[go: up one dir, main page]

US20170335491A1 - Method for producing acrylic fiber - Google Patents

Method for producing acrylic fiber Download PDF

Info

Publication number
US20170335491A1
US20170335491A1 US15/673,494 US201715673494A US2017335491A1 US 20170335491 A1 US20170335491 A1 US 20170335491A1 US 201715673494 A US201715673494 A US 201715673494A US 2017335491 A1 US2017335491 A1 US 2017335491A1
Authority
US
United States
Prior art keywords
mass
amount
acrylic copolymer
polyphosphate
fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US15/673,494
Inventor
Satoru Yoshimura
Masaru Anahara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaneka Corp
Original Assignee
Kaneka Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kaneka Corp filed Critical Kaneka Corp
Assigned to KANEKA CORPORATION reassignment KANEKA CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YOSHIMURA, SATORU, ANAHARA, MASARU
Publication of US20170335491A1 publication Critical patent/US20170335491A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/40Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/06Wet spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties

Definitions

  • One or more embodiments of the invention relate to a method for producing acrylic fiber in which a spinning solution is subjected to wet spinning, the spinning solution being obtained by dissolving an acrylic copolymer obtained through copolymerization of acrylonitrile, vinyl chloride, and a sulfonic acid group-containing monomer in dimethyl sulfoxide.
  • Acrylic fiber especially, acrylic fiber constituted by an acrylic copolymer comprising vinyl chloride or a vinylidene chloride as one of the copolymer components is suitably used as fiber for artificial hair used in a head decoration product such as a wig, hairpiece, or weaving due to its soft texture.
  • acrylic fiber used as artificial hair is produced through wet spinning using a spinning solution obtained by dissolving an acrylic copolymer in a good solvent such as dimethyl sulfoxide.
  • Patent Document 1 discloses that acrylic fiber constituted by an acrylic copolymer constituted by acrylonitrile, vinylidene chloride, and a sulfonic acid group-containing vinyl monomer is produced using a wet spinning method in which a good solvent is used.
  • Patent Document 1 is problematic in that vinylidene chloride is used as one of the copolymer components that is copolymerized with acrylonitrile, and has poor curl setting properties with hot water. In view of this, in order to increase the curl setting properties with hot water, vinyl chloride has been used as one of the copolymer components that are copolymerized with acrylonitrile.
  • the inventors have found that when a highly-safe dimethyl sulfoxide was used as the good solvent and a spinning solution obtained by dissolving, in dimethyl sulfoxide, an acrylic copolymer obtained through copolymerization of acrylonitrile, vinyl chloride, and a sulfonic acid group-containing monomer was subjected to wet spinning to produce acrylic fiber, the acrylic fiber discolored to yellow or brown.
  • One or more embodiments of the present invention provide a method for producing acrylic fiber, according to which, even if a spinning solution obtained by dissolving an acrylic copolymer comprising vinyl chloride as a copolymer component in dimethyl sulfoxide is subjected to wet spinning, it is possible to suppress discoloration of the obtained acrylic fiber.
  • One or more embodiments of the present invention relate to a method for producing acrylic fiber in which a spinning solution obtained by dissolving an acrylic copolymer in an organic solvent is subjected to wet spinning, in which the acrylic copolymer comprises acrylonitrile in an amount of 20 to 85 mass %, vinyl chloride in an amount of 14.5 to 79.5 mass %, and a sulfonic acid group-containing monomer in an amount of 0.5 to 10 mass % with respect to the total mass of the acrylic copolymer, the organic solvent is dimethyl sulfaxide, and the spinning solution comprises water and a polyphosphate.
  • the spinning solution comprises the polyphosphate in an amount of 0.05 to 5 mass % with respect to the total mass of the acrylic copolymer.
  • the polyphosphate may be at least one compound selected from the group consisting of a pyrophosphate, a tripolyphosphate, a tetrapolyphosphate, a trimetaphosphate, and a tetrametaphosphate, and in one or more embodiments, is a tripolyphosphate.
  • acrylic fiber in which discoloration into yellow or brown is suppressed even if a spinning solution obtained by dissolving an acrylic copolymer comprising vinyl chloride as a copolymer component in dimethyl sulfoxide is subjected to wet spinning.
  • the polyphosphate is used as a phosphorus flame retardant for increasing the flame-retardancy of fiber
  • the inventors found that by adding a polyphosphate together with water to a spinning solution obtained by dissolving, in dimethyl sulfoxide, an acrylic copolymer obtained through copolymerization of acrylonitrile, vinyl chloride, and a sulfonic acid group-containing monomer and subjecting the resulting mixture to wet spinning, discoloration of the acrylic fiber to yellow or brown was suppressed.
  • the acrylic copolymer comprises acrylonitrile in an amount of 20 to 85 mass %, vinyl chloride in an amount of 14.5 to 79.5 mass %, and a sulfonic acid group-containing monomer in an amount of 0.5 to 10 mass % with respect to the total mass of the acrylic copolymer.
  • the acrylic copolymer comprises vinyl chloride in an amount of 14.5 to 79.5 mass %
  • the fiber has good flame-retardancy.
  • the acrylic copolymer comprises acrylonitrile in an amount of 20 to 85 mass %
  • the fiber has good heat resistance and a processing temperature during curl setting can be set as appropriate.
  • the acrylic copolymer comprising the sulfonic acid group-containing monomer in an amount of 0.5 to 10 mass %, its hydrophilicity increases and void fraction decreases.
  • the acrylic copolymer may comprise acrylonitrile in an amount of 20 to 80 mass %, vinyl chloride in an amount of 19.5 to 79.5 mass %, and a sulfonic acid group-containing monomer in an amount of 0.5 to 5 mass %, and in one or more embodiments, comprises acrylonitrile in an amount of 20 to 75 mass %, vinyl chloride in an amount of 24.5 to 79.5 mass %, and a sulfonic acid group-containing monomer in an amount of 0.5 to 5 mass %.
  • the sulfonic acid group-containing monomer for example, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and metal salts such as sodium salts thereof: amine salts thereof and the like can be used thereas.
  • the sulfonic acid group-containing monomer can be used alone or in combination of two or more.
  • the acrylic copolymer is dissolved in dimethyl sulfaxide.
  • dimethyl sulfrxide as an organic solvent, its safety increases.
  • the spinning solution may comprise a polyphosphate in an amount of 0.05 mass % or more, or in an amount of 0.06 mass % or more, or in an amount of 0.07 mass % or more with respect to the total mass of the acrylic copolymer.
  • the spinning solution may comprise the polyphosphate in an amount of 5 mass % or less, or in an amount of 4.5 mass % or less, or in an amount of 4 mass % or less, or in an amount of 3.5 mass % or less, or in an amount of 3 mass % or less, or in an amount of 2.5 mass % or less, or in an amount of 2 mass % or less, or in an amount of 1.5 mass % or less, or in an amount of 1 mass % or less, or in an amount of 0.9 mass % or less, or in an amount of 0.7 mass % or less, or in an amount of 0.5 mass % or less with respect to the total mass of the acrylic copolymer.
  • the polyphosphate need only be an inorganic polyphosphate, and has no limitation.
  • pyrophosphates, tripolyphosphates, tetrapolyphosphates, trimetaphosphates, tetrametaphosphates, and the like can be used.
  • tripolyphosphates may be preferable.
  • the type of salt and any salts such as sodium salts, potassium salts, and ammonium salts can be used.
  • salt may be a watersoluble salt such as a sodium salt and a potassium salt.
  • Examples of the pyrophosphates include sodium pyrophosphate and potassium pyrophosphate.
  • Examples of the tripolyphosphates include sodium tripolyphosphate, aluminum dihydrogen tripolyphosphate, and potassium tripolyphosphate.
  • Examples of the tetrapolyphosphates include sodium tetrapolyphosphate and potassium tetrapolyphosphate.
  • the spinning solution may comprise water in an amount of 8 to 16 mass %, or in an amount of 8 to 15 mass %, or in an amount of 8 to 14 mass %, or in an amount of 8 to 13 mass %, or in an amount of 8 to 12.5 mass % with respect to the total mass of the acrylic copolymer.
  • the spinning solution may comprise, with respect to the total mass of the spinning solution, the acrylic copolymer in an amount of 20 to 30 mass %, DMSO in an amount of 65.2 to 78.49 mass %, water in an amount of 1.5 to 4.8 mass %, and the polyphosphate in an amount of 0.01 to 1.5 mass %, or comprises the acrylic copolymer in an amount of 22 to 30 mass %, DMSO in an amount of 66 to 75.99 mass %, water in an amount of 2 to 4 mass %, and the polyphosphate in an amount of 0.01 to 1.5 mass %, or comprises the acrylic copolymer in an amount of 25 to 30 mass %, DMSO in an amount of 66.5 to 72.49 mass %, water in an amount of 2.5 to 3.5 mass %, and the polyphosphate in an amount of 0.01 to 1.5 mass %, for example.
  • the spinning solution may also comprise other additives for improving fiber properties as needed.
  • the additives include gloss adjusting agents such as titanium dioxide, silicon dioxide, esters and ethers of cellulose derivatives including cellulose acetate, coloring agents such as organic pigments, inorganic pigments, and dyes, and stabilizers for increasing light resistance and heat resistance.
  • the spinning solution although not particularly limited, can be prepared by mixing the acrylic copolymer, DMSO, water, and the polyphosphate.
  • the spinning solution may be prepared by mixing the acrylic copolymer, DMSO, and an aqueous solution of the polyphosphate.
  • the spinning solution may be prepared by, after DMSO and the aqueous solution of the polyphosphate are added to the acrylic copolymer, stirring the resulting mixture at 40 to 80° C. for 3 to 12 hours, or may be prepared by stirring the resulting mixture at 50 to 75° C. for 4 to 10 hours, or may be prepared by stirring the resulting mixture at 60 to 70° C.
  • hydrochloric acid may be produced through dehydrochlorination of the acrylic copolymer, but the produced hydrochloric acid (hydrogen ions) is utilized in an equilibrium reaction with a phosphate group derived from the polyphosphate, and thereby decomposition of DMSO by hydrochloric acid is prevented and discoloration of fiber to yellow or brown is suppressed.
  • An acrylic copolymer comprising moisture may also be used as the acrylic copolymer.
  • the total mass of the acrylic copolymer refers to the dry mass of the acrylic copolymer, and the dry mass of the acrylic copolymer is obtained by drying a watercomprising acrylic copolymer at 60° C. for 10 hours, removing moisture, and then measuring the resulting mass thereof.
  • DMSO comprising moisture may be used as DMSO.
  • the acrylic copolymer refers to an acrylic copolymer that comprises no moisture
  • DMSO refers to DMSO that comprises no moisture.
  • Acrylic fiber is obtained by wet spinning the spinning solution with an ordinary method.
  • the spinning solution is discharged directly or through a spinning nozzle into a coagulation liquid (coagulation bath) with an aqueous solution of DMSO, and coagulated so as to obtain fiber.
  • the coagulation bath can be prepared using an aqueous solution of DMSO having a DMSO concentration of 40 to 70 mass % at a temperature of 5 to 40° C., for example. If the concentration of the good solvent such as DMSO in the coagulation bath is excessively low, the spinning solution tends to coagulate fast, its coagulated structure tends to be rough, and voids tend to form in the fiber.
  • the fiber may be introduced into an aqueous solution of DMSO whose concentration is lower than that of the coagulation liquid and that has a temperature of 30° C. or more, or into warm water having a temperature of 30° C. or more, may be subjected to solvent removal, water washing, and drawing, and relaxing may also be performed after drawing as needed.
  • the fiber is washed with warm water having a temperature of 30° C. or more. The solvent is removed by water washing.
  • the draw ratio although not particularly limited, may be 2 to 8-fold, or 2 to 7-fold, or 2 to 6-fold. It is inferred that during the steps of solvent removal, water washing, and drawing in the aqueous solution of DMSO as well, if fiber is processed at 80° C. or more for 1 hour or more, for example, hydrochloric acid may be produced through dehydrochlorination of the acrylic copolymer, but the produced hydrochloric acid (hydrogen ions) is utilized in the equilibrium reaction with a phosphate group derived from the polyphosphate, as a result of which decomposition of DMSO by hydrochloric acid is prevented and discoloration of fiber to yellow or brown is suppressed.
  • the fiber may be dried.
  • a finishing oil may also be attached to the fiber as needed.
  • the drying temperature may be 110 to 190° C., and in one or more embodiments, 110 to 160° C., for example.
  • the dried fiber may also be further drawn thereafter as needed, and the draw ratio may be 1 to 4-fold. In one or more embodiments, the total draw ratio including drawing before drying is 2 to 12-fold.
  • the fiber that is obtained by drying or obtained by drawing after drying may be subjected to relaxing processing at 15% or more.
  • the relaxing processing can be performed in dry heat or a superheated steam atmosphere at a high temperature of 150 to 200° C., and in one or more embodiments, 150 to 190° C., for example.
  • the relaxing processing can be performed in a pressurized water vapor atmosphere or a heated pressurized water vapor atmosphere at 120 to 180° C. and 0.05 to 0.4 MPa, and in one or more embodiments, 0.1 to 0.4 MPa.
  • the single fiber fineness of the acrylic fiber may be 30 to 100 dtex, or 40 to 80 dtex, or 45 to 70 dtex.
  • the single fiber fineness means the average value of the finenesses of any 100 single fibers.
  • the acrylic fiber may also comprise phosphorus derived from the polyphosphate.
  • the acrylic fiber may also comprise phosphorus in an amount of 5 to 250 ppm, in an amount of 10 to 150 ppm, and in an amount of 15 to 80 ppm with respect to the total mass of the acrylic fiber.
  • the amount of phosphorus can be determined as follows.
  • an acrylic copolymer constituted by 45.7 mass % acrylonitrile, 52.3 mass % vinyl chloride, and 2.0 mass % sodium styrene sulfonate, 1223 g of DMSO, and 62.5 g of an aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass % were added to a 7-L stainless steel container, the acrylic copolymer was dissolved through stirring at 70° C. for 12 hours, and thereby a spinning solution was produced.
  • the obtained spinning solution was subjected to wet spinning at a spinning speed of 2 m/min in a coagulation bath with an aqueous solution of DMSO having a temperature of 20° C. and a concentration of 57 mass %, using a spinning nozzle (hole diameter: 0.3 mm, number of holes: 50 holes), and then drawn 3-fold in a drawing bath with an aqueous solution of DMSO solution having a temperature of 80° C. and a concentration of 50 mass %.
  • acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained by drying and drawing 2-fold at 140° C., and performing 20%-relaxing processing at 160° C.
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that an aqueous solution of sodium tripolyphosphate having a concentration of 1.22 mass % was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that an aqueous solution of sodium tripolyphosphate having a concentration of 2.44 mass % was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that an aqueous solution of sodium tripolyphosphate having a concentration of 3.66 mass % was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that an aqueous solution of sodium pyrophosphate having a concentration of 1.22 mass % was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that an aqueous solution of sodium tetrapolyphosphate having a concentration of 1.22 mass % was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that pure water was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • an acrylic copolymer constituted by 45.7 mass % acrylonitrile, 52.3 mass % vinyl chloride, and 2.0 mass % sodium styrene sulfonate, 1223 g of DMSO, and 0.7625 g of sodium tripolyphosphate were added to a 7-L stainless steel container, the acrylic copolymer was dissolved by stirring at 70° C. for 12 hours, and thereby a spinning solution was produced.
  • the obtained spinning solution was subjected to wet spinning at a spinning speed of 2 m/min in a coagulation bath with an aqueous solution of DMSO having a temperature of 20° C. and a concentration of 57 mass %, using a spinning nozzle (hole diameter: 0.3 mm, number of holes: 50 holes), and then drawn 3-fold in a drawing bath with an aqueous solution of DMSO having a temperature of 80° C. and a concentration of 50 mass %.
  • acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained by drying and drawing 2-fold at 140° C., and performing 20%-relaxing processing at 160° C. 50 yarns broke in the coagulation bath in the 2 hours after spinning started, and operability was extremely unstable.
  • the color of the acrylic fibers of Examples 1 to 6 and Comparative Examples 1 and 2 was measured using the following colorimetry method, and the results are shown in Table 1 below. Also, the content ofphosphorus in the acrylic fibers of Examples 1 to 6 and Comparative Examples 1 and 2 was measured using the following phosphorus quantification method, and the results are shown in Table 1 below. Table 1 below also shows the blending amount of a polyphosphate and the blending amount of water with respect to the total mass of the acrylic copolymer in the spinning solution.
  • a sample for colorimetry was produced such that the fiber bundle of 500 fibers had a width of 5 mm, colorimetry was performed at any 4 positions using a spectrophotometer (“CM-2600d” produced by KONICA MINOLTA, INC), in conditions of diffused lighting with 10 degrees, light receiving method of D65, measurement diameter of a 8 mm, and an SCE method, and the average value of those measurement values was obtained as the color.
  • CM-2600d produced by KONICA MINOLTA, INC
  • Sulfuric acid, nitric acid, hydrofluoric acid, and perchloric acid were added to fibers that were cut to a cut length of 0.5 cm, and the fibers were decomposed by heating at 120° C. in reflux conditions. After the resulting mixture was condensed by heating until sulfuric acid produced white smoke, the condensate was dissolved by warming with diluted nitric acid at 100° C. for 45 minutes, and calibrated to a certain volume. The obtained liquid with the certain volume was used to quantify the phosphorus element with an ICP emission spectrophotometer (“SPS4000” produced by Seiko Instruments Inc).
  • SPS4000 ICP emission spectrophotometer

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

A method for producing acrylic fiber includes preparing a spinning solution including an acrylic copolymer, dimethyl sulfoxide, water, and a polyphosphate; and subjecting the spinning solution to wet spinning, wherein the acrylic copolymer includes acrylonitrile in an amount of 20 to 85 mass %, vinyl chloride in an amount of 14.5 to 79.5 mass %, and a sulfonic acid group-containing monomer in an amount of 0.5 to 10 mass % with respect to a total mass of the acrylic copolymer.

Description

    TECHNICAL FIELD
  • One or more embodiments of the invention relate to a method for producing acrylic fiber in which a spinning solution is subjected to wet spinning, the spinning solution being obtained by dissolving an acrylic copolymer obtained through copolymerization of acrylonitrile, vinyl chloride, and a sulfonic acid group-containing monomer in dimethyl sulfoxide.
  • BACKGROUND
  • Acrylic fiber, especially, acrylic fiber constituted by an acrylic copolymer comprising vinyl chloride or a vinylidene chloride as one of the copolymer components is suitably used as fiber for artificial hair used in a head decoration product such as a wig, hairpiece, or weaving due to its soft texture. In general, acrylic fiber used as artificial hair is produced through wet spinning using a spinning solution obtained by dissolving an acrylic copolymer in a good solvent such as dimethyl sulfoxide. For example, Patent Document 1 discloses that acrylic fiber constituted by an acrylic copolymer constituted by acrylonitrile, vinylidene chloride, and a sulfonic acid group-containing vinyl monomer is produced using a wet spinning method in which a good solvent is used.
  • However, Patent Document 1 is problematic in that vinylidene chloride is used as one of the copolymer components that is copolymerized with acrylonitrile, and has poor curl setting properties with hot water. In view of this, in order to increase the curl setting properties with hot water, vinyl chloride has been used as one of the copolymer components that are copolymerized with acrylonitrile.
  • Patent Document
  • [Patent Document 1] JP 2002-315765A
  • However, the inventors have found that when a highly-safe dimethyl sulfoxide was used as the good solvent and a spinning solution obtained by dissolving, in dimethyl sulfoxide, an acrylic copolymer obtained through copolymerization of acrylonitrile, vinyl chloride, and a sulfonic acid group-containing monomer was subjected to wet spinning to produce acrylic fiber, the acrylic fiber discolored to yellow or brown.
  • SUMMARY
  • One or more embodiments of the present invention provide a method for producing acrylic fiber, according to which, even if a spinning solution obtained by dissolving an acrylic copolymer comprising vinyl chloride as a copolymer component in dimethyl sulfoxide is subjected to wet spinning, it is possible to suppress discoloration of the obtained acrylic fiber.
  • One or more embodiments of the present invention relate to a method for producing acrylic fiber in which a spinning solution obtained by dissolving an acrylic copolymer in an organic solvent is subjected to wet spinning, in which the acrylic copolymer comprises acrylonitrile in an amount of 20 to 85 mass %, vinyl chloride in an amount of 14.5 to 79.5 mass %, and a sulfonic acid group-containing monomer in an amount of 0.5 to 10 mass % with respect to the total mass of the acrylic copolymer, the organic solvent is dimethyl sulfaxide, and the spinning solution comprises water and a polyphosphate.
  • In one or more embodiments, the spinning solution comprises the polyphosphate in an amount of 0.05 to 5 mass % with respect to the total mass of the acrylic copolymer.
  • The polyphosphate may be at least one compound selected from the group consisting of a pyrophosphate, a tripolyphosphate, a tetrapolyphosphate, a trimetaphosphate, and a tetrametaphosphate, and in one or more embodiments, is a tripolyphosphate.
  • According to one or more embodiments of the present invention, it is possible to provide acrylic fiber in which discoloration into yellow or brown is suppressed even if a spinning solution obtained by dissolving an acrylic copolymer comprising vinyl chloride as a copolymer component in dimethyl sulfoxide is subjected to wet spinning.
  • DESCRIPTION OF THE EMBODIMENTS
  • In order to prevent the acrylic fiber discoloring to yellow or brown when a spinning solution obtained by dissolving, in dimethyl sulfoxide (DMSO), an acrylic copolymer comprising acrylonitrile, vinyl chloride, and a sulfonic acid group-containing monomer is subjected to wet spinning, the inventors conducted intensive studies and found that by adding water and a polyphosphate to the spinning solution, discoloration of the acrylic fiber to yellow or brown was suppressed while having good spinning properties. It is inferred that when the spinning solution obtained by dissolving the acrylic copolymer into dimethyl sulfoxide is subjected to wet spinning, in the producing step, the acrylic copolymer undergoes dehydrochlorination, dimethyl sulfoxide is decomposed by the produced hydrochloric acid, and thereby the fiber discolors to yellow or brown. If a step of dissolving the acrylic copolymer into dimethyl sullfxide is performed at a temperature higher than room temperature for a long period of time, the acrylic copolymer significantly undergoes dehydrochlorination. In general, the polyphosphate is used as a phosphorus flame retardant for increasing the flame-retardancy of fiber, and surprisingly, the inventors found that by adding a polyphosphate together with water to a spinning solution obtained by dissolving, in dimethyl sulfoxide, an acrylic copolymer obtained through copolymerization of acrylonitrile, vinyl chloride, and a sulfonic acid group-containing monomer and subjecting the resulting mixture to wet spinning, discoloration of the acrylic fiber to yellow or brown was suppressed. Although the mechanism by which the discoloration of the acrylic fiber is suppressed by adding the polyphosphate together with water to a spinning solution and performing wet spinning is not clear, it is inferred that the suppression was caused by hydrochloric acid (hydrogen ions) produced through dehydrochlorination of the acrylic copolymer being utilized in an equilibrium reaction with a phosphate group derived from the polyphosphate that dissolved in water, whereby DMSO is prevented from being decomposed by hydrochloric acid.
  • The acrylic copolymer comprises acrylonitrile in an amount of 20 to 85 mass %, vinyl chloride in an amount of 14.5 to 79.5 mass %, and a sulfonic acid group-containing monomer in an amount of 0.5 to 10 mass % with respect to the total mass of the acrylic copolymer. When the acrylic copolymer comprises vinyl chloride in an amount of 14.5 to 79.5 mass %, the fiber has good flame-retardancy. When the acrylic copolymer comprises acrylonitrile in an amount of 20 to 85 mass %, the fiber has good heat resistance and a processing temperature during curl setting can be set as appropriate. Due to the acrylic copolymer comprising the sulfonic acid group-containing monomer in an amount of 0.5 to 10 mass %, its hydrophilicity increases and void fraction decreases. The acrylic copolymer may comprise acrylonitrile in an amount of 20 to 80 mass %, vinyl chloride in an amount of 19.5 to 79.5 mass %, and a sulfonic acid group-containing monomer in an amount of 0.5 to 5 mass %, and in one or more embodiments, comprises acrylonitrile in an amount of 20 to 75 mass %, vinyl chloride in an amount of 24.5 to 79.5 mass %, and a sulfonic acid group-containing monomer in an amount of 0.5 to 5 mass %.
  • Although there is no particular limitation on the sulfonic acid group-containing monomer, for example, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and metal salts such as sodium salts thereof: amine salts thereof and the like can be used thereas. The sulfonic acid group-containing monomer can be used alone or in combination of two or more.
  • The acrylic copolymer is dissolved in dimethyl sulfaxide. By using dimethyl sulfrxide as an organic solvent, its safety increases.
  • From the viewpoint of effectively suppressing discoloration of the acrylic fiber, the spinning solution may comprise a polyphosphate in an amount of 0.05 mass % or more, or in an amount of 0.06 mass % or more, or in an amount of 0.07 mass % or more with respect to the total mass of the acrylic copolymer. From the viewpoint of spinning properties and prevention of discoloration, with regard to the upper limit of the polyphosphate, the spinning solution may comprise the polyphosphate in an amount of 5 mass % or less, or in an amount of 4.5 mass % or less, or in an amount of 4 mass % or less, or in an amount of 3.5 mass % or less, or in an amount of 3 mass % or less, or in an amount of 2.5 mass % or less, or in an amount of 2 mass % or less, or in an amount of 1.5 mass % or less, or in an amount of 1 mass % or less, or in an amount of 0.9 mass % or less, or in an amount of 0.7 mass % or less, or in an amount of 0.5 mass % or less with respect to the total mass of the acrylic copolymer.
  • The polyphosphate need only be an inorganic polyphosphate, and has no limitation. For example, pyrophosphates, tripolyphosphates, tetrapolyphosphates, trimetaphosphates, tetrametaphosphates, and the like can be used. Among these, from the viewpoint of a high solubility and ease of acquisition, tripolyphosphates may be preferable. There is no particular limitation on the type of salt, and any salts such as sodium salts, potassium salts, and ammonium salts can be used. From the viewpoint of excellent solubility in water, salt may be a watersoluble salt such as a sodium salt and a potassium salt. Examples of the pyrophosphates (also referred to as “diphosphate”) include sodium pyrophosphate and potassium pyrophosphate. Examples of the tripolyphosphates include sodium tripolyphosphate, aluminum dihydrogen tripolyphosphate, and potassium tripolyphosphate. Examples of the tetrapolyphosphates include sodium tetrapolyphosphate and potassium tetrapolyphosphate.
  • From the viewpoint of spinnability and solubility of the polyphosphate, the spinning solution may comprise water in an amount of 8 to 16 mass %, or in an amount of 8 to 15 mass %, or in an amount of 8 to 14 mass %, or in an amount of 8 to 13 mass %, or in an amount of 8 to 12.5 mass % with respect to the total mass of the acrylic copolymer.
  • Although the composition of the spinning solution depends on the composition of the acrylic copolymer, the spinning solution may comprise, with respect to the total mass of the spinning solution, the acrylic copolymer in an amount of 20 to 30 mass %, DMSO in an amount of 65.2 to 78.49 mass %, water in an amount of 1.5 to 4.8 mass %, and the polyphosphate in an amount of 0.01 to 1.5 mass %, or comprises the acrylic copolymer in an amount of 22 to 30 mass %, DMSO in an amount of 66 to 75.99 mass %, water in an amount of 2 to 4 mass %, and the polyphosphate in an amount of 0.01 to 1.5 mass %, or comprises the acrylic copolymer in an amount of 25 to 30 mass %, DMSO in an amount of 66.5 to 72.49 mass %, water in an amount of 2.5 to 3.5 mass %, and the polyphosphate in an amount of 0.01 to 1.5 mass %, for example.
  • The spinning solution may also comprise other additives for improving fiber properties as needed. Examples of the additives include gloss adjusting agents such as titanium dioxide, silicon dioxide, esters and ethers of cellulose derivatives including cellulose acetate, coloring agents such as organic pigments, inorganic pigments, and dyes, and stabilizers for increasing light resistance and heat resistance.
  • The spinning solution, although not particularly limited, can be prepared by mixing the acrylic copolymer, DMSO, water, and the polyphosphate. From the viewpoint of the solubility of the polyphosphate, the spinning solution may be prepared by mixing the acrylic copolymer, DMSO, and an aqueous solution of the polyphosphate. In order to increase the solubility of the acrylic copolymer, the spinning solution may be prepared by, after DMSO and the aqueous solution of the polyphosphate are added to the acrylic copolymer, stirring the resulting mixture at 40 to 80° C. for 3 to 12 hours, or may be prepared by stirring the resulting mixture at 50 to 75° C. for 4 to 10 hours, or may be prepared by stirring the resulting mixture at 60 to 70° C. for 5 to 8 hours. Note that it is inferred that in the preparation of the spinning solution, if a mixture of the acrylic copolymer, DMSO, and the aqueous solution of the polyphosphate is processed at 60° C. or more for 5 hours or more, for example, hydrochloric acid may be produced through dehydrochlorination of the acrylic copolymer, but the produced hydrochloric acid (hydrogen ions) is utilized in an equilibrium reaction with a phosphate group derived from the polyphosphate, and thereby decomposition of DMSO by hydrochloric acid is prevented and discoloration of fiber to yellow or brown is suppressed. An acrylic copolymer comprising moisture may also be used as the acrylic copolymer. When the acrylic copolymer comprising moisture (hereinafter, also simply referred to as watercomprising acrylic copolymer) is used as the acrylic copolymer, in one or more embodiments of the present invention, the total mass of the acrylic copolymer refers to the dry mass of the acrylic copolymer, and the dry mass of the acrylic copolymer is obtained by drying a watercomprising acrylic copolymer at 60° C. for 10 hours, removing moisture, and then measuring the resulting mass thereof. DMSO comprising moisture may be used as DMSO. In this specification, unless otherwise stated, the acrylic copolymer refers to an acrylic copolymer that comprises no moisture, and DMSO refers to DMSO that comprises no moisture.
  • Acrylic fiber is obtained by wet spinning the spinning solution with an ordinary method. For example, first, the spinning solution is discharged directly or through a spinning nozzle into a coagulation liquid (coagulation bath) with an aqueous solution of DMSO, and coagulated so as to obtain fiber. The coagulation bath can be prepared using an aqueous solution of DMSO having a DMSO concentration of 40 to 70 mass % at a temperature of 5 to 40° C., for example. If the concentration of the good solvent such as DMSO in the coagulation bath is excessively low, the spinning solution tends to coagulate fast, its coagulated structure tends to be rough, and voids tend to form in the fiber.
  • Next, the fiber (coagulated yarn) may be introduced into an aqueous solution of DMSO whose concentration is lower than that of the coagulation liquid and that has a temperature of 30° C. or more, or into warm water having a temperature of 30° C. or more, may be subjected to solvent removal, water washing, and drawing, and relaxing may also be performed after drawing as needed. In one or more embodiments, after the fiber is drawn in the aqueous solution of DMSO whose concentration is lower than that of the coagulation liquid and that has a temperature of 30° C. or more, the fiber is washed with warm water having a temperature of 30° C. or more. The solvent is removed by water washing. From the viewpoint of increasing the strength and productivity of fiber, the draw ratio, although not particularly limited, may be 2 to 8-fold, or 2 to 7-fold, or 2 to 6-fold. It is inferred that during the steps of solvent removal, water washing, and drawing in the aqueous solution of DMSO as well, if fiber is processed at 80° C. or more for 1 hour or more, for example, hydrochloric acid may be produced through dehydrochlorination of the acrylic copolymer, but the produced hydrochloric acid (hydrogen ions) is utilized in the equilibrium reaction with a phosphate group derived from the polyphosphate, as a result of which decomposition of DMSO by hydrochloric acid is prevented and discoloration of fiber to yellow or brown is suppressed.
  • Next, the fiber (drawn yarn) may be dried. During drying, a finishing oil may also be attached to the fiber as needed. In general, it is suffcient to use the finishing oil that is used to prevent static electricity, and prevent fiber from sticking each other, and improve texture of fiber in the spinning step, and a known finishing oil can be used. The drying temperature, although not particularly limited, may be 110 to 190° C., and in one or more embodiments, 110 to 160° C., for example. The dried fiber may also be further drawn thereafter as needed, and the draw ratio may be 1 to 4-fold. In one or more embodiments, the total draw ratio including drawing before drying is 2 to 12-fold.
  • In one or more embodiments, the fiber that is obtained by drying or obtained by drawing after drying may be subjected to relaxing processing at 15% or more. The relaxing processing can be performed in dry heat or a superheated steam atmosphere at a high temperature of 150 to 200° C., and in one or more embodiments, 150 to 190° C., for example. Alternatively, the relaxing processing can be performed in a pressurized water vapor atmosphere or a heated pressurized water vapor atmosphere at 120 to 180° C. and 0.05 to 0.4 MPa, and in one or more embodiments, 0.1 to 0.4 MPa.
  • From the viewpoint of suitable use as artificial hair, the single fiber fineness of the acrylic fiber may be 30 to 100 dtex, or 40 to 80 dtex, or 45 to 70 dtex. Herein, the single fiber fineness means the average value of the finenesses of any 100 single fibers.
  • The acrylic fiber may also comprise phosphorus derived from the polyphosphate. For example, the acrylic fiber may also comprise phosphorus in an amount of 5 to 250 ppm, in an amount of 10 to 150 ppm, and in an amount of 15 to 80 ppm with respect to the total mass of the acrylic fiber. The amount of phosphorus can be determined as follows.
  • EXAMPLES
  • One or more embodiments of the present invention will be described in further detail using the following Examples. Note that the present invention is not limited to the following Examples.
  • Example 1
  • Spinning Solution
  • 500 g of an acrylic copolymer constituted by 45.7 mass % acrylonitrile, 52.3 mass % vinyl chloride, and 2.0 mass % sodium styrene sulfonate, 1223 g of DMSO, and 62.5 g of an aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass % were added to a 7-L stainless steel container, the acrylic copolymer was dissolved through stirring at 70° C. for 12 hours, and thereby a spinning solution was produced.
  • Spinning Conditions
  • The obtained spinning solution was subjected to wet spinning at a spinning speed of 2 m/min in a coagulation bath with an aqueous solution of DMSO having a temperature of 20° C. and a concentration of 57 mass %, using a spinning nozzle (hole diameter: 0.3 mm, number of holes: 50 holes), and then drawn 3-fold in a drawing bath with an aqueous solution of DMSO solution having a temperature of 80° C. and a concentration of 50 mass %. Next, after water washing was performed using warm water having a temperature of 90° C., acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained by drying and drawing 2-fold at 140° C., and performing 20%-relaxing processing at 160° C.
  • Example 2
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that an aqueous solution of sodium tripolyphosphate having a concentration of 1.22 mass % was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Example 3
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that an aqueous solution of sodium tripolyphosphate having a concentration of 2.44 mass % was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Example 4
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that an aqueous solution of sodium tripolyphosphate having a concentration of 3.66 mass % was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Example 5
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that an aqueous solution of sodium pyrophosphate having a concentration of 1.22 mass % was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Example 6
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that an aqueous solution of sodium tetrapolyphosphate having a concentration of 1.22 mass % was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Comparative Example 1
  • Acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained similarly to Example 1, except that pure water was used instead of the aqueous solution of sodium tripolyphosphate having a concentration of 0.61 mass %.
  • Comparative Example 2
  • Spinning Solution
  • 500 g of an acrylic copolymer constituted by 45.7 mass % acrylonitrile, 52.3 mass % vinyl chloride, and 2.0 mass % sodium styrene sulfonate, 1223 g of DMSO, and 0.7625 g of sodium tripolyphosphate were added to a 7-L stainless steel container, the acrylic copolymer was dissolved by stirring at 70° C. for 12 hours, and thereby a spinning solution was produced.
  • Spinning Conditions
  • The obtained spinning solution was subjected to wet spinning at a spinning speed of 2 m/min in a coagulation bath with an aqueous solution of DMSO having a temperature of 20° C. and a concentration of 57 mass %, using a spinning nozzle (hole diameter: 0.3 mm, number of holes: 50 holes), and then drawn 3-fold in a drawing bath with an aqueous solution of DMSO having a temperature of 80° C. and a concentration of 50 mass %. Next, after water washing was performed using warm water having a temperature of 90° C., acrylic fiber having a single fiber fineness of approximately 46 dtex was obtained by drying and drawing 2-fold at 140° C., and performing 20%-relaxing processing at 160° C. 50 yarns broke in the coagulation bath in the 2 hours after spinning started, and operability was extremely unstable.
  • The color of the acrylic fibers of Examples 1 to 6 and Comparative Examples 1 and 2 was measured using the following colorimetry method, and the results are shown in Table 1 below. Also, the content ofphosphorus in the acrylic fibers of Examples 1 to 6 and Comparative Examples 1 and 2 was measured using the following phosphorus quantification method, and the results are shown in Table 1 below. Table 1 below also shows the blending amount of a polyphosphate and the blending amount of water with respect to the total mass of the acrylic copolymer in the spinning solution.
  • Method for Measuring Color of Fiber
  • A sample for colorimetry was produced such that the fiber bundle of 500 fibers had a width of 5 mm, colorimetry was performed at any 4 positions using a spectrophotometer (“CM-2600d” produced by KONICA MINOLTA, INC), in conditions of diffused lighting with 10 degrees, light receiving method of D65, measurement diameter of a 8 mm, and an SCE method, and the average value of those measurement values was obtained as the color.
  • Phosphorus Quantification Method
  • Sulfuric acid, nitric acid, hydrofluoric acid, and perchloric acid were added to fibers that were cut to a cut length of 0.5 cm, and the fibers were decomposed by heating at 120° C. in reflux conditions. After the resulting mixture was condensed by heating until sulfuric acid produced white smoke, the condensate was dissolved by warming with diluted nitric acid at 100° C. for 45 minutes, and calibrated to a certain volume. The obtained liquid with the certain volume was used to quantify the phosphorus element with an ICP emission spectrophotometer (“SPS4000” produced by Seiko Instruments Inc).
  • TABLE 1
    Blending Content of
    amount of Blending phosphorus
    poly- amount of Type of in acrylic
    phosphate water poly- fiber Color of acrylic fiber
    (mass %) (mass %) phosphate (ppm) a value b value
    Ex. 1 0.0763 12.4238 sodium 18 1.30 21.16
    Ex. 2 0.1525 12.3475 tripoly- 46 1.82 21.60
    Ex. 3 0.3050 12.1950 phosphate 57 2.01 22.00
    Ex. 4 0.4575 12.0425 74 1.66 21.92
    Ex. 5 0.1525 12.3475 sodium 21 1.44 21.70
    pyro-
    phosphate
    Ex. 6 0.1525 12.3475 sodium 77 1.72 21.34
    tetrapoly-
    phosphate
    Comp. 12.5 0 2.63 22.71
    Ex. 1
    Comp. 0.1525 sodium not not not
    Ex. 2 tripoly- measured measured measured
    phosphate
  • As is clear from the result of Table 1 above, in wet spinning using the spinning solution obtained by dissolving, in dimethyl sulfoxide, the acrylic copolymer comprising acrylonitrile, vinyl chloride, and a sulfonic acid group-containing monomer, in Examples 1 to 6 in which the spinning solutions contained water and polyphosphates, a values and b values were lower compared to Comparative Example 1 in which no polyphosphate was added to the spinning solution, and in particular, the b value was at least 0.5 lower than that of Comparative Example 1, and discoloration of the acrylic fiber was reduced. Note that although the polyphosphate was added to the spinning solution, in Comparative Example 2 in which no water was added, as described above, yarn broke and spinnability were poor.
  • Although the disclosure has been described with respect to only a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that various other embodiments may be devised without departing from the scope of the present invention. Accordingly, the scope of the invention should be limited only by the attached claims.

Claims (6)

What is claimed is:
1. A method for producing acrylic fiber, comprising:
preparing a spinning solution comprising an acrylic copolymer, dimethyl sulfoxide, water, and a polyphosphate; and
subjecting the spinning solution to wet spinning,
wherein the acrylic copolymer comprises acrylonitrile in an amount of 20 to 85 mass %, vinyl chloride in an amount of 14.5 to 79.5 mass %, and a sulfonic acid group-containing monomer in an amount of 0.5 to 10 mass % with respect to a total mass of the acrylic copolymer.
2. The method for producing acrylic fiber according to claim 1, wherein the spinning solution comprises the polyphosphate in an amount of 0.05 to 5 mass % with respect to the total mass of the acrylic copolymer.
3. The method for producing acrylic fiber according to claim 1, wherein the polyphosphate is at least one compound selected from the group consisting of a pyrophosphate, a tripolyphosphate, a tetrapolyphosphate, a trimetaphosphate, and a tetrametaphosphate.
4. The method for producing acrylic fiber according to claim 2, wherein the polyphosphate is at least one compound selected from the group consisting of a pyrophosphate, a tripolyphosphate, a tetrapolyphosphate, a trimetaphosphate, and a tetrametaphosphate.
5. The method for producing acrylic fiber according to claim 3, wherein the polyphosphate is a tripolyphosphate.
6. The method for producing acrylic fiber according to claim 4, wherein the polyphosphate is a tripolyphosphate.
US15/673,494 2015-02-16 2017-08-10 Method for producing acrylic fiber Abandoned US20170335491A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2015027998 2015-02-16
JP2015-027998 2015-02-16
PCT/JP2016/052936 WO2016132877A1 (en) 2015-02-16 2016-02-01 Method for producing acrylic fiber

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/052936 Continuation WO2016132877A1 (en) 2015-02-16 2016-02-01 Method for producing acrylic fiber

Publications (1)

Publication Number Publication Date
US20170335491A1 true US20170335491A1 (en) 2017-11-23

Family

ID=56692238

Family Applications (1)

Application Number Title Priority Date Filing Date
US15/673,494 Abandoned US20170335491A1 (en) 2015-02-16 2017-08-10 Method for producing acrylic fiber

Country Status (4)

Country Link
US (1) US20170335491A1 (en)
CN (1) CN107250449B (en)
TW (1) TW201638408A (en)
WO (1) WO2016132877A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190021425A1 (en) * 2016-03-25 2019-01-24 Kaneka Corporation Acrylic fiber for artificial hair, method for producing same, and head decoration article containing same
CN112251824A (en) * 2020-09-21 2021-01-22 吉林富博纤维研究院有限公司 Preparation process of polyacrylonitrile fiber and polyacrylonitrile fiber

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117468112A (en) * 2023-11-09 2024-01-30 邵阳阳光发品有限公司 Fiber material for wigs and preparation method thereof
CN118772328A (en) * 2024-07-26 2024-10-15 东华大学 A high-spinnability polyacrylonitrile spinning solution and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3354113A (en) * 1964-10-02 1967-11-21 Monsanto Co Color improvement of acrylic spin dopes
US3784511A (en) * 1972-03-28 1974-01-08 Monsanto Co Color stabilization of fibers from acrylonitrile polymers
JPH08269814A (en) * 1995-04-03 1996-10-15 Kanebo Ltd Flame retardant acrylic synthetic fiber excellent in weather resistance
CN1401829A (en) * 2002-08-13 2003-03-12 中国科学院山西煤炭化学研究所 Process for preparing polyacrylonitrile spinning solution
US20040074509A1 (en) * 2001-01-29 2004-04-22 Shoichi Murata Artificial hair and method for production thereof
JP2007291571A (en) * 2006-04-26 2007-11-08 Kaneka Corp Flame-retardant synthetic fiber, flame-retardant fiber complex body and flame-retardant mattress using the same
US20120322923A1 (en) * 2009-12-31 2012-12-20 Chemische Fabrik Budenheim Kg Flame retardant composition for thermoplastic molding compounds
US20130075136A1 (en) * 2011-09-22 2013-03-28 Li-Chih Yu Resin composition and prepreg, laminate and circuit board thereof

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB920808A (en) * 1958-06-20 1963-03-13 Osaka Kinzoku Kogyo Kabushiki Method for producing fibers and filaments
JPS491021B1 (en) * 1970-11-05 1974-01-11
JPS5144149B1 (en) * 1971-02-17 1976-11-26
US3784512A (en) * 1972-03-28 1974-01-08 Monsanto Co Color stabilized acid-dyeable acrylonitrile-containing fibers
US3884872A (en) * 1973-08-07 1975-05-20 Firestone Tire & Rubber Co Inorganic zinc salts as color stabilizers for acrylonitrile vinyl chloride dyesite containing copolymers
US4091066A (en) * 1976-07-04 1978-05-23 Japan Exlan Company Limited Process for producing flame retardant acrylic fibers with improved properties
JPS58174433A (en) * 1982-04-07 1983-10-13 Asahi Chem Ind Co Ltd Melt molding of acrylic polymer composition
JPS5994677A (en) * 1982-11-15 1984-05-31 帝人株式会社 Treatment of chlorine synthetic fiber
JPH0473219A (en) * 1990-07-11 1992-03-09 Mitsubishi Rayon Co Ltd Method for manufacturing acrylic fiber with excellent whiteness
JPH083813A (en) * 1994-06-15 1996-01-09 Japan Exlan Co Ltd Production of flame-retardant acrylonitrile synthetic fiber
CN1132862C (en) * 1999-02-02 2003-12-31 索罗蒂亚公司 :Modacrylic copolymer composition
JP4191930B2 (en) * 2001-01-30 2008-12-03 株式会社カネカ Artificial hair and method for producing the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3354113A (en) * 1964-10-02 1967-11-21 Monsanto Co Color improvement of acrylic spin dopes
US3784511A (en) * 1972-03-28 1974-01-08 Monsanto Co Color stabilization of fibers from acrylonitrile polymers
JPH08269814A (en) * 1995-04-03 1996-10-15 Kanebo Ltd Flame retardant acrylic synthetic fiber excellent in weather resistance
US20040074509A1 (en) * 2001-01-29 2004-04-22 Shoichi Murata Artificial hair and method for production thereof
CN1401829A (en) * 2002-08-13 2003-03-12 中国科学院山西煤炭化学研究所 Process for preparing polyacrylonitrile spinning solution
JP2007291571A (en) * 2006-04-26 2007-11-08 Kaneka Corp Flame-retardant synthetic fiber, flame-retardant fiber complex body and flame-retardant mattress using the same
US20120322923A1 (en) * 2009-12-31 2012-12-20 Chemische Fabrik Budenheim Kg Flame retardant composition for thermoplastic molding compounds
US20130075136A1 (en) * 2011-09-22 2013-03-28 Li-Chih Yu Resin composition and prepreg, laminate and circuit board thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190021425A1 (en) * 2016-03-25 2019-01-24 Kaneka Corporation Acrylic fiber for artificial hair, method for producing same, and head decoration article containing same
US10869514B2 (en) * 2016-03-25 2020-12-22 Kaneka Corporation Acrylic fiber for artificial hair, method for producing same, and head decoration article containing same
CN112251824A (en) * 2020-09-21 2021-01-22 吉林富博纤维研究院有限公司 Preparation process of polyacrylonitrile fiber and polyacrylonitrile fiber

Also Published As

Publication number Publication date
CN107250449A (en) 2017-10-13
WO2016132877A1 (en) 2016-08-25
CN107250449B (en) 2020-09-15
TW201638408A (en) 2016-11-01

Similar Documents

Publication Publication Date Title
US20170335491A1 (en) Method for producing acrylic fiber
RU2609913C2 (en) Coloured in spinning purely aromatic polyamide meta-type fibre
RU2662477C2 (en) Flame-resistant moulded cellulose bodies produced according to direct dissolving method
EP3315038A1 (en) Acrylic fiber for artificial hair, manufacturing method therefor and head accessory containing same
US10869514B2 (en) Acrylic fiber for artificial hair, method for producing same, and head decoration article containing same
WO2018047344A1 (en) Modified acrylonitrile-based fiber, method for producing said fiber, and fibrous structure containing said fiber
US10477908B2 (en) Acrylic fiber for artificial hair, method for producing same, and head decoration product comprising same
CN106367949B (en) A kind of manufacturing method of flame retardant viscose fiber
CN109957854A (en) A kind of polyamide blended fiber and its preparation method and application
JP2011252251A (en) Method for producing acrylic synthetic fiber
JP4128024B2 (en) Fiber for artificial hair with improved devitrification and method for producing the same
TW201631231A (en) Acrylic fiber production method
JP7187911B2 (en) Hygroscopic acrylonitrile fiber, method for producing said fiber, and fiber structure containing said fiber
US9702061B2 (en) Method for manufacturing pile fabric
JPS6130042B2 (en)
CN108774873A (en) A kind of low damage type soybean fiber fabric bleaching agent
JPH02300326A (en) Production of acrylic fiber having improved
JP4745194B2 (en) Acrylic fiber and method for producing the same
KR20240128093A (en) Antibacterial polyacrylonitrile-based synthetic fiber, its manufacturing method and head decoration product
JP5014799B2 (en) Hollow acrylic synthetic fiber
JP2519185B2 (en) Flame-retardant acrylic composite fiber
JPH0559608A (en) Anti-pilling acrylic fiber and method for producing the same
WO2023107050A2 (en) Synthetic hair production from acrylic fiber
JPH05279912A (en) Production of antipilling acrylic fiber
JP2003183931A (en) Acrylic synthetic fiber having excellent discharge printing properties

Legal Events

Date Code Title Description
AS Assignment

Owner name: KANEKA CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YOSHIMURA, SATORU;ANAHARA, MASARU;SIGNING DATES FROM 20170622 TO 20170703;REEL/FRAME:043550/0976

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION