 times from the viewpoint of enhancing the strength and productivity of the fiber. More preferably.
  • the acrylic fiber may be dried.
  • an oil agent may be attached as necessary.
  • the oil agent may be any oil agent as long as it is usually used for the purpose of preventing static electricity, preventing fiber sticking and improving the texture in the spinning process, and a known oil agent can be used.
  • the drying temperature is not particularly limited, but is, for example, 110 to 190 ° C., preferably 110 to 160 ° C.
  • the dried fiber may be further stretched if necessary, and the stretch ratio is preferably 1 to 4 times.
  • the total stretching ratio including stretching before drying is preferably 2 to 12 times.
  • the fiber obtained by further stretching after drying or drying is further relaxed in a thermal relaxation treatment step.
  • the relaxation rate is not particularly limited, but is preferably 5% or more, and more preferably 10% or more, for example.
  • the thermal relaxation treatment can be performed in a dry heat atmosphere or a superheated steam atmosphere at a high temperature, for example, 130 to 200 ° C., preferably 140 to 190 ° C. Alternatively, it can be carried out in a pressurized steam or heated and pressurized steam atmosphere of 0.05 to 0.4 MPa, preferably 0.1 to 0.4 MPa at 120 to 180 ° C.
  • the acrylic fiber for artificial hair preferably has a single fiber fineness of 10 to 100 dtex, more preferably 20 to 95 dtex, and even more preferably 30 to 90 dtex, from the viewpoint of suitable use as artificial hair. Even more preferably, it is 40 to 80 dtex, and even more preferably 45 to 70 dtex.
  • the single fiber fineness means an average value of fineness of any 100 single fibers.
  • the acrylic fiber for artificial hair has good combability. Combability can be evaluated, for example, as described below.
  • a headdress product can be constructed using the acrylic fiber for artificial hair.
  • the head decoration product may include other artificial hair fibers in addition to the artificial hair acrylic fibers.
  • Other artificial hair fibers are not particularly limited, and examples thereof include polyvinyl chloride fibers, nylon fibers, polyester fibers, and regenerated collagen fibers.
  • hair ornament products include hair bundles for hair, weaving, wigs, blades, two-pieces, hair extensions and hair accessories.
  • the acrylic copolymer was produced by continuously performing emulsion polymerization in a single reaction tank. First, 162.2 parts of ion exchange water, 0.87 part of sodium lauryl sulfate, 0.6 part of sodium hydrogen sulfite, 0.0039 part of iron sulfate, 0.3 part of sulfuric acid, 3.5 parts of acrylonitrile, 54.5 parts of vinyl was added, and polymerization was carried out at 49 ° C. for 5 hours and 40 minutes while continuously adding acrylonitrile and ammonium persulfate at a constant rate.
  • the addition amount of acrylonitrile and the addition amount of ammonium persulfate were 40 parts and 0.2644 parts, respectively.
  • sodium parastyrenesulfonate was charged into the reaction vessel at a constant rate, and a total of 2 parts until the polymerization reaction was completed. I put it in. After completion of the polymerization reaction, unreacted vinyl chloride was recovered to obtain an acrylic copolymer latex.
  • the resulting acrylic copolymer latex was coagulated by salting out, followed by heat treatment, filtration, washing with water, dehydration and drying to obtain 46.0% acrylonitrile, 52.0% vinyl chloride, 2.0 % Acrylic copolymer consisting of sodium parastyrene sulfonate was obtained.
  • the composition analysis of the acrylic copolymer was performed by confirming the acrylonitrile content by elemental analysis and confirming the sodium styrenesulfonate content by sulfur analysis.
  • the film was stretched 3 times in a stretching bath composed of an aqueous solution of dimethyl sulfoxide at 50 ° C. at 50 ° C. Subsequently, after washing with warm water of 90 ° C., drying at 140 ° C., stretching twice, and applying a 20% relaxation treatment at 160 ° C., an acrylic fiber having a single fiber fineness of about 46 dtex is obtained. It was.
  • Example 2 Manufacture of acrylic copolymer> After starting the polymerization reaction, from the time when the yield of the acrylic copolymer reached 19% of the target amount, sodium parastyrenesulfonate was charged into the reaction vessel at a constant rate, and a total of 2 parts were charged until the polymerization reaction was completed. In the same manner as in Example 1, an acrylic copolymer was produced. The polymerization reaction was carried out for 5 hours and 40 minutes. ⁇ Wet spinning> An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1 except that the acrylic copolymer obtained above was used.
  • Example 3 An acrylic copolymer was prepared in the same manner as in Example 1 except that the iron sulfate used in the polymerization reaction was changed to 0.0018 part. The polymerization reaction was carried out for 5 hours and 40 minutes. ⁇ Wet spinning> An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1 except that the acrylic copolymer obtained above was used.
  • the initiator is an azo compound that generates free radicals
  • the solvent is N, N-dimethylformamide
  • the blending ratio of the four copolymer monomers is 50 parts of acrylonitrile, 38.5 parts of vinylidene chloride, 0.5 parts of methyl methacrylate. Part and 5.0 parts of methylpropenesulfonic acid.
  • Each component used for the polymerization was continuously added to the reaction vessel at a temperature of 55 ° C. by a metering pump, and solution polymerization was performed.
  • the spinning dope is discharged into a coagulation bath composed of an aqueous solution of 50% by weight of dimethylformamide at 20 ° C. using a spinning nozzle to coagulate and fiberize, and then an aqueous solution having a dimethylformamide concentration of 30%, 20% Solvents were sequentially removed in a bath into which an aqueous solution and a 15% aqueous solution were introduced, and primary stretching was performed four times.
  • Drying and densification were performed at 140 ° C., secondary stretching at 1.3 times at 117 ° C. was performed, and relaxation treatment was performed at 125 ° C. by 10% to obtain an acrylic fiber having a single fiber fineness of 46 dtx.
  • the number average molecular weight, weight average molecular weight, and sulfur content of the acrylic copolymers obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured and calculated as follows. Further, the diffusion coefficient of the main chain and the diffusion coefficient of the sulfonic acid group-containing component in the acrylic copolymers obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured and calculated as follows. These results are shown in Table 1 below. Table 1 below also shows the weight average molecular weight (Mw ′) of the sulfonic acid group-containing component calculated based on the above formula (1).
  • the analysis of the absorbing solution was performed using an ion chromatograph “ICS1500” manufactured by DIONEX, using a mixed solution of 2.7 mmol / L Na 2 CO 3 and 0.3 mmol / L NaHCO 3 as a mobile phase, and a flow rate. It was measured at 1.5 mL / min using an electrical conductivity detector.
  • the diffusion coefficient was measured using NMR method, specifically, DOSY method (Diffusion-ordered NMR spectroscopy).
  • NMR measurement was performed with a nuclear magnetic resonance apparatus “VNMRS 600” manufactured by VARIAN using a solution in which 10 mg of a sample was dissolved in 0.5 mL of heavy DMF. The measurement conditions were as follows.
  • Measurement temperature 40 ° C Pulse series: BPP-STE-LED Relaxation delay time: 5s Magnetic field gradient pulse width: 6ms Spreading time: 100ms Magnetic field gradient strength: 0.04 to 0.60 T / m Array point: 16 points Integration number: 128 times (2) Analysis conditions Data processing was performed by the maximum entropy method using NMRnotebook manufactured by NMRtec. FID import points: 4096 Window function (LB): 3Hz After writing the DOSY spectrum ( 1 HDOSY spectrum) as text data, the average value of the diffusion coefficient of each region is calculated, the peak top is read from the obtained diffusion coefficient distribution, and the diffusion coefficient of the main chain in the acrylic copolymer And the diffusion coefficient of the sulfonic acid group-containing component was determined.
  • LB Window function
  • the surface roughness of the acrylic fibers of Examples 1 to 3 and Comparative Examples 1 to 3 was measured as follows. Further, the combability of the acrylic fibers of Examples 1 to 3 and Comparative Examples 1 to 3 was evaluated as follows. These results are shown in Table 1 below.
  • a polyacetal resin comb manufactured by Uehara Cell Co., Ltd., trade name “New Delrin Comb # 826) is used as the tow filament at a speed of 0.3 m / s. It was allowed to pass 30 times or more completely from the upper 3 cm to the bottom, and the ease of combing was evaluated according to the following criteria.
  • C There is resistance or it is caught in the middle, and the comb is difficult to pass.
  • the acrylic fibers composed of the acrylic copolymers of Comparative Examples 1 to 3 having a weight average molecular weight exceeding 100,000 and D / D ′ exceeding 1.07 have a surface roughness. It was big and the combing ability was bad.

Abstract

In an embodiment of the present invention, an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and/or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer has a weight-average molecular weight of 100,000 or less and a sulfur content of 0.35 wt% or more, and the ratio of the diffusion coefficient of the main chain to the diffusion coefficient of the sulfonic acid group-containing component, as measured by DOSY, is 1.07 or less. In an embodiment of the present invention, an acrylic fiber for artificial hair comprises the acrylic copolymer. In an embodiment of the present invention, when continuously polymerizing the monomer in a single reaction tank, the acrylic copolymer is prepared not by feeding the sulfonic acid group-containing vinyl monomer into the reaction tank at the start of the polymerization reaction, but rather by continuously feeding the sulfonic acid group-containing vinyl monomer at a constant rate after the start of the polymerization reaction, from the time when the yield of the acrylic copolymer reaches a predetermined amount of 8-21 wt% of the target amount of the acrylic copolymer, until the polymerization reaction is complete.

Description

アクリル系共重合体、人工毛髪用アクリル系繊維及びそれらの製造方法Acrylic copolymer, acrylic fiber for artificial hair, and production method thereof
　本発明は、アクリロニトリルと、塩化ビニル及び／又は塩化ビニリデンと、スルホン酸基含有ビニル単量体を共重合したアクリル系共重合体、アクリル系共重合体で構成された人工毛髪用アクリル系繊維及びそれらの製造方法に関する。 The present invention relates to an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride and a sulfonic acid group-containing vinyl monomer, an acrylic fiber for artificial hair composed of an acrylic copolymer, and The present invention relates to a manufacturing method thereof.
　アクリル系繊維、特に共重合成分の一つとして塩化ビニル又は塩化ビニリデンを含むアクリル系共重合体で構成されるアクリル系繊維は、ソフトな触感から、かつら、ヘアピース、ウィービング等の頭飾製品に用いる人工毛髪用繊維として好適に用いられている。また、染色時の透明性を向上させることから、アクリロニトリル、塩化ビニル及び／又は塩化ビニリデンに、さらにスルホン酸基含有ビニル単量体を共重合させたアクリル系共重合体を用いることが好まれていた。例えば、特許文献１～３には、アクリロニトリル、塩化ビニル等のハロゲン含有ビニル系単量体、及びスルホン酸基含有ビニル単量体を共重合したアクリル系共重合体で構成されたアクリル系繊維を人工毛髪として用いることが提案されている。 Acrylic fibers, especially acrylic fibers composed of an acrylic copolymer containing vinyl chloride or vinylidene chloride as one of the copolymer components, are artificially used for headdress products such as wigs, hairpieces, and weaving because of their soft touch. It is suitably used as a hair fiber. In addition, it is preferable to use an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride with a sulfonic acid group-containing vinyl monomer in order to improve transparency during dyeing. It was. For example, Patent Documents 1 to 3 describe acrylic fibers composed of an acrylic copolymer obtained by copolymerizing a halogen-containing vinyl monomer such as acrylonitrile and vinyl chloride, and a sulfonic acid group-containing vinyl monomer. It has been proposed to be used as artificial hair.
特開２００２－２２７０１８号公報JP 2002-227018 A 特開２００２－２２７０２８号公報Japanese Patent Laid-Open No. 2002-227028 特開２０１１－２５２２５１号公報JP2011-252251A
　しかし、スルホン酸基含有ビニル単量体を共重合成分とするアクリル系共重合体は、ジメチルスルホキシド等の有機溶媒に溶解し、該溶液を紡糸原液として用いて湿式紡糸した場合、得られたアクリル系繊維の櫛通り性が悪い傾向があった。 However, an acrylic copolymer having a sulfonic acid group-containing vinyl monomer as a copolymer component is dissolved in an organic solvent such as dimethyl sulfoxide, and the resulting acrylic polymer is obtained when the solution is used as a spinning dope for wet spinning. There was a tendency for the combing property of the system fibers to be poor.
　本発明は、前記従来の問題を解決するため、櫛通り性が良好なアクリル系繊維を得ることができるアクリル系共重合体、櫛通り性が良好な人工毛髪用アクリル系繊維及びそれらの製造方法を提供する。 In order to solve the above-mentioned conventional problems, the present invention provides an acrylic copolymer capable of obtaining an acrylic fiber having a good combing property, an acrylic fiber for artificial hair having a good combing property, and a method for producing the same. I will provide a.
　本発明は、アクリロニトリルと、塩化ビニル及び／又は塩化ビニリデンと、スルホン酸基含有ビニル単量体を共重合したアクリル系共重合体であって、前記アクリル系共重合体は、重量平均分子量が１００，０００以下であり、硫黄含有量が０．３５重量％以上であり、前記アクリル系共重合体において、ＤＯＳＹ法にて測定した主鎖の拡散係数Ｄとスルホン酸基含有成分の拡散係数Ｄ’の比Ｄ／Ｄ’が１．０７以下であることを特徴とするアクリル系共重合体に関する。 The present invention is an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer, and the acrylic copolymer has a weight average molecular weight of 100. , 000 or less, a sulfur content of 0.35% by weight or more, and in the acrylic copolymer, the diffusion coefficient D of the main chain and the diffusion coefficient D ′ of the sulfonic acid group-containing component measured by the DOSY method The ratio D / D ′ is 1.07 or less, and the present invention relates to an acrylic copolymer.
　本発明は、また、アクリロニトリルと、塩化ビニル及び／又は塩化ビニリデンと、スルホン酸基含有ビニル単量体を共重合したアクリル系共重合体で構成された人工毛髪用アクリル系繊維であって、前記アクリル系共重合体は、重量平均分子量が１００，０００以下であり、硫黄含有量が０．３５重量％以上であり、前記アクリル系共重合体において、ＤＯＳＹ法にて測定した主鎖の拡散係数Ｄとスルホン酸基含有成分の拡散係数Ｄ’の比Ｄ／Ｄ’が１．０７以下であることを特徴とする人工毛髪用アクリル系繊維に関する。 The present invention is also an acrylic fiber for artificial hair comprising an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer, The acrylic copolymer has a weight average molecular weight of 100,000 or less and a sulfur content of 0.35% by weight or more. In the acrylic copolymer, the main chain diffusion coefficient measured by the DOSY method is used. The present invention relates to an acrylic fiber for artificial hair, wherein the ratio D / D ′ of D and the diffusion coefficient D ′ of the sulfonic acid group-containing component is 1.07 or less.
　本発明は、また、前記のアクリル系共重合体の製造方法であって、アクリロニトリルと、塩化ビニル及び／又は塩化ビニリデンと、スルホン酸基含有ビニル単量体の重合を単一反応槽において連続的に行う際、重合反応開始時にはスルホン酸基含有ビニル単量体を反応槽に投入せず、重合反応開始後、アクリル系共重合体の収量がアクリル系共重合体の目的量の８重量％以上２１重量％以下の所定の量になる時点から、重合反応が終了するまで、スルホン酸基含有ビニル単量体を一定の速度で連続的に反応槽に投入することを特徴とするアクリル系共重合体の製造方法に関する。 The present invention also relates to a method for producing the acrylic copolymer, wherein polymerization of acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer is continuously performed in a single reaction vessel. When the polymerization reaction is started, the sulfonic acid group-containing vinyl monomer is not charged into the reaction vessel at the start of the polymerization reaction. After the polymerization reaction is started, the yield of the acrylic copolymer is 8% by weight or more of the target amount of the acrylic copolymer. Acrylic copolymer having a sulfonic acid group-containing vinyl monomer continuously fed into a reaction vessel at a constant rate from the time when a predetermined amount of 21% by weight or less is reached until the polymerization reaction is completed. The present invention relates to a method for manufacturing coalescence.
　本発明は、また、前記の人工毛髪用アクリル系繊維の製造方法であって、アクリル系共重合体をジメチルスルホキシド、ジメチルアセトアミド及びＮ，Ｎ－ジメチルホルムアミドからなる群から選べる一種以上の有機溶媒に溶解して得られた紡糸原液を湿式紡糸することを特徴とする人工毛髪用アクリル系繊維の製造方法に関する。 The present invention also relates to the above-described method for producing an acrylic fiber for artificial hair, wherein the acrylic copolymer is used as one or more organic solvents selected from the group consisting of dimethyl sulfoxide, dimethylacetamide and N, N-dimethylformamide. The present invention relates to a method for producing acrylic fiber for artificial hair, characterized by wet spinning a spinning dope obtained by dissolution.
　本発明のアクリル系共重合体を用いることで、櫛通り性が良好な人工毛髪用アクリル系繊維を得ることができる。本発明の人工毛髪用アクリル系繊維は、櫛通り性が良好である。 By using the acrylic copolymer of the present invention, it is possible to obtain acrylic fiber for artificial hair having good combability. The acrylic fiber for artificial hair of the present invention has good combability.
　本発明のアクリル系共重合体の製造方法によると、重量平均分子量が１００，０００以下であり、硫黄含有量が０．３５重量％以上であり、ＤＯＳＹ法にて測定した主鎖の拡散係数Ｄとスルホン酸基含有成分の拡散係数Ｄ’の比Ｄ／Ｄ’が１．０７以下のアクリル系共重合体を得ることができる。 According to the method for producing an acrylic copolymer of the present invention, the weight average molecular weight is 100,000 or less, the sulfur content is 0.35% by weight or more, and the main chain diffusion coefficient D measured by the DOSY method. An acrylic copolymer having a ratio D / D ′ of 1.07 or less of the diffusion coefficient D ′ of the sulfonic acid group-containing component can be obtained.
　本発明の人工毛髪用アクリル系繊維の製造方法によると、前記のアクリル系重合体と、ジメチルスルホキシド、ジメチルアセトアミド及びＮ，Ｎ－ジメチルホルムアミドからなる群から選べる一種以上の有機溶媒を用いることで、生産性よく、櫛通り性が良好な人工毛髪用アクリル系繊維を得ることができる。 According to the method for producing acrylic fiber for artificial hair of the present invention, by using one or more organic solvents selected from the group consisting of the acrylic polymer and dimethyl sulfoxide, dimethylacetamide and N, N-dimethylformamide, An acrylic fiber for artificial hair with good productivity and good combing property can be obtained.
　本発明の発明者らは、アクリロニトリルと、塩化ビニル及び／又は塩化ビニリデンと、スルホン酸基含有ビニル単量体を共重合したアクリル系共重合体で構成されたアクリル系繊維の櫛通り性を改善することについて検討を重ねた。その結果、アクリル系共重合体において、重量平均分子量を１００，０００以下にし、硫黄含有量を０．３５重量％以上にし、且つＤＯＳＹ法にて測定した主鎖の拡散係数Ｄとスルホン酸基含有成分の拡散係数Ｄ’の比Ｄ／Ｄ’を１．０７以下にすることで、該アクリル系共重合体で構成されたアクリル系繊維の櫛通り性が改善することを見出し、本発明に至った。重量平均分子量が１００，０００以下であり、硫黄含有量が０．３５重量％以上であり、ＤＯＳＹ法にて測定した主鎖の拡散係数Ｄとスルホン酸基含有成分の拡散係数Ｄ’の比Ｄ／Ｄ’が１．０７以下であるアクリル系共重合体はジメチルスルホキシド等の有機溶媒に溶解させて紡糸原液とし、該紡糸原液を湿式紡糸した場合、平滑な表面を有する繊維を形成しやすく、繊維の櫛通り性が改善されることになる。 The inventors of the present invention improved the combing property of acrylic fibers composed of an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer. We made a lot of discussions about what to do. As a result, in the acrylic copolymer, the weight average molecular weight is 100,000 or less, the sulfur content is 0.35% by weight or more, and the main chain diffusion coefficient D and sulfonic acid group content measured by the DOSY method are used. The ratio D / D ′ of the component diffusion coefficient D ′ is set to 1.07 or less, and it has been found that the combing property of the acrylic fiber composed of the acrylic copolymer is improved, leading to the present invention. It was. The weight average molecular weight is 100,000 or less, the sulfur content is 0.35% by weight or more, and the ratio D between the diffusion coefficient D of the main chain and the diffusion coefficient D ′ of the sulfonic acid group-containing component measured by the DOSY method An acrylic copolymer having / D ′ of 1.07 or less is dissolved in an organic solvent such as dimethyl sulfoxide to form a spinning stock solution, and when the spinning stock solution is wet-spun, fibers having a smooth surface are easily formed. The combability of the fiber will be improved.
　前記アクリル系共重合体は、アクリル系共重合体の全体重量に対して、アクリロニトリルを３０～７０重量％、塩化ビニル及び／又は塩化ビニリデンを２５～６９．５重量％、並びにスルホン酸基含有ビニル単量体を０．５～５重量％含むことが好ましい。すなわち、前記アクリル系共重合体は、アクリロニトリル３０～７０重量％と、塩化ビニル及び／又は塩化ビニリデン２５～６９．５重量％と、スルホン酸基含有ビニル単量体０．５～５重量％を含む合計１００重量％の単量体混合物を重合したものである。前記アクリル系共重合体において、アクリロニトリルの含有量が３０～７０重量％であると、耐熱性が良好になり、該アクリル系共重合体で構成されたアクリル系繊維のカールセット時の加工温度を適宜に設定することができる。前記アクリル系共重合体において、塩化ビニル及び／又は塩化ビニリデンの含有量が２５～６９．５重量％であると、難燃性が良好になる。前記アクリル系共重合体がスルホン酸基含有ビニル単量体を０．５～５重量％含むことにより、染色性が良好になるとともに、親水性が増加し、ボイド率が低くなる。前記アクリル系共重合体は、アクリル系共重合体の全体重量に対して、スルホン酸基含有ビニル単量体を１重量％以上含むことが好ましく、１．５重量％以上含むことがさらに好ましい。また、前記アクリル系共重合体は、アクリル系共重合体の全体重量に対して、塩化ビニル及び／又は塩化ビニリデンを６９重量％以下含むことがより好ましく、６８．５重量％以下含むことがさらに好ましい。 The acrylic copolymer comprises 30 to 70% by weight of acrylonitrile, 25 to 69.5% by weight of vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl based on the total weight of the acrylic copolymer. It is preferable to contain 0.5 to 5% by weight of monomer. That is, the acrylic copolymer contains 30 to 70% by weight of acrylonitrile, 25 to 69.5% by weight of vinyl chloride and / or vinylidene chloride, and 0.5 to 5% by weight of sulfonic acid group-containing vinyl monomer. A total of 100% by weight of the monomer mixture is polymerized. In the acrylic copolymer, when the acrylonitrile content is 30 to 70% by weight, the heat resistance is improved, and the processing temperature at the curl setting of the acrylic fiber composed of the acrylic copolymer is set. It can be set appropriately. In the acrylic copolymer, when the content of vinyl chloride and / or vinylidene chloride is 25 to 69.5% by weight, the flame retardancy is good. When the acrylic copolymer contains 0.5 to 5% by weight of the sulfonic acid group-containing vinyl monomer, the dyeability is improved, the hydrophilicity is increased, and the void ratio is lowered. The acrylic copolymer preferably contains 1% by weight or more, more preferably 1.5% by weight or more of the sulfonic acid group-containing vinyl monomer with respect to the total weight of the acrylic copolymer. The acrylic copolymer preferably contains 69% by weight or less, more preferably 68.5% by weight or less of vinyl chloride and / or vinylidene chloride based on the total weight of the acrylic copolymer. preferable.
　触感により優れる観点から、前記アクリル系共重合体は塩化ビニルを含むことが好ましい。 From the viewpoint of superior tactile sensation, the acrylic copolymer preferably contains vinyl chloride.
　前記スルホン酸基含有ビニル単量体としては、特に限定されないが、例えば、アリルスルホン酸、メタリルスルホン酸、スチレンスルホン酸、イソプレンスルホン酸、２－アクリルアミド－２－メチルプロパンスルホン酸等のスルホン酸化合物、パラスチレンスルホン酸ナトリウム等のこれらのスルホン酸化合物のナトリウム塩等の金属塩類、スチレンスルホン酸アミン塩等のこれらのスルホン酸化合物のアミン塩類等を用いることができる。前記スルホン酸基含有ビニル単量体は単独もしくは２種以上組み合わせて用いることができる。 The sulfonic acid group-containing vinyl monomer is not particularly limited, and examples thereof include sulfonic acids such as allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid. Compounds, metal salts such as sodium salts of these sulfonic acid compounds such as sodium parastyrene sulfonate, and amine salts of these sulfonic acid compounds such as styrene sulfonic acid amine salts can be used. The sulfonic acid group-containing vinyl monomers can be used alone or in combination of two or more.
　前記アクリル系共重合体は、重量平均分子量（Ｍｗ）が１００，０００以下である。前記アクリル系共重合体の重量平均分子量が１００，０００以下であると、紡糸原液の樹脂濃度が高い場合でも、紡糸原液の粘度が紡糸に適した粘度になりやすい。他方、重量平均分子量が低いと、繊維強度が弱くなり、櫛通り性が良好な繊維が得られにくい傾向がある。紡糸原液の樹脂濃度を高め、緻密な繊維構造を実現すること、及び繊維強度を両立する観点から、前記アクリル系共重合体は、重量平均分子量が６０，０００～１００，０００であることが好ましく、より好ましくは７０，０００～１００，０００である。 The acrylic copolymer has a weight average molecular weight (Mw) of 100,000 or less. When the acrylic copolymer has a weight average molecular weight of 100,000 or less, the viscosity of the spinning solution tends to be suitable for spinning even when the resin concentration of the spinning solution is high. On the other hand, if the weight average molecular weight is low, the fiber strength tends to be weak, and it is difficult to obtain fibers with good combing properties. The acrylic copolymer preferably has a weight average molecular weight of 60,000 to 100,000 from the viewpoint of increasing the resin concentration of the spinning dope, realizing a dense fiber structure, and achieving both fiber strength. More preferably, it is 70,000 to 100,000.
　前記アクリル系共重合体は、特に限定されないが、紡糸原液の樹脂濃度を高め、緻密な繊維構造を実現すること、及び繊維強度を両立する観点から、数平均分子量（Ｍｎ）が２０，０００～５０，０００であることが好ましく、３０，０００～５０，０００であることがより好ましい。本発明の実施形態において、アクリル系共重合体の重量平均分子量、数平均分子量は、ゲル浸透クロマトグラフで測定することができる。 The acrylic copolymer is not particularly limited, but has a number average molecular weight (Mn) of 20,000 to 20,000 from the viewpoint of increasing the resin concentration of the spinning dope, realizing a dense fiber structure, and achieving both fiber strength. It is preferably 50,000, and more preferably 30,000 to 50,000. In the embodiment of the present invention, the weight average molecular weight and number average molecular weight of the acrylic copolymer can be measured by gel permeation chromatography.
　前記アクリル系共重合体は、特に限定されないが、繊維強度を高め、櫛通り性が良好な繊維を得る観点から、数平均分子量に対する重量平均分子量の比（Ｍｗ／Ｍｎ）で示される分子量分布（ＰＤＩとも記す。）が２．０～４．０であることが好ましく、２．０～３．０であることがより好ましい。 The acrylic copolymer is not particularly limited, but a molecular weight distribution (Mw / Mn) represented by a ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) from the viewpoint of increasing fiber strength and obtaining fibers having good combability. (Also referred to as PDI)) is preferably 2.0 to 4.0, more preferably 2.0 to 3.0.
　前記アクリル系共重合体は、硫黄含有量が０．３５重量％以上である。前記アクリル系共重合体中の硫黄含有量が０．３５重量％以上であると、該アクリル系共重合体を用いて湿式紡糸を行う際、緻密な凝固になりやすい。前記アクリル系共重合体中の硫黄含有量が０．３５～１．０重量％であることが好ましく、０．４～０．６重量％であることがより好ましい。本発明の実施形態において、硫黄含有量は、後述するとおりに測定することができる。 The acrylic copolymer has a sulfur content of 0.35% by weight or more. When the sulfur content in the acrylic copolymer is 0.35% by weight or more, when wet spinning is performed using the acrylic copolymer, dense solidification tends to occur. The sulfur content in the acrylic copolymer is preferably 0.35 to 1.0% by weight, and more preferably 0.4 to 0.6% by weight. In embodiments of the present invention, the sulfur content can be measured as described below.
　前記アクリル系共重合体において、ＤＯＳＹ法にて測定した主鎖の拡散係数Ｄとスルホン酸基含有成分の拡散係数Ｄ’の比Ｄ／Ｄ’（以下において、単に「Ｄ／Ｄ’」とも記す。）が１．０７以下である。Ｄ／Ｄ’が１．０７以下のアクリル系共重合体をジメチルスルホキシド等の有機溶媒に溶解して得られた紡糸原液を湿式紡糸した場合、平滑な表面を有する繊維が得られやすい。Ｄ／Ｄ’が１．０７を超えると、スルホン酸基の親水性が発揮されにくく、緻密な凝固体が得られない。Ｄ／Ｄ’は、０．４以上１．０７以下であることが好ましく、０．６以上１．０７以下であることがより好ましい。本発明の実施形態において、ＤＯＳＹ法による拡散係数の測定は後述するとおりに行うことができる。 In the acrylic copolymer, the ratio D / D ′ (hereinafter also simply referred to as “D / D ′”) of the diffusion coefficient D ′ of the main chain measured by the DOSY method and the diffusion coefficient D ′ of the sulfonic acid group-containing component. .) Is 1.07 or less. When a spinning dope obtained by dissolving an acrylic copolymer having a D / D 'of 1.07 or less in an organic solvent such as dimethyl sulfoxide is wet-spun, fibers having a smooth surface are easily obtained. When D / D 'exceeds 1.07, the hydrophilicity of the sulfonic acid group is difficult to be exhibited, and a dense solidified body cannot be obtained. D / D ′ is preferably 0.4 or more and 1.07 or less, and more preferably 0.6 or more and 1.07 or less. In the embodiment of the present invention, the measurement of the diffusion coefficient by the DOSY method can be performed as described later.
　前記アクリル系共重合体において、スルホン酸基含有成分の拡散係数は１７～５０μｍ２／ｓｅｃであることが好ましく、より好ましくは２０～３５μｍ２／ｓｅｃである。スルホン酸基含有成分の拡散係数が小さすぎると、スルホン酸基含有成分中に占めるスルホン酸の割合が低くなり、親水性が低下し、紡糸時に緻密な凝固が得られにくい傾向がある。また、スルホン酸基含有成分の拡散係数が大きすぎると、分子鎖の親水性が過度に高くなり、スルホン酸基含有の成分が紡糸時に浴中に溶出してしまう恐れがある。 In the acrylic copolymer, the diffusion coefficient of the sulfonic acid group-containing component is preferably 17 to 50 μm 2 / sec, more preferably 20 to 35 μm 2 / sec. If the diffusion coefficient of the sulfonic acid group-containing component is too small, the proportion of the sulfonic acid in the sulfonic acid group-containing component is reduced, the hydrophilicity is lowered, and there is a tendency that dense solidification is difficult to obtain during spinning. If the diffusion coefficient of the sulfonic acid group-containing component is too large, the hydrophilicity of the molecular chain becomes excessively high and the sulfonic acid group-containing component may be eluted into the bath during spinning.
　前記アクリル系共重合体において、下記数式（１）で示されるスルホン酸基含有成分の重量平均分子量は２４，０００～１１０，０００であることが好ましく、３６，０００～１００，０００であることがより好ましい。紡糸工程において緻密な凝固を実現することができるとともに、スルホン酸基含有の成分の浴中への溶出を効果的に防ぐことができる。下記数式（１）において、Ｍｗ’はスルホン酸基含有成分の重量平均分子量であり、Ｍｗはアクリル系共重合体の重量平均分子量である。
Ｍｗ’＝（Ｄ／Ｄ’）２×Ｍｗ　　（１） In the acrylic copolymer, the weight average molecular weight of the sulfonic acid group-containing component represented by the following formula (1) is preferably 24,000 to 110,000, and preferably 36,000 to 100,000. More preferred. Dense solidification can be realized in the spinning process, and elution of the sulfonic acid group-containing component into the bath can be effectively prevented. In the following mathematical formula (1), Mw ′ is the weight average molecular weight of the sulfonic acid group-containing component, and Mw is the weight average molecular weight of the acrylic copolymer.
Mw ′ = (D / D ′) 2 × Mw (1)
　前記アクリル系共重合体は、アクリロニトリル、塩化ビニル及び／又は塩化ビニリデン、及びスルホン酸基含有ビニル単量体を共重合することで作製することができる。共重合の方法は、特に限定されず、通常のビニル重合法、例えば、スラリー重合法、乳化重合法、溶液重合法等の方法を用いることができる。Ｄ／Ｄ’が１．０７以下であり、所望の分子量を有するアクリル系共重合体を容易に得ることができる観点から、重合は乳化重合法で行うことが好ましく、生産工程の安定性から、単一の反応槽にて連続的に行うことが好ましい。 The acrylic copolymer can be prepared by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer. The method of copolymerization is not particularly limited, and usual vinyl polymerization methods such as slurry polymerization method, emulsion polymerization method, solution polymerization method and the like can be used. From the viewpoint that D / D ′ is 1.07 or less and an acrylic copolymer having a desired molecular weight can be easily obtained, the polymerization is preferably carried out by an emulsion polymerization method, from the stability of the production process, It is preferable to carry out continuously in a single reaction vessel.
　アクリロニトリルと、塩化ビニル及び／又は塩化ビニリデンと、スルホン酸基含有ビニル単量体の重合を単一反応槽において連続的に行う際、重合反応開始時にはスルホン酸基含有ビニル単量体を反応槽に投入せず、重合反応開始後、アクリル系共重合体の収量がアクリル系共重合体の目的量の８重量％以上２１重量％以下の所定の量になる時点から、重合反応が終了するまで、スルホン酸基含有ビニル単量体を一定の速度で連続的に投入することで、重量平均分子量が１００，０００以下であり、硫黄含有量が０．３５重量％以上であり、Ｄ／Ｄ’が１．０７以下のアクリル系共重合体を得ることができる。アクリル系共重合体の収量がアクリル系共重合体の目的量の８重量％に達していない時点でスルホン酸基含有ビニル単量体を反応槽に投入すると、スルホン酸基含有ビニル単量体同士が重合しやすくなる。一方、アクリル系共重合体の収量がアクリル系共重合体の目的量の２１重量％を超えた後にスルホン酸基含有ビニル単量体を応槽に投入すると、Ｄ／Ｄ’が１．０７より大きくなってしまう。 When polymerization of acrylonitrile, vinyl chloride and / or vinylidene chloride, and sulfonic acid group-containing vinyl monomer is continuously performed in a single reaction tank, the sulfonic acid group-containing vinyl monomer is added to the reaction tank at the start of the polymerization reaction. Without starting, after starting the polymerization reaction, from the time when the yield of the acrylic copolymer becomes a predetermined amount of 8 wt% to 21 wt% of the target amount of the acrylic copolymer, until the polymerization reaction is completed, By continuously adding the sulfonic acid group-containing vinyl monomer at a constant rate, the weight average molecular weight is 100,000 or less, the sulfur content is 0.35% by weight or more, and D / D ′ is An acrylic copolymer of 1.07 or less can be obtained. When the yield of the acrylic copolymer does not reach 8% by weight of the target amount of the acrylic copolymer, when the sulfonic acid group-containing vinyl monomer is introduced into the reaction vessel, the sulfonic acid group-containing vinyl monomers Becomes easy to polymerize. On the other hand, when the yield of the acrylic copolymer exceeds 21% by weight of the target amount of the acrylic copolymer and the sulfonic acid group-containing vinyl monomer is introduced into the reaction vessel, D / D ′ is 1.07 or more. It gets bigger.
　前記乳化重合は、スルホン酸基含有ビニル単量体の反応槽への投入を上述するとおりに行う以外は、一般的な方法と同様に水溶性開始剤の存在下、乳化剤を用いて行うことができる。 The emulsion polymerization can be carried out using an emulsifier in the presence of a water-soluble initiator in the same manner as a general method, except that the sulfonic acid group-containing vinyl monomer is charged into the reaction vessel as described above. it can.
　水溶性開始剤としては、特に限定されないが、酸化剤として機能する過硫酸塩を用いることが好ましい。活性化エネルギーが低く低温でも収率を高めることができる。過硫酸塩は、単量体の合計重量を１００重量部とした場合、０．１～０．４重量部添加することが好ましく、０．２～０．３重量部添加することがより好ましい。 The water-soluble initiator is not particularly limited, but it is preferable to use a persulfate that functions as an oxidizing agent. The activation energy is low and the yield can be increased even at low temperatures. The persulfate is preferably added in an amount of 0.1 to 0.4 parts by weight, more preferably 0.2 to 0.3 parts by weight, when the total weight of the monomers is 100 parts by weight.
　過硫酸塩としては、例えば、過硫酸アンモニウム、過硫酸カリウム等が挙げられるが、これらに限定されるものではない。還元剤としては、例えば、亜硫酸水素ナトリウム、重亜硫酸水素ナトリウム、亜硫酸等が挙げられるが、これらに限定されるものではない。その他に、硫酸鉄や硫酸銅等の触媒分解促進剤、ｔ－ブチルメルカプタン、２－メルカプトエタノール等の連鎖移動剤を併用しても良い。触媒分解促進剤は、所望の分子量のアクリル系共重合体が得られやすい観点から、単量体の合計重量を１００重量部とした場合、０．００１８～０．００３９重量部であることが好ましい。乳化剤は、通常乳化重合で使用されるアニオン性界面活性剤が好ましく、例えば、アルキルベンゼンスルホン酸塩、アルキルアルコール硫酸エステル塩等が挙げられるが、これらに限定されるものではない。アルキルアルコール硫酸エステル塩としては、例えば、ラウリル硫酸ナトリウム等を用いることができる。 Examples of the persulfate include, but are not limited to, ammonium persulfate and potassium persulfate. Examples of the reducing agent include, but are not limited to, sodium bisulfite, sodium bisulfite, and sulfurous acid. In addition, catalyst decomposition accelerators such as iron sulfate and copper sulfate, and chain transfer agents such as t-butyl mercaptan and 2-mercaptoethanol may be used in combination. From the viewpoint of easily obtaining an acrylic copolymer having a desired molecular weight, the catalyst decomposition accelerator is preferably 0.0018 to 0.0039 parts by weight when the total weight of the monomers is 100 parts by weight. . The emulsifier is preferably an anionic surfactant usually used in emulsion polymerization, and examples thereof include, but are not limited to, alkylbenzene sulfonate and alkyl alcohol sulfate. As the alkyl alcohol sulfate ester salt, for example, sodium lauryl sulfate can be used.
　重合温度は、アクリル系共重合体の生産性や品質の点から４０～７０℃であることが好ましく、より好ましくは４５～５５℃である。反応槽へ連続的に添加する単量体、開始剤、乳化剤及び水等の原料類は、定量ポンプの制御下で正確に添加するが、反応槽内で発生する重合熱の除熱量を確保するため必要に応じて予め冷却しても良い。反応槽からのラテックスの払い出しは、反応槽内部の圧力を保持しかつ添加原料と同量の共重合体液を払い出すように反応槽底部あるいは側面下部から定量ポンプ若しくは流量制御弁を用いて行うのが好ましい。反応槽内部の平均滞留時間（反応槽の容積を１時間あたりの追加原料量で除した時間）は、通常０．５～１０時間、好ましくは１．５～３時間とするのがラテックスの機械的安定性及び共重合体を繊維とした際の品質の面で好ましい。払い出されたアクリル系共重合体のラテックスには、必要に応じて重合禁止剤、凝固剤、難燃剤、ｐＨ調節剤を添加しても良く、未反応単量体の回収や後重合を行っても良い。その後、凝固、熱処理、脱水、水洗、乾燥等公知の方法を経てアクリル系共重合体を得ることができる。 The polymerization temperature is preferably 40 to 70 ° C., more preferably 45 to 55 ° C. from the viewpoint of productivity and quality of the acrylic copolymer. Raw materials such as monomers, initiators, emulsifiers and water that are continuously added to the reaction tank are accurately added under the control of the metering pump, but the amount of heat removed from the polymerization heat generated in the reaction tank is ensured. Therefore, you may cool beforehand as needed. The latex is discharged from the reaction tank using a metering pump or a flow control valve from the bottom of the reaction tank or from the lower side of the reaction tank so as to maintain the pressure inside the reaction tank and to discharge the same amount of copolymer liquid as the added raw material. Is preferred. The average residence time inside the reaction tank (time obtained by dividing the volume of the reaction tank by the amount of additional raw materials per hour) is usually 0.5 to 10 hours, preferably 1.5 to 3 hours. It is preferable in terms of mechanical stability and quality when the copolymer is a fiber. If necessary, a polymerization inhibitor, a coagulant, a flame retardant, and a pH adjuster may be added to the discharged acrylic copolymer latex, and unreacted monomers are recovered and post-polymerized. May be. Thereafter, an acrylic copolymer can be obtained through known methods such as coagulation, heat treatment, dehydration, washing with water, and drying.
　本発明の実施形態の人工毛髪用アクリル系繊維は、前記アクリル系共重合体で構成されている。人工毛髪用アクリル系繊維を構成したアクリル系共重合体の重量平均分子量（Ｍｗ）、数量平均分子量（Ｍｎ）、硫黄含有量、主鎖の拡散係数及びスルホン酸基含有成分の拡散係数は、上述した繊維を構成する前のアクリル系共重合体と同様であり、試料として繊維を用いる以外は、アクリル系共重合体の場合と同様にして測定することができる。 The acrylic fiber for artificial hair according to the embodiment of the present invention is composed of the acrylic copolymer. The weight average molecular weight (Mw), the number average molecular weight (Mn), the sulfur content, the diffusion coefficient of the main chain and the diffusion coefficient of the sulfonic acid group-containing component of the acrylic copolymer constituting the acrylic fiber for artificial hair are described above. It is the same as that of the acrylic copolymer before constituting the prepared fiber, and can be measured in the same manner as in the case of the acrylic copolymer except that the fiber is used as a sample.
　前記人工毛髪用アクリル系繊維は、櫛通り性に優れる観点から、繊維側面の縦４０μｍ、横８０μｍの領域において、表面粗さが６１００μｍ２以下であることが好ましく、より好ましくは６０００μｍ２以下であり、さらに好ましくは５９００μｍ２以下である。本発明の実施形態において、表面粗さは、後述するとおりに測定算出することができる。 From the viewpoint of excellent combability, the acrylic fiber for artificial hair preferably has a surface roughness of 6100 μm 2 or less, more preferably 6000 μm 2 or less in the region of 40 μm length and 80 μm width on the fiber side surface. More preferably, it is 5900 μm 2 or less. In the embodiment of the present invention, the surface roughness can be measured and calculated as described later.
　前記人工毛髪用アクリル系繊維は、前記アクリル系共重合体を有機溶媒に溶解して得られた紡糸原液を湿式紡糸することで作製することができる。生産性の観点から、有機溶媒は、ジメチルスルホキシド（ＤＭＳＯ）、ジメチルアセトアミド（ＤＭＡｃ）及びＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）からなる群から選べる一種以上の有機溶媒であることが好ましく、生産性及び安全性の観点から、有機溶媒はジメチルスルホキシドであることがより好ましい。 The acrylic fiber for artificial hair can be produced by wet-spinning a spinning stock solution obtained by dissolving the acrylic copolymer in an organic solvent. From the viewpoint of productivity, the organic solvent is preferably one or more organic solvents selected from the group consisting of dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc) and N, N-dimethylformamide (DMF). From the viewpoint of safety, the organic solvent is more preferably dimethyl sulfoxide.
　前記紡糸原液は、アクリル系共重合体の組成にもよるが、紡糸原液の全体重量に対して、アクリル系共重合体を２０～３０重量％含むことが好ましく、より好ましくはアクリル系共重合体を２２～３０重量％含み、さらに好ましくはアクリル系共重合体を２５～３０重量％含む。前記紡糸原液は、ボイド形成を抑制する観点から、少量の水を含んでもよい。例えば、紡糸原液の全体重量に対して、水を１～５重量％含むことが好ましく、より好ましくは２～４重量％含む。 Although the spinning dope depends on the composition of the acrylic copolymer, it preferably contains 20-30% by weight of the acrylic copolymer, more preferably the acrylic copolymer, based on the total weight of the spinning dope. Is contained in an amount of 22 to 30% by weight, more preferably 25 to 30% by weight of an acrylic copolymer. The spinning dope may contain a small amount of water from the viewpoint of suppressing void formation. For example, the water content is preferably 1 to 5% by weight, more preferably 2 to 4% by weight, based on the total weight of the spinning dope.
　前記紡糸原液は、本発明の効果を阻害しない範囲内であれば、必要に応じて、繊維特性を改良するための他の添加剤を含んでもよい。添加剤としては、例えば、二酸化チタン、二酸化ケイ素、酢酸セルロースをはじめとするセルロース誘導体のエステル及びエーテル等の光沢調整剤、有機顔料、無機顔料及び染料等の着色剤、耐光性や耐熱性向上のための安定剤等が挙げられる。 The spinning undiluted solution may contain other additives for improving the fiber characteristics, if necessary, as long as the effects of the present invention are not impaired. Examples of additives include gloss modifiers such as esters and ethers of cellulose derivatives such as titanium dioxide, silicon dioxide, and cellulose acetate, colorants such as organic pigments, inorganic pigments, and dyes, and improvements in light resistance and heat resistance. Stabilizers and the like.
　前記紡糸原液を通常の方法で湿式紡糸することでアクリル系繊維を得る。例えば、まず、前記紡糸原液を、紡糸ノズルを通して或いは直接凝固浴へ吐出して凝固させて繊維化する。凝固浴は、例えばジメチルスルホキシド等の有機溶媒の濃度が４０～７０重量％の水溶液を用いることができる。凝固浴の温度は５～４０℃とすることができる。凝固浴中のジメチルスルホキシド等の有機溶媒の濃度が低すぎると、凝固が速くなって凝固構造が粗になり繊維内部にボイドを形成する傾向がある。 Acrylic fibers are obtained by wet-spinning the spinning dope using a conventional method. For example, the spinning solution is first solidified by discharging through a spinning nozzle or directly into a coagulation bath to coagulate. As the coagulation bath, for example, an aqueous solution having an organic solvent concentration of 40 to 70% by weight such as dimethyl sulfoxide can be used. The temperature of the coagulation bath can be 5 to 40 ° C. If the concentration of the organic solvent such as dimethyl sulfoxide in the coagulation bath is too low, coagulation is accelerated and the coagulation structure becomes rough and voids tend to form inside the fiber.
　次いで、繊維（凝固糸）は、水洗する。水洗により有機溶剤を除去する。なお、紡糸原液に用いた有機溶剤は繊維から完全に除去することはできず、極微小量であるが、残存することがある。水洗には、３０℃以上の温水又は凝固浴より有機溶媒の濃度が低い有機溶媒の水溶液を用いることができる。また、水洗工程の前或いは水洗工程の後に、延伸浴中で浴延伸してもよい。延伸浴としては、３０℃以上の温水又は凝固浴より有機溶媒の濃度が低い有機溶媒の水溶液を用いることができる。例えば、３０℃以上の凝固液より有機溶媒の濃度が低い水溶液で浴延伸した後、３０℃以上の温水で水洗することが好ましい。浴延伸の延伸倍率は、特に限定されないが、繊維の強度及び生産性を高める観点から、２～８倍であることが好ましく、２～７倍であることがより好ましく、２～６倍であることがさらに好ましい。 Next, the fiber (coagulated yarn) is washed with water. The organic solvent is removed by washing with water. Note that the organic solvent used in the spinning dope cannot be completely removed from the fiber and may remain in an extremely small amount. For washing with water, warm water of 30 ° C. or higher or an aqueous solution of an organic solvent having a lower concentration of the organic solvent than the coagulation bath can be used. In addition, bath stretching may be performed in a stretching bath before or after the water washing step. As the stretching bath, warm water of 30 ° C. or higher or an aqueous solution of an organic solvent having a lower organic solvent concentration than the coagulation bath can be used. For example, it is preferable to perform bath stretching with an aqueous solution having a lower organic solvent concentration than the coagulating liquid at 30 ° C. or higher, and then wash with warm water at 30 ° C. or higher. The draw ratio of the bath drawing is not particularly limited, but is preferably 2 to 8 times, more preferably 2 to 7 times, and more preferably 2 to 6 times from the viewpoint of enhancing the strength and productivity of the fiber. More preferably.
　次いで、アクリル系繊維は乾燥させてもよい。乾燥時には、必要に応じて、油剤を付着させてもよい。油剤は、紡糸工程において、通常、静電防止、繊維の膠着防止や風合い改良を目的として用いられるものであればよく、公知の油剤を用いることができる。乾燥温度としては、特に限定されないが、例えば、１１０～１９０℃、好ましくは１１０～１６０℃である。乾燥した繊維は、そののち、必要により、さらに延伸してもよく、その延伸比は１～４倍が好ましい。乾燥前の延伸を含めた全延伸比は、２～１２倍であることが好ましい。 Next, the acrylic fiber may be dried. When drying, an oil agent may be attached as necessary. The oil agent may be any oil agent as long as it is usually used for the purpose of preventing static electricity, preventing fiber sticking and improving the texture in the spinning process, and a known oil agent can be used. The drying temperature is not particularly limited, but is, for example, 110 to 190 ° C., preferably 110 to 160 ° C. Thereafter, the dried fiber may be further stretched if necessary, and the stretch ratio is preferably 1 to 4 times. The total stretching ratio including stretching before drying is preferably 2 to 12 times.
　乾燥或いは乾燥した後にさらに延伸して得られた繊維は、さらに、熱緩和処理工程にて緩和されることが好ましい。緩和率は、特に限定されないが、例えば、５％以上であることが好ましく、１０％以上であることがより好ましい。熱緩和処理は、高温、例えば１３０～２００℃、好ましくは１４０～１９０℃の乾熱雰囲気下又は過熱水蒸気雰囲気下で行うことができる。或いは、１２０～１８０℃の０．０５～０．４ＭＰａ、好ましくは０．１～０．４ＭＰａの加圧水蒸気又は加熱加圧水蒸気雰囲気下で行なうことができる。 It is preferable that the fiber obtained by further stretching after drying or drying is further relaxed in a thermal relaxation treatment step. The relaxation rate is not particularly limited, but is preferably 5% or more, and more preferably 10% or more, for example. The thermal relaxation treatment can be performed in a dry heat atmosphere or a superheated steam atmosphere at a high temperature, for example, 130 to 200 ° C., preferably 140 to 190 ° C. Alternatively, it can be carried out in a pressurized steam or heated and pressurized steam atmosphere of 0.05 to 0.4 MPa, preferably 0.1 to 0.4 MPa at 120 to 180 ° C.
　前記人工毛髪用アクリル系繊維は、人工毛髪として好適に用いる観点から、単繊維繊度が１０～１００ｄｔｅｘであることが好ましく、２０～９５ｄｔｅｘであることがより好ましく、３０～９０ｄｔｅｘであることがさらに好ましく、さらにより好ましくは４０～８０ｄｔｅｘ、さらにより好ましくは４５～７０ｄｔｅｘである。ここで、単繊維繊度とは任意の１００本の単繊維の繊度の平均値を意味する。 The acrylic fiber for artificial hair preferably has a single fiber fineness of 10 to 100 dtex, more preferably 20 to 95 dtex, and even more preferably 30 to 90 dtex, from the viewpoint of suitable use as artificial hair. Even more preferably, it is 40 to 80 dtex, and even more preferably 45 to 70 dtex. Here, the single fiber fineness means an average value of fineness of any 100 single fibers.
　前記人工毛髪用アクリル系繊維は、櫛通り性が良好である。櫛通り性は、例えば、後述するとおりに評価することができる。 The acrylic fiber for artificial hair has good combability. Combability can be evaluated, for example, as described below.
　前記人工毛髪用アクリル系繊維を用いて頭飾製品を構成することができる。前記頭飾製品は、前記人工毛髪用アクリル系繊維に加えて他の人工毛髪用繊維を含んでもよい。他の人工毛髪用繊維としては、特に限定されないが、例えば、ポリ塩化ビニル系繊維、ナイロン繊維、ポリエステル繊維、再生コラーゲン繊維等が挙げられる。 A headdress product can be constructed using the acrylic fiber for artificial hair. The head decoration product may include other artificial hair fibers in addition to the artificial hair acrylic fibers. Other artificial hair fibers are not particularly limited, and examples thereof include polyvinyl chloride fibers, nylon fibers, polyester fibers, and regenerated collagen fibers.
　頭飾製品としては、頭髪用繊維束、ウィービング、ウィッグ、ブレード、ツーペ、ヘアーエクステンション及びヘアアクセサリー等が挙げられる。 Examples of hair ornament products include hair bundles for hair, weaving, wigs, blades, two-pieces, hair extensions and hair accessories.
　以下実施例により本発明を更に具体的に説明する。なお、本発明は下記の実施例に限定されるものではない。下記において、特に指摘がない場合、「部」は「重量部」を意味し、「％」は「重量％」を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example. In the following, unless otherwise indicated, “part” means “part by weight”, and “%” means “% by weight”.
　（実施例１）
　＜アクリル系共重合体の製造＞
　アクリル系共重合体は、乳化重合を単一反応槽において連続的に行うことで作製した。まず、１４Ｌ反応槽にイオン交換水１６２．２部、ラウリル硫酸ナトリウム０．８７部、亜硫酸水素ナトリウム０．６部、硫酸鉄０．００３９部、硫酸０．３部、アクリロニトリル３．５部、塩化ビニル５４．５部を投入し、温度４９℃で、アクリロニトリル及び過硫酸アンモニウムを一定速度で連続的に追加しながら５時間４０分重合を行った。重合反応終了まで、アクリロニトリルの追加投入量及び過硫酸アンモニウムの投入量は、それぞれ、４０部及び０．２６４４部であった。また、重合反応開始後、アクリル系共重合体の収量が目的量の９．０％となった時点から、パラスチレンスルホン酸ナトリウムを一定速度で反応槽へ投入し、重合反応終了まで計２部投入した。重合反応終了後、未反応の塩化ビニルを回収し、アクリル系共重合体ラテックスを得た。得られたアクリル系共重合体ラテックスを塩析により凝固し、続いて熱処理、濾過、水洗、脱水及び乾燥を行い、４６．０％のアクリロニトリルと、５２．０％の塩化ビニルと、２．０％のパラスチレンスルホン酸ナトリウムからなるアクリル系共重合体を得た。なお、アクリル系共重合体の組成分析は、元素分析によりアクリロニトリル含有率を確認し、硫黄分析によりスチレンスルホン酸ナトリウム含有量を確認することで行った。
　＜湿式紡糸＞
　上記で得られた４６．０％のアクリロニトリルと、５２．０％の塩化ビニルと、２．０％のパラスチレンスルホン酸ナトリウムからなるアクリル系共重合体をジメチルスルホキシドに溶解し、樹脂濃度が２８．５％の紡糸原液を得た。なお、紡糸原液は、３．５％の水を含むように調整した。得られた紡糸原液の粘度は５０℃で１１０００ｍＰａ・Ｓであった。該紡糸原液を、紡糸ノズル（孔径０．３ｍｍ、孔数５０個）を用いて２０℃、５７重量％のジメチルスルホキシドの水溶液からなる凝固浴中に吐出して凝固させて繊維化した後、８０℃、５０重量％のジメチルスルホキシドの水溶液からなる延伸浴中で３倍に延伸した。続いて９０℃の温水にて水洗を実施した後、１４０℃で乾燥してから２倍に延伸し、１６０℃にて２０％緩和処理を施して単繊維繊度が約４６ｄｔｅｘのアクリル系繊維を得た。 (Example 1)
<Manufacture of acrylic copolymer>
The acrylic copolymer was produced by continuously performing emulsion polymerization in a single reaction tank. First, 162.2 parts of ion exchange water, 0.87 part of sodium lauryl sulfate, 0.6 part of sodium hydrogen sulfite, 0.0039 part of iron sulfate, 0.3 part of sulfuric acid, 3.5 parts of acrylonitrile, 54.5 parts of vinyl was added, and polymerization was carried out at 49 ° C. for 5 hours and 40 minutes while continuously adding acrylonitrile and ammonium persulfate at a constant rate. Until the polymerization reaction was completed, the addition amount of acrylonitrile and the addition amount of ammonium persulfate were 40 parts and 0.2644 parts, respectively. In addition, after the polymerization reaction started, when the yield of the acrylic copolymer reached 9.0% of the target amount, sodium parastyrenesulfonate was charged into the reaction vessel at a constant rate, and a total of 2 parts until the polymerization reaction was completed. I put it in. After completion of the polymerization reaction, unreacted vinyl chloride was recovered to obtain an acrylic copolymer latex. The resulting acrylic copolymer latex was coagulated by salting out, followed by heat treatment, filtration, washing with water, dehydration and drying to obtain 46.0% acrylonitrile, 52.0% vinyl chloride, 2.0 % Acrylic copolymer consisting of sodium parastyrene sulfonate was obtained. The composition analysis of the acrylic copolymer was performed by confirming the acrylonitrile content by elemental analysis and confirming the sodium styrenesulfonate content by sulfur analysis.
<Wet spinning>
An acrylic copolymer composed of 46.0% acrylonitrile, 52.0% vinyl chloride, and 2.0% sodium parastyrene sulfonate obtained above was dissolved in dimethyl sulfoxide, and the resin concentration was 28. A 5% spinning dope was obtained. The spinning dope was adjusted to contain 3.5% water. The viscosity of the obtained spinning dope was 11000 mPa · S at 50 ° C. The spinning stock solution was discharged into a coagulation bath composed of an aqueous solution of 57% by weight of dimethyl sulfoxide using a spinning nozzle (pore diameter: 0.3 mm, number of holes: 50), and solidified to give a fiber. The film was stretched 3 times in a stretching bath composed of an aqueous solution of dimethyl sulfoxide at 50 ° C. at 50 ° C. Subsequently, after washing with warm water of 90 ° C., drying at 140 ° C., stretching twice, and applying a 20% relaxation treatment at 160 ° C., an acrylic fiber having a single fiber fineness of about 46 dtex is obtained. It was.
　（実施例２）
　＜アクリル系共重合体の製造＞
　重合反応開始後、アクリル系共重合体の収量が目的量の１９％となった時点から、パラスチレンスルホン酸ナトリウムを一定速度で反応槽へ投入し、重合反応終了まで計２部投入した以外は、実施例１と同様にしてアクリル系共重合体を作製した。重合反応は５時間４０分行った。
　＜湿式紡糸＞
　上記で得られたアクリル系共重合体を用いた以外は、実施例１と同様にして、単繊維繊度が約４６ｄｔｅｘのアクリル系繊維を得た。 (Example 2)
<Manufacture of acrylic copolymer>
After starting the polymerization reaction, from the time when the yield of the acrylic copolymer reached 19% of the target amount, sodium parastyrenesulfonate was charged into the reaction vessel at a constant rate, and a total of 2 parts were charged until the polymerization reaction was completed. In the same manner as in Example 1, an acrylic copolymer was produced. The polymerization reaction was carried out for 5 hours and 40 minutes.
<Wet spinning>
An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1 except that the acrylic copolymer obtained above was used.
　（実施例３）
　重合反応に使用する硫酸鉄を０．００１８部へと変更した以外は、実施例１と同様にしてアクリル系共重合体を作成した。重合反応は５時間４０分行った。
＜湿式紡糸＞
　上記で得られたアクリル系共重合体を用いた以外は、実施例１と同様にして、単繊維繊度が約４６ｄｔｅｘのアクリル系繊維を得た。 (Example 3)
An acrylic copolymer was prepared in the same manner as in Example 1 except that the iron sulfate used in the polymerization reaction was changed to 0.0018 part. The polymerization reaction was carried out for 5 hours and 40 minutes.
<Wet spinning>
An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1 except that the acrylic copolymer obtained above was used.
　（比較例１）
　＜アクリル系共重合体の製造＞
　重合反応に使用する硫酸鉄を０．００１３部とし、また、重合反応開始後、アクリル系共重合体の収量が目的量の２２％となった時点から、パラスチレンスルホン酸ナトリウムを一定速度で反応槽へ投入し、重合反応終了まで計２部投入した以外は、実施例１と同様にしてアクリル系共重合体を作製した。重合反応は５時間４０分行った。
　＜湿式紡糸＞
　上記で得られたアクリル系共重合体を用いた以外は、実施例１と同様にして、単繊維繊度が約４６ｄｔｅｘのアクリル系繊維を得た。 (Comparative Example 1)
<Manufacture of acrylic copolymer>
The iron sulfate used for the polymerization reaction is 0.0013 parts, and after the polymerization reaction starts, when the yield of the acrylic copolymer reaches 22% of the target amount, sodium parastyrenesulfonate is reacted at a constant rate. An acrylic copolymer was prepared in the same manner as in Example 1 except that it was charged into the tank and a total of 2 parts were charged until the polymerization reaction was completed. The polymerization reaction was carried out for 5 hours and 40 minutes.
<Wet spinning>
An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1 except that the acrylic copolymer obtained above was used.
　（比較例２）
　＜アクリル系共重合体の製造＞
　重合反応開始後、アクリル系共重合体の終了が目的量の４４％時点からパラスチレンスルホン酸ナトリウムを一定速度で反応槽に投入し、重合反応終了まで合計０．５部投入した以外は、比較例１と同様にしてアクリル系共重合体を作成した。重合反応は５時間４０分行った。
＜湿式紡糸＞
　上記で得られたアクリル系共重合体を用いた以外は、実施例１と同様にして、単繊維繊度が約４６ｄｔｅｘのアクリル系繊維を得た。 (Comparative Example 2)
<Manufacture of acrylic copolymer>
Comparison was made except that after completion of the polymerization reaction, the end of the acrylic copolymer was 44% of the target amount, and sodium parastyrene sulfonate was charged into the reaction vessel at a constant rate and a total of 0.5 parts was charged until the completion of the polymerization reaction. An acrylic copolymer was prepared in the same manner as in Example 1. The polymerization reaction was carried out for 5 hours and 40 minutes.
<Wet spinning>
An acrylic fiber having a single fiber fineness of about 46 dtex was obtained in the same manner as in Example 1 except that the acrylic copolymer obtained above was used.
　（比較例３）
　＜アクリル系共重合体の製造＞
　開始剤はフリーラジカルを生成するアゾ類化合物とし、溶剤はＮ，Ｎ－ジメチルホルムアミドとし、４種類の共重合モノマーの配合割合はアクリロニトリル５０部、塩化ビニリデン３８．５部、メタクリル酸メチル０．５部、メチルプロペンスルホン酸５．０部とした。重合に用いる各成分は、定量ポンプによって、温度５５℃で連続的に反応槽に追加し、溶液重合を行った。重合の釜から流出する反応物は、未反応のモノマーを除去し、樹脂濃度を２３％に調整し、紡糸原液の貯蔵タンクに送液した。該紡糸原液の粘度は５５℃で２００００ｍＰａ・Ｓであった。
　＜湿式紡糸＞
　上記紡糸原液を、紡糸ノズルを用いて２０℃、５０重量％のジメチルホルムアミドの水溶液からなる凝固浴中に吐出して凝固させて繊維化した後、ジメチルホルムアミド濃度が３０％の水溶液、２０％の水溶液及び１５％の水溶液がそれぞれ導入された浴槽にて順番に脱溶剤し、４倍の一次延伸を行った。１４０℃で乾燥及び緻密化を行い、１１７℃での１．３倍の二次延伸を行い、１２５℃で１０％の緩和処理を行い、単繊維繊度が４６ｄｔｘのアクリル系繊維を得た。 (Comparative Example 3)
<Manufacture of acrylic copolymer>
The initiator is an azo compound that generates free radicals, the solvent is N, N-dimethylformamide, and the blending ratio of the four copolymer monomers is 50 parts of acrylonitrile, 38.5 parts of vinylidene chloride, 0.5 parts of methyl methacrylate. Part and 5.0 parts of methylpropenesulfonic acid. Each component used for the polymerization was continuously added to the reaction vessel at a temperature of 55 ° C. by a metering pump, and solution polymerization was performed. Unreacted monomer was removed from the reaction product flowing out from the polymerization kettle, the resin concentration was adjusted to 23%, and the solution was sent to the spinning stock storage tank. The spinning solution had a viscosity of 20,000 mPa · S at 55 ° C.
<Wet spinning>
The spinning dope is discharged into a coagulation bath composed of an aqueous solution of 50% by weight of dimethylformamide at 20 ° C. using a spinning nozzle to coagulate and fiberize, and then an aqueous solution having a dimethylformamide concentration of 30%, 20% Solvents were sequentially removed in a bath into which an aqueous solution and a 15% aqueous solution were introduced, and primary stretching was performed four times. Drying and densification were performed at 140 ° C., secondary stretching at 1.3 times at 117 ° C. was performed, and relaxation treatment was performed at 125 ° C. by 10% to obtain an acrylic fiber having a single fiber fineness of 46 dtx.
　実施例１～３及び比較例１～３で得られたアクリル系共重合体の数平均分子量及び重量平均分子量、並びに硫黄含有量を下記のように測定算出した。また、実施例１～３及び比較例１～３で得られたアクリル系共重合体における主鎖の拡散係数及びスルホン酸基含有成分の拡散係数を下記のように測定算出した。これらの結果を下記表１に示した。下記表１には、上述した数式（１）に基づいて算出したスルホン酸基含有成分の重量平均分子量（Ｍｗ’）も併せて示した。 The number average molecular weight, weight average molecular weight, and sulfur content of the acrylic copolymers obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured and calculated as follows. Further, the diffusion coefficient of the main chain and the diffusion coefficient of the sulfonic acid group-containing component in the acrylic copolymers obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured and calculated as follows. These results are shown in Table 1 below. Table 1 below also shows the weight average molecular weight (Mw ′) of the sulfonic acid group-containing component calculated based on the above formula (1).
　（重量平均分子量及び数平均分子量の測定）
　重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、東ソー社製のＧＰＣ（ゲル浸透クロマトグラフ）装置「ＨＬＣ－８３２０ＧＰＣ」を用い、カラムに「ＴＳＫ－ＧＥＬ　ＳＵＰＥＲ　ＡＷＭ－Ｈ」を用い、溶離液はジメチルホルムアミドで測定を行った。分子量算出に用いる標準物質は、東ソー社製のＴＳＫｇｅｌ　ｓｔａｎｄａｒｄ　Ｐｏｌｙ（ｅｔｈｙｌｅｎｅ　ｏｘｉｄｅ）　ＳＥ－２、ＳＥ－５、ＳＥ－８、ＳＥ－１５、ＳＥ－３０、ＳＥ－７０を用いた。また、試料溶媒は３Ｌのジメチルホルムアミドに臭化リチウム一水和物を１７．１ｇ添加した溶媒を用いた。 (Measurement of weight average molecular weight and number average molecular weight)
For weight average molecular weight (Mw) and number average molecular weight (Mn), use GPC (gel permeation chromatograph) “HLC-8320GPC” manufactured by Tosoh Corporation, and “TSK-GEL SUPER AWM-H” for the column. The liquid was measured with dimethylformamide. TSKgel standard Poly (ethylene oxide) SE-2, SE-5, SE-8, SE-15, SE-30, and SE-70 manufactured by Tosoh Corporation were used as the standard substances used for molecular weight calculation. As a sample solvent, a solvent obtained by adding 17.1 g of lithium bromide monohydrate to 3 L of dimethylformamide was used.
　（硫黄含有量の測定）
　試料を燃焼装置内で燃焼させた発生ガスを溶液に吸収後、吸収液中の硫酸イオン濃度を求め、硫酸イオン濃度から試料中の硫黄濃度を分析した。試料の燃焼は、三菱化学製の自動試料燃焼装置「ＡＱＦ－１００　ＧＡ－１００」を用いた。また、電気炉温度は入口９００℃、出口１０００℃、Ａｒ／Ｏ２混合気体２００ｍＬ／ｍｉｎ、Ｏ２４００ｍＬ／ｍｉｎの条件で燃焼を行った。また、吸収液の分析は、ＤＩＯＮＥＸ社製のイオンクロマトグラフ「ＩＣＳ１５００」を用い、移動相に２．７ｍｍｏｌ／ＬのＮａ２ＣＯ３及び０．３ｍｍｏｌ／ＬのＮａＨＣＯ３の混合溶液を用い、流速１．５ｍＬ／ｍｉｎで、電気伝導度検出器を用いて測定した。 (Measurement of sulfur content)
After the generated gas obtained by burning the sample in the combustion apparatus was absorbed into the solution, the sulfate ion concentration in the absorption liquid was determined, and the sulfur concentration in the sample was analyzed from the sulfate ion concentration. For sample combustion, an automatic sample combustion apparatus “AQF-100 GA-100” manufactured by Mitsubishi Chemical was used. The electric furnace was burned under the conditions of an inlet 900 ° C., an outlet 1000 ° C., an Ar / O 2 mixed gas 200 mL / min, and O 2 400 mL / min. Further, the analysis of the absorbing solution was performed using an ion chromatograph “ICS1500” manufactured by DIONEX, using a mixed solution of 2.7 mmol / L Na 2 CO 3 and 0.3 mmol / L NaHCO 3 as a mobile phase, and a flow rate. It was measured at 1.5 mL / min using an electrical conductivity detector.
　（アクリル系共重合体における主鎖の拡散係数及びスルホン酸基含有成分の拡散係数の測定）
　拡散係数はＮＭＲ法、具体的にはＤＯＳＹ法（Ｄｉｆｆｕｓｉｏｎ－ｏｒｄｅｒｅｄ　ＮＭＲ　ｓｐｅｃｔｒｏｓｃｏｐｙ）を用いて測定した。
（１）測定条件
　試料１０ｍｇを重ＤＭＦ０．５ｍＬに溶解させた溶液を用いてＶＡＲＩＡＮ社製の核磁気共鳴装置「ＶＮＭＲＳ　６００」でＮＭＲ測定を行った。測定条件は、以下のとおりであった。
測定温度：４０℃
パルス系列：ＢＰＰ－ＳＴＥ－ＬＥＤ
緩和遅延時間：５ｓ
磁場勾配パルス幅：６ｍｓ
拡散時間：１００ｍｓ
磁場勾配強度：０．０４～０．６０Ｔ／ｍ
アレイポイント：１６点
積算回数：１２８回
（２）解析条件
　データ処理は、ＮＭＲｔｅｃ社製のＮＭＲｎｏｔｅｂｏｏｋを用いて最大エントロピー法で行った。
ＦＩＤ取り込みポイント：４０９６
窓関数（ＬＢ）：３Ｈｚ
　ＤＯＳＹスペクトル（１ＨＤＯＳＹスペクトル）をテキストデータに書き出した後、各領域の拡散係数の平均値を算出し、得られた拡散係数分布からピークトップを読み取り、アクリル系共重合体における主鎖の拡散係数及びスルホン酸基含有成分の拡散係数を求めた。 (Measurement of diffusion coefficient of main chain and diffusion coefficient of sulfonic acid group-containing component in acrylic copolymer)
The diffusion coefficient was measured using NMR method, specifically, DOSY method (Diffusion-ordered NMR spectroscopy).
(1) Measurement conditions NMR measurement was performed with a nuclear magnetic resonance apparatus “VNMRS 600” manufactured by VARIAN using a solution in which 10 mg of a sample was dissolved in 0.5 mL of heavy DMF. The measurement conditions were as follows.
Measurement temperature: 40 ° C
Pulse series: BPP-STE-LED
Relaxation delay time: 5s
Magnetic field gradient pulse width: 6ms
Spreading time: 100ms
Magnetic field gradient strength: 0.04 to 0.60 T / m
Array point: 16 points Integration number: 128 times (2) Analysis conditions Data processing was performed by the maximum entropy method using NMRnotebook manufactured by NMRtec.
FID import points: 4096
Window function (LB): 3Hz
After writing the DOSY spectrum ( 1 HDOSY spectrum) as text data, the average value of the diffusion coefficient of each region is calculated, the peak top is read from the obtained diffusion coefficient distribution, and the diffusion coefficient of the main chain in the acrylic copolymer And the diffusion coefficient of the sulfonic acid group-containing component was determined.
　実施例１～３及び比較例１～３のアクリル系繊維の表面粗さを下記のように測定した。また、実施例１～３及び比較例１～３のアクリル系繊維の櫛通り性を下記のように評価した。これらの結果を下記表１に示した。 The surface roughness of the acrylic fibers of Examples 1 to 3 and Comparative Examples 1 to 3 was measured as follows. Further, the combability of the acrylic fibers of Examples 1 to 3 and Comparative Examples 1 to 3 was evaluated as follows. These results are shown in Table 1 below.
　（表面粗さ）
　超深度カラー３Ｓ形状測定顕微鏡（キーエンス製、型式「ＶＫ－９５００」）を用い、繊維側面を３０００倍の倍率（対物レンズ１５０倍、内蔵レンズ２０）で観察し、得られた画像から、画像解析ソフトＶＫ　Ａｎａｌｙｚｅｒ（キーエンス製、型式「ＶＫ－Ｈ１ＸＡ」）を用い、任意に縦４０μｍ、横８０μｍの領域を選択し、該縦４０μｍ、横８０μｍの領域の表面積を測定した。ｎ＝６とし、平均値を測定し、表面粗さとした。 (Surface roughness)
Using an ultra-deep color 3S shape measuring microscope (manufactured by Keyence, model “VK-9500”), the side of the fiber is observed at a magnification of 3000 times (objective lens 150 ×, built-in lens 20), and image analysis is performed from the obtained image. Using a soft VK Analyzer (manufactured by Keyence, model “VK-H1XA”), an area of 40 μm in length and 80 μm in width was arbitrarily selected, and the surface area of the area of 40 μm in length and 80 μm in width was measured. The average value was measured with n = 6, and the surface roughness was obtained.
　（櫛通り性）
　長さ３０ｃｍ、総繊度１０万ｄｔｅｘのトウフィラメントを用い、トウフィラメントにポリアセタール樹脂製くし（株式会社植原セル製、商品名「ニューデルリンコーム＃８２６）を０．３ｍ／ｓの速さでトウフィラメントの上部３ｃｍの所から下へ、完全に３０回以上通過させ、くしの通り易さを下記の基準で評価した。
Ａ：抵抗がなく、櫛がとおりやすい
Ｂ：若干抵抗があり、櫛がやや通りにくい。
Ｃ：抵抗がある或いは途中で引っかかり、櫛が通りにくい。 (Combability)
Using a tow filament with a length of 30 cm and a total fineness of 100,000 dtex, a polyacetal resin comb (manufactured by Uehara Cell Co., Ltd., trade name “New Delrin Comb # 826) is used as the tow filament at a speed of 0.3 m / s. It was allowed to pass 30 times or more completely from the upper 3 cm to the bottom, and the ease of combing was evaluated according to the following criteria.
A: There is no resistance and the comb is easy to pass. B: There is some resistance and the comb is a little difficult to pass.
C: There is resistance or it is caught in the middle, and the comb is difficult to pass.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記表１の結果から明らかなように、重量平均分子量が１００，０００以下であり、Ｄ／Ｄ’が１．０７以下であり、硫黄含有量が０．３５重量％以上である実施例１～３のアクリル系共重合体で構成されたアクリル系繊維は、表面粗さが小さく、櫛通り性が良好であった。一方、重量平均分子量が１００，０００を超えており、Ｄ／Ｄ’が１．０７を超えている比較例１～３のアクリル系共重合体で構成されたアクリル系繊維は、表面粗さが大きく、櫛通り性が悪かった。
  As is apparent from the results in Table 1 above, Examples 1 to 3 having a weight average molecular weight of 100,000 or less, D / D ′ of 1.07 or less, and a sulfur content of 0.35% by weight or more. The acrylic fiber composed of the acrylic copolymer 3 had a small surface roughness and a good combing property. On the other hand, the acrylic fibers composed of the acrylic copolymers of Comparative Examples 1 to 3 having a weight average molecular weight exceeding 100,000 and D / D ′ exceeding 1.07 have a surface roughness. It was big and the combing ability was bad.

Claims (10)

  1. 　アクリロニトリルと、塩化ビニル及び／又は塩化ビニリデンと、スルホン酸基含有ビニル単量体を共重合したアクリル系共重合体であって、
    　前記アクリル系共重合体は、重量平均分子量が１００，０００以下であり、硫黄含有量が０．３５重量％以上であり、
    　前記アクリル系共重合体において、ＤＯＳＹ法にて測定した主鎖の拡散係数Ｄとスルホン酸基含有成分の拡散係数Ｄ’の比Ｄ／Ｄ’が１．０７以下であることを特徴とするアクリル系共重合体。     An acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer,
    The acrylic copolymer has a weight average molecular weight of 100,000 or less, a sulfur content of 0.35% by weight or more,
    In the acrylic copolymer, the ratio D / D ′ of the diffusion coefficient D of the main chain and the diffusion coefficient D ′ of the sulfonic acid group-containing component measured by the DOSY method is 1.07 or less. Copolymer.
  2. 　前記アクリル系共重合体は、アクリル系共重合体の全体重量に対して、アクリロニトリルを３０～７０重量％、塩化ビニル及び／又は塩化ビニリデンを２５～６９．５重量％、並びにスルホン酸基含有ビニル単量体を０．５～５重量％含む請求項１に記載のアクリル系共重合体。 The acrylic copolymer comprises 30 to 70% by weight of acrylonitrile, 25 to 69.5% by weight of vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl based on the total weight of the acrylic copolymer. The acrylic copolymer according to claim 1, comprising 0.5 to 5% by weight of a monomer.
  3. 　前記アクリル系共重合体において、ＤＯＳＹ法にて測定したスルホン酸基含有成分の拡散係数が１７μｍ２／ｓｅｃ以上である請求項１又は２に記載のアクリル系共重合体。 The acrylic copolymer according to claim 1 or 2, wherein a diffusion coefficient of the sulfonic acid group-containing component measured by the DOSY method in the acrylic copolymer is 17 µm 2 / sec or more.
  4. 　アクリロニトリルと、塩化ビニル及び／又は塩化ビニリデンと、スルホン酸基含有ビニル単量体を共重合したアクリル系共重合体で構成された人工毛髪用アクリル系繊維であって、
    　前記アクリル系共重合体は、重量平均分子量が１００，０００以下であり、硫黄含有量が０．３５重量％以上であり、
    　前記アクリル系共重合体において、ＤＯＳＹ法にて測定した主鎖の拡散係数Ｄとスルホン酸基含有成分の拡散係数Ｄ’の比Ｄ／Ｄ’が１．０７以下であることを特徴とする人工毛髪用アクリル系繊維。     An acrylic fiber for artificial hair composed of an acrylic copolymer obtained by copolymerizing acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer,
    The acrylic copolymer has a weight average molecular weight of 100,000 or less, a sulfur content of 0.35% by weight or more,
    In the acrylic copolymer, the ratio D / D ′ of the diffusion coefficient D ′ of the main chain and the diffusion coefficient D ′ of the sulfonic acid group-containing component measured by the DOSY method is 1.07 or less. Acrylic fiber for hair.
  5. 　前記アクリル系共重合体は、アクリル系共重合体の全体重量に対して、アクリロニトリルを３０～７０重量％、塩化ビニル及び／又は塩化ビニリデンを２５～６９．５重量％、並びにスルホン酸基含有ビニル単量体を０．５～５重量％含む請求項４に記載の人工毛髪用アクリル系繊維。 The acrylic copolymer comprises 30 to 70% by weight of acrylonitrile, 25 to 69.5% by weight of vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl based on the total weight of the acrylic copolymer. The acrylic fiber for artificial hair according to claim 4, comprising 0.5 to 5% by weight of a monomer.
  6. 　前記アクリル系共重合体において、ＤＯＳＹ法にて測定したスルホン酸基含有成分の拡散係数が１７μｍ２／ｓｅｃ以上である請求項４又は５に記載の人工毛髪用アクリル系繊維。 The acrylic fiber for artificial hair according to claim 4 or 5, wherein in the acrylic copolymer, the diffusion coefficient of the sulfonic acid group-containing component measured by the DOSY method is 17 µm 2 / sec or more.
  7. 　前記人工毛髪用アクリル系繊維は、繊維側面の縦４０μｍ、横８０μｍの領域において、表面粗さが６１００μｍ２以下である請求項４～６のいずれか１項に記載の人工毛髪用アクリル系繊維。 The acrylic fiber for artificial hair according to any one of claims 4 to 6, wherein the acrylic fiber for artificial hair has a surface roughness of 6100 µm 2 or less in a region of 40 µm in length and 80 µm in width on the side of the fiber.
  8. 　請求項１～３のいずれか１項に記載のアクリル系共重合体の製造方法であって、アクリロニトリルと、塩化ビニル及び／又は塩化ビニリデンと、スルホン酸基含有ビニル単量体の重合を単一反応槽において連続的に行う際、重合反応開始時にはスルホン酸基含有ビニル単量体を反応槽に投入せず、重合反応開始後、アクリル系共重合体の収量がアクリル系共重合体の目的量の８重量％以上２１重量％以下の所定の量になる時点から、重合反応が終了するまで、スルホン酸基含有ビニル単量体を一定の速度で連続的に投入することを特徴とするアクリル系共重合体の製造方法。 The method for producing an acrylic copolymer according to any one of claims 1 to 3, wherein polymerization of acrylonitrile, vinyl chloride and / or vinylidene chloride, and a sulfonic acid group-containing vinyl monomer is performed in a single manner. When the polymerization reaction is continuously performed, the sulfonic acid group-containing vinyl monomer is not charged into the reaction tank at the start of the polymerization reaction, and after the polymerization reaction starts, the yield of the acrylic copolymer is the target amount of the acrylic copolymer. A sulfonic acid group-containing vinyl monomer is continuously charged at a constant rate from the time when a predetermined amount of 8 wt% to 21 wt% is reached until the polymerization reaction is completed. A method for producing a copolymer.
  9. 　前記アクリロニトリルと、塩化ビニル及び／又は塩化ビニリデンと、スルホン酸基含有ビニル単量体の重合は、水溶性開始剤の存在下、乳化剤を用いて行う乳化重合で行う請求項８に記載のアクリル系共重合体の製造方法。 The acrylic system according to claim 8, wherein the polymerization of the acrylonitrile, vinyl chloride and / or vinylidene chloride, and the sulfonic acid group-containing vinyl monomer is carried out by emulsion polymerization using an emulsifier in the presence of a water-soluble initiator. A method for producing a copolymer.
  10. 　請求項４～７のいずれか１項に記載の人工毛髪用アクリル系繊維の製造方法であって、
    　アクリル系共重合体をジメチルスルホキシド、ジメチルアセトアミド及びＮ，Ｎ－ジメチルホルムアミドからなる群から選べる一種以上の有機溶媒に溶解して得られた紡糸原液を湿式紡糸することを特徴とする人工毛髪用アクリル系繊維の製造方法。     A method for producing acrylic fiber for artificial hair according to any one of claims 4 to 7,
    Acrylic for artificial hair characterized by wet-spinning a spinning dope obtained by dissolving an acrylic copolymer in one or more organic solvents selected from the group consisting of dimethyl sulfoxide, dimethylacetamide and N, N-dimethylformamide A method for producing fiber.
PCT/JP2016/068533 2015-06-26 2016-06-22 Acrylic copolymer, acrylic fiber for artificial hair and method for manufacturing same WO2016208630A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023107050A3 (en) * 2021-11-23 2023-08-10 Aksa Akri̇li̇k Ki̇mya Sanayi̇i̇ Anoni̇m Şi̇rketi̇ Synthetic hair production from acrylic fiber

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5710613A (en) * 1980-05-28 1982-01-20 Kanegafuchi Chem Ind Co Ltd Preparation of acrylonitrile type copolymer
JPS5891710A (en) * 1981-11-26 1983-05-31 Kanegafuchi Chem Ind Co Ltd Acrylonitrile polymer, production thereof and synthetic fiber therefrom
JPS5891711A (en) * 1981-11-26 1983-05-31 Kanegafuchi Chem Ind Co Ltd Acrylonitrile polymer, production thereof and modacrylic synthetic fiber therefrom
JPH01148806A (en) * 1987-12-02 1989-06-12 Kanegafuchi Chem Ind Co Ltd Acrylic synthetic fiber for wig
JP2000290830A (en) * 1999-04-02 2000-10-17 Kanegafuchi Chem Ind Co Ltd Acrylic synthetic fiber excellent in gloss and dyeing properties
WO2002061187A1 (en) * 2001-01-29 2002-08-08 Kaneka Corporation Artificial hair and method for production thereof
JP2002227028A (en) * 2001-01-29 2002-08-14 Kanegafuchi Chem Ind Co Ltd Acrylic artificial hair fiber and head decoration composed thereof
JP2004143192A (en) * 2002-10-21 2004-05-20 Kanegafuchi Chem Ind Co Ltd Method for producing acrylic copolymer
JP2004339643A (en) * 2003-05-15 2004-12-02 Kanegafuchi Chem Ind Co Ltd Acrylic synthetic fiber having high discharge performance
JP2005314853A (en) * 2004-04-30 2005-11-10 Kaneka Corp Acrylic synthetic fiber and pile fabric having excellent discharge printing performance

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5710613A (en) * 1980-05-28 1982-01-20 Kanegafuchi Chem Ind Co Ltd Preparation of acrylonitrile type copolymer
JPS5891710A (en) * 1981-11-26 1983-05-31 Kanegafuchi Chem Ind Co Ltd Acrylonitrile polymer, production thereof and synthetic fiber therefrom
JPS5891711A (en) * 1981-11-26 1983-05-31 Kanegafuchi Chem Ind Co Ltd Acrylonitrile polymer, production thereof and modacrylic synthetic fiber therefrom
JPH01148806A (en) * 1987-12-02 1989-06-12 Kanegafuchi Chem Ind Co Ltd Acrylic synthetic fiber for wig
JP2000290830A (en) * 1999-04-02 2000-10-17 Kanegafuchi Chem Ind Co Ltd Acrylic synthetic fiber excellent in gloss and dyeing properties
WO2002061187A1 (en) * 2001-01-29 2002-08-08 Kaneka Corporation Artificial hair and method for production thereof
JP2002227028A (en) * 2001-01-29 2002-08-14 Kanegafuchi Chem Ind Co Ltd Acrylic artificial hair fiber and head decoration composed thereof
JP2004143192A (en) * 2002-10-21 2004-05-20 Kanegafuchi Chem Ind Co Ltd Method for producing acrylic copolymer
JP2004339643A (en) * 2003-05-15 2004-12-02 Kanegafuchi Chem Ind Co Ltd Acrylic synthetic fiber having high discharge performance
JP2005314853A (en) * 2004-04-30 2005-11-10 Kaneka Corp Acrylic synthetic fiber and pile fabric having excellent discharge printing performance

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023107050A3 (en) * 2021-11-23 2023-08-10 Aksa Akri̇li̇k Ki̇mya Sanayi̇i̇ Anoni̇m Şi̇rketi̇ Synthetic hair production from acrylic fiber

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