EP3779004B1 - Tissu et produit textile - Google Patents

Tissu et produit textile Download PDF

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Publication number
EP3779004B1
EP3779004B1 EP19782317.2A EP19782317A EP3779004B1 EP 3779004 B1 EP3779004 B1 EP 3779004B1 EP 19782317 A EP19782317 A EP 19782317A EP 3779004 B1 EP3779004 B1 EP 3779004B1
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EP
European Patent Office
Prior art keywords
fiber
aromatic polyamide
meta
cloth
cloth according
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.)
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Application number
EP19782317.2A
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German (de)
English (en)
Other versions
EP3779004A1 (fr
EP3779004A4 (fr
Inventor
Hiroki Shimada
Kenji Iwashita
Kiho NABETANI
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.)
Teijin Ltd
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Teijin Ltd
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Publication of EP3779004A1 publication Critical patent/EP3779004A1/fr
Publication of EP3779004A4 publication Critical patent/EP3779004A4/fr
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Classifications

    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00—Woven fabrics designed to make specified articles
    • D03D1/0035—Protective fabrics
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/08—Heat resistant; Fire retardant
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/08—Heat resistant; Fire retardant
    • A41D31/085—Heat resistant; Fire retardant using layered materials
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/06—Dyes
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
    • 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
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/47—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads multicomponent, e.g. blended yarns or threads
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/513—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads heat-resistant or fireproof
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/533—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads antistatic; electrically conductive
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/54—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads coloured
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D10B2321/101—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide modacrylic
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/16—Physical properties antistatic; conductive
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments

Definitions

  • the present invention relates to a cloth having extremely excellent flame retardancy and having excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties, and a fiber product.
  • US2013/055491A1 relates to a yarn having high moisture regain for use in arc and flame protection and fabrics and garments containing the yarn.
  • US2014/026303A1 relates to a fiber blend, yarn, fabric, and/or garment suitable for use in arc and flame protection.
  • JP2014/210985A relates to a spun yarn having a protective ability against flame, heat, arc, etc., having high dyeing fastness, being difficult to yellow over time, and having excellent moisture absorption and release properties.
  • JP2017/008454A relates to a fabric and a textile product excellent in deepness of color, hardly causing skin burn.
  • JP2009/221632A relates to a sheath-core conjugate conductive acrylic fiber containing conductive fine particles in the core part at a high concentration and having an optimized core/sheath ratio, thereby establishing compatibility between high electric conductivity and stable processability.
  • an object of the invention is to provide a cloth which is advantageous in that the cloth has extremely excellent flame retardancy, and further has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties, preferably in that the whole of the cloth can be uniformly dyed, and a fiber product.
  • the present inventors have conducted extensive and intensive studies with a view toward achieving the above-mentioned object. As a result, it has been found that, by appropriately selecting the type of the fiber constituting the cloth and the like, there can be obtained a cloth which is advantageous not only in that the cloth has extremely excellent flame retardancy, and further has excellent washing shrinkage resistance and excellent hand, but also in that the whole of the cloth can be uniformly dyed, and further extensive and intensive studies have been made, and the present invention has been completed.
  • a cloth comprising a spun yarn which comprises a meta-type wholly aromatic polyamide fiber, a modacrylic fiber, and an electrically conductive fiber, wherein the conductive fiber is an acrylic fiber.
  • the spun yarn contains the meta-type wholly aromatic polyamide fiber in an amount of 5% by weight or more, based on the weight of the spun yarn. Further, it is preferred that the spun yarn contains the modacrylic fiber in an amount of 30% by weight or more, based on the weight of the spun yarn. It is preferred that the spun yarn contains the conductive fiber in an amount of 1% by weight or more, based on the weight of the spun yarn.
  • the spun yarn comprises only the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the conductive fiber. It is preferred that the meta-type wholly aromatic polyamide fiber has a residual solvent content of 0.1% by weight or less. It is preferred that the meta-type wholly aromatic polyamide fiber has a crystallinity in the range of from 15 to 25%.
  • a meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber is an aromatic polyamide having an aromatic polyamide skeleton comprising repeating structural units representedby the formula (1) below, wherein an aromatic diamine component different from the main constituent units of the repeating structure, or an aromatic dicarboxylic acid halide component is copolymerized as a third component with the aromatic polyamide skeleton so that the amount of the third component becomes 1 to 10 mol%, based on the total mole of the repeating structural units of the aromatic polyamide: -(NH-Ar1-NH-CO-Ar1-CO)- Formula (1) wherein Ar1 is a divalent aromatic group having a bonding group at a position other than the meta position or the parallel axis direction.
  • the aromatic diamine is the following formula (2) or (3)
  • the aromatic dicarboxylic acid halide is the following formula (4) or (5): H 2 N-Ar2-NH 2 Formula (2) H 2 N-Ar2-Y-Ar2-NH 2 Formula (3) XOC-Ar3-COX Formula (4) XOC-Ar3-Y-Ar3-COX Formula (5) wherein Ar2 represents a divalent aromatic group different from Ar1, Ar3 represents a divalent aromatic group different from Ar1, Y represents at least one atom or functional group selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group, and X represents a halogen atom.
  • the meta-type wholly aromatic polyamide fiber further contains an organic dye, an organic pigment, or an inorganic pigment.
  • the conductive fiber is an acrylic fiber. It is preferred that the modacrylic fiber and the conductive fiber are dyed with the same dye.
  • the cloth of the invention it is preferred that the cloth contains an ultraviolet light absorber and/or a reflective agent. Further, it is preferred that the cloth has a weight per unit in the range of from 130 to 300 g/m 2 . It is preferred that the cloth has an afterflame time of 2 seconds or less, as measured by the method prescribed in ISO 15025: 2000 A method. It is preferred that the cloth has a carbonized area of 30 cm 2 or less, as measured by the method prescribed in JIS L1091:1999 A-1 method. It is preferred that the cloth has a shrinkage rate of 5% or less, as measured after subjected to washing 5 times in accordance with the method prescribed in ISO 5077.
  • the cloth has a thermal shrinkage rate of 10% or less, as measured after subjected to heat treatment at 180°C for 5 minutes in accordance with the method prescribed in ISO17493. It is preferred that the cloth has a water absorbing time of 30 seconds or less, as measured by the method prescribed in JIS L1907:2010 (dropping method) . It is preferred that the cloth has a bending resistance of 7.0 cm or less, as measured by the method prescribed in JIS L1096:2010 Amethod (cantilever) . It is preferred that the cloth has an antistaticity of 7.0 ⁇ C or less, as measured by the method prescribed in JIS L1094:2014 (antistatic properties).
  • a fiber product using the above-mentioned cloth which is any one fiber product selected from the group consisting of protective clothing, fire-fighting fireproof clothing, fire fighting clothing, rescue clothing, workwear, a police uniform, Self-Defense Forces official clothing, and military clothing.
  • the cloth of the invention comprises a spun yarn which comprises ameta-type wholly aromatic polyamide fiber, a modacrylic fiber, and an electrically conductive fiber.
  • the meta-type wholly aromatic polyamide fiber used in the invention is a fiber formed from a polymer in which 85 mol% or more of the repeating units are m-phenyleneisophthalamide.
  • the meta-type wholly aromatic polyamide may be a copolymer containing a third component in an amount in the range of less than 15 mol%.
  • the meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method, and there is preferably used the meta-type wholly aromatic polyamide having, in terms of the degree of polymerization of the polymer, an intrinsic viscosity (I.V.) in the range of from 1.3 to 1.9 dl/g, as measured in the form of an N-methyl-2-pyrrolidone solution having a concentration of 0.5 g/100 ml.
  • I.V. intrinsic viscosity
  • the meta-type wholly aromatic polyamide may contain an alkylbenzenesulfonic acid onium salt.
  • alkylbenzenesulfonic acid onium salts include compounds, such as tetrabutylphosphonium hexylbenzenesulfonate, tributylbenzylphosphonium hexylbenzenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate, tributyltetradecylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, and tributylbenzylammonium dodecylbenzenesulfonate.
  • tetrabutylphosphonium dodecylbenzenesulfonate or tributylbenzylammonium dodecylbenzenesulfonate because they are easily available and have excellent thermal stability as well as high solubility in N-methyl-2-pyrrolidone.
  • the amount of the alkylbenzenesulfonic acid onium salt contained is preferably 2.5 mol% or more, preferably in the range of from 3.0 to 7.0 mol%, based on the mole of the poly-m-phenyleneisophthalamide.
  • an aromatic diamine component different from the main constituent units of the repeating structure, or an aromatic dicarboxylic acid halide component can be copolymerized as a third component with the aromatic polyamide skeleton so that the amount of the third component becomes 1 to 10 mol%, based on the total mole of the repeating structural units of the aromatic polyamide: -(NH-Ar1-NH-CO-Ar1-CO)- Formula (1) wherein Ar1 is a divalent aromatic group having a bonding group at a position other than the meta position or the parallel axis direction.
  • aromatic diamines which are represented by the formula (2) or (3), and which can be copolymerized as a third component, include p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, acetylphenylenediamine, aminoanisidine, benzidine, bis(aminophenyl) ether, bis(aminophenyl) sulfone, diaminobenzanilide, and diaminoazobenzene.
  • aromatic dicarboxylic acid dichlorides represented by the formula (4) or (5) include terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4'-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, and bis(chlorocarbonylphenyl) ether.
  • Ar2 represents a divalent aromatic group different from Ar1
  • Ar3 represents a divalent aromatic group different from Ar1
  • Y represents at least one atom or functional group selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group
  • X represents a halogen atom.
  • the crystallinity of the meta-type wholly aromatic polyamide fiber is preferably 5 to 35% because the absorption for a dye is excellent such that an intended color can be easily achieved even when using the dye in a reduced amount or even under poor dyeing conditions. Further, the crystallinity is more preferably 15 to 25% because localization of a dye in the surface is unlikely to occur and a high resistance to discoloration and color fading is obtained and further dimensional stability required for the practical use can be secured.
  • the residual solvent content of the meta-type wholly aromatic polyamide fiber is preferably 0.1% by weight or less (preferably 0.001 to 0.1% by weight) because excellent flame retardancy of the meta-type wholly aromatic polyamide fiber is not sacrificed.
  • the meta-type wholly aromatic polyamide fiber can be produced by the method mentioned below, and, particularly by the below-mentioned method, the crystallinity and residual solvent content in the above-mentioned respective ranges can be achieved.
  • the polymerization method for the meta-type wholly aromatic polyamide polymer there is no particular limitation, and, for example, the solution polymerization method or interfacial polymerization method described in JP-B-35-14399 , U.S. Patent No. 3,360,595 , JP-B-47-10863 , or the like may be used.
  • the spinning solution is not particularly limited, but an amide-solvent solution containing an aromatic copolyamide polymer obtained by the above-mentioned solution polymerization, interfacial polymerization, or the like may be used, or a solution obtained by isolating the polymer from the above-mentioned polymerization solution and dissolving the polymer in an amide solvent may be used.
  • amide solvents used include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethylsulfoxide, and especially preferred is N,N-dimethylacetamide.
  • the copolymerized aromatic polyamide polymer solution obtained as mentioned above further contains an alkali metal salt or an alkaline earth metal salt
  • the solution is stabilized and can be advantageously used in a higher concentration at low temperatures.
  • the amount of the alkali metal salt and alkaline earth metal salt is preferably 1% by weight or less, more preferably 0.1% by weight or less, based on the mass of the polymer solution.
  • the above-obtained spinning solution (meta-type wholly aromatic polyamide polymer solution) is discharged into a coagulation liquid so as to undergo coagulation.
  • the spinning apparatus there is no particular limitation, and a conventionally known wet spinning apparatus can be used. Further, with respect to the number of spinning holes of a spinning nozzle, the arrangement of the holes, the form of the hole, and the like, there is no particular limitation as long as wet spinning can be stably made, and, for example, a multihole spinning nozzle for rayon yarn having 1,000 to 30,000 holes and having a spinning hole diameter of 0.05 to 0.2 mm, or the like may be used.
  • the temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) being discharged from a spinning nozzle is suitably in the range of from 20 to 90°C.
  • an aqueous solution containing substantially no inorganic salt and having an amide solvent, preferably NMP concentration of 45 to 60% by weight at a bath solution temperature in the range of from 10 to 50°C is used.
  • the amide solvent (preferably NMP) concentration is less than 45% by weight, a structure having a thick skin is disadvantageously formed, so that the washing efficiency in the washing step is lowered, making it difficult to reduce the residual solvent content of the fiber.
  • the amide solvent (preferably NMP) concentration is more than 60% by weight, coagulation throughout the inside of the fiber cannot be achieved, making it difficult to reduce the residual solvent content of the fiber.
  • the time for immersing the fiber in the coagulation bath is suitably in the range of from 0.1 to 30 seconds.
  • the fiber is subjected to drawing at a draw ratio of 3 to 4 times. After drawing, the resultant fiber is well washed through an aqueous solution having an NMP concentration of 20 to 40% by weight at 10 to 30°C and further through a warm water bath at 50 to 70°C.
  • an aqueous solution having an amide solvent preferably NMP concentration of 45 to 60% by weight at a bath solution temperature in the range of from 10 to 50°C.
  • the fiber after being washed is subjected to dry heat treatment at a temperature of 270 to 290°C, obtaining a meta-type wholly aromatic aramid fiber which satisfies the crystallinity and residual solvent content in the above-mentioned respective ranges.
  • the fiber is preferably in the form of a short fiber having a fiber length of 25 to 200 mm in view of mixing with another fiber.
  • the single fiber fineness is preferably in the range of from 1 to 5 dtex.
  • the spun yarn contains the meta-type wholly aromatic polyamide fiber in an amount of 5% by weight or more (more preferably 5 to 50% by weight), based on the weight of the spun yarn.
  • the amount of the meta-type wholly aromatic polyamide fiber contained is smaller than the above range, there is a possibility that the cloth becomes poor in flame retardancy.
  • the modacrylic fiber is a fiber formed from a linear synthetic polymer comprising repeating units for acrylonitrile group in an amount of 35 to less than 85% by weight, as measured in accordance with JIS L0204-2 (2001).
  • the modacrylic fiber is advantageous in that woven fabric formed from the modacrylic fiber is wrinkle resistant and excellent in fireproofness, chemical resistance, beautiful appearance, hand, washing shrinkage resistance, and the like.
  • the spun yarn contains the modacrylic fiber in an amount of 30% by weight or more (more preferably 50 to 90% by weight, especially preferably 60 to 80% by weight), based on the weight of the spun yarn.
  • the amount of the modacrylic fiber contained is smaller than the above range, there is a possibility that the cloth becomes poor in hand, washing shrinkage resistance, and the like.
  • the spun yarn contains not only the meta-type wholly aromatic polyamide fiber and modacrylic fiber but also a conductive fiber.
  • the cloth of the invention contains the meta-type wholly aromatic polyamide fiber and an acrylic fiber, such that when the cloth is dyed with a cationic dye, all the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the acrylic fiber are dyed deep color, and the whole of the cloth is uniformly dyed. In this case, it is preferred that the meta-type wholly aromatic polyamide fiber and the conductive fiber are dyed the same color.
  • the color difference between the meta-type wholly aromatic polyamide fiber and the conductive fiber, in terms of ⁇ E, is preferably 3 or less.
  • the acrylic fiber preferred is a fiber having conductive carbon incorporated into an acrylic fiber, a sheath-core manner conjugate fiber comprising a core portion containing conductive fine particles and a sheath portion containing no conductive fine particle, or the like.
  • a sheath-core manner conjugate fiber or an eccentric sheath-core manner conjugate fiber having a sheath portion comprising an acryl containing no conductive fine particle, and a core portion comprising a conductive carbon-containing polymer, or the like.
  • an acrylic fiber described in JP-A-2009-221632 is preferred.
  • a sheath-core manner conductive acrylic fiber comprising a core portion containing conductive fine particles and a sheath portion containing no conductive fine particle, wherein the acrylic fiber has a core-sheath ratio of 15/85 to 50/50, the content of the conductive fine particles in the core portion is 20 to 60% by mass, and the acrylic fiber has a single fiber specific resistance of 10 1 to 10 6 ⁇ cm.
  • the fiber may be in the form of either a continuous fiber (multifilament) or a short fiber.
  • a short fiber having a fiber length of 25 to 200 mm (more preferably 30 to 150 mm) is preferred.
  • the single fiber fineness is preferably in the range of from 1 to 5 dtex.
  • the spun yarn contains the conductive fiber in an amount of 1% by weight or more (more preferably 1 to 5% by weight), based on the weight of the spun yarn.
  • the weight percentage of the conductive fiber is smaller than the above range, there is a possibility that the cloth becomes poor in antistatic properties.
  • the spun yarn comprises only the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the conductive fiber, but the spun yarn may further contain an additional fiber.
  • a flame-retardant fiber such as a para-type wholly aromatic polyamide fiber, a wholly aromatic polyester fiber, apolybenzoxazole (PBO) fiber, apolybenzimidazole (PBI) fiber, apolybenzothiazole (PBTZ) fiber, apolyimide (PI) fiber, a polysulfonamide (PSA) fiber, a polyether ether ketone (PEEK) fiber, apolyetherimide (PEI) fiber, apolyarylate (PAr) fiber, a melamine fiber, a phenolic fiber, a fluorine fiber, or a polyphenylene sulfide (PPS) fiber, maybe contained in the spun yarn.
  • PBO apolybenzoxazole
  • PBI apolybenzimidazole
  • PBTZ apo
  • a cellulose fiber, a polyolefin fiber, an acrylic fiber, a rayon fiber, a cotton fiber, an animal hair fiber, a polyurethane fiber, a polyvinyl chloride fiber, a polyvinylidene chloride fiber, an acetate fiber, a polycarbonate fiber, or the like is contained in the spun yarn, water absorption properties, dyeing properties, comfortability to wear, or the like is advantageously imparted to the cloth.
  • the method for producing the cloth there is no particular limitation, and any known method can be used.
  • spun yarns of the above-mentioned fibers are mixed to obtain a spun yarn, and then the spun yarn in the form of a single yarn or a two folded yarn is woven using a rapier loom or the like into a weave structure, such as twill weave or plain weave.
  • the cloth is constituted solely by the spun yarn, but the spun yarn may be interwoven or interknitted with the above-mentioned additional fiber.
  • post-processing steps include steps, such as scouring, drying, relaxation, singeing, dyeing, and a function imparting treatment.
  • the cloth is subjected to dyeing processing using a dye bath containing the above-mentioned cationic dye.
  • a method can be preferably employed in which the cloth is dyed at 115 to 135°C and then subj ected to reduction treatment, and dried, or the like , but the method is not limited to this.
  • a carrier is preferably used, and it is preferred that the cloth is subjected to dyeing treatment in the bath of cationic dye which is the same bath as the carrier . Further, when the cloth is treated with a special surfactant before subjected to cationic dyeing, the cloth can be dyed deep color in the open width dyeing.
  • the carrier is, for example, at least one member selected from DL- ⁇ -ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol, 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamyl alcohol, p-anisyl alcohol, and benzhydrol.
  • benzyl alcohol DOWANOL PPH, manufactured by The Dow Chemical Company, andCINDYE DNK, manufactured by BOZZETTO Group. Further, from the viewpoint of further improving the dyeing properties, benzyl alcohol, especially, 2,5-dimethylbenzyl alcohol or 2-nitrobenzyl alcohol is preferably used.
  • the amount of the carrier is preferably 1 to 10 parts by weight (more preferably 1 to 5 parts by weight), relative to 100 parts by weight of the meta-type wholly aromatic polyamide fiber.
  • an open width treatment or a jet scouring or relaxation treatment may be employed.
  • a method is employed in which a treatment is conducted using an open width non-tension machine in continuous scouring or continuous drying.
  • a method using a Sofcer scouring machine, a tenter dryer, a Shrink Surfer, a short loop, a Luciole dryer, or the like is employed.
  • the scouring or relaxation step can be optionally omitted.
  • the cloth may be subjected to clipping and/or singeing.
  • a sweat absorber a water repellent, a thermal storage agent, an ultraviolet light screening agent, an antistatic agent, an anti-fungus agent, a deodorant, a mothproofing agent, a mosquito repellent, a phosphorescent agent, a retroreflective agent, or the like may be applied to the cloth.
  • the woven or knitted fabric used may be spun-dyed yarn fabric, fiber or yarn colored fabric, or piece dyed fabric.
  • polyethylene glycol diacryate a polyethylene glycol diacryate derivative, a polyethylene terephthalate-polyethylene glycol copolymer, or a water-soluble polyurethane.
  • a padding treatment method As examples of the method for applying a sweat absorber to the cloth, there can be mentioned a padding treatment method, and a method in which a treatment is made using the same bath as the dyeing solution during the dyeing processing.
  • the thus obtained cloth contains the above-mentioned spun yarn, and therefore has extremely excellent flame retardancy and has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties.
  • an acrylic fiber is used as the conductive fiber, such that when the cloth is dyed with a cationic dye, all the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the acrylic fiber are dyed deep color, and the whole of the cloth is uniformly dyed.
  • the cloth of the invention it is preferred that the cloth has a weight per unit in the range of from 130 to 300 g/m 2 . Further, it is preferred that the cloth has an afterflame time of 2 seconds or less, as measured by the method prescribed in ISO 15025:2000 A method. It is preferred that the cloth has a carbonized area of 30 cm 2 or less, as measured by the method prescribed in JIS L1091:1999 A-1 method. It is preferred that the cloth has a shrinkage rate of 5% or less, as measured after subjected to washing 5 times in accordance with the method prescribed in ISO 5077.
  • the cloth has a thermal shrinkage rate of 10% or less, as measured after subjected to heat treatment at 180°C for 5 minutes in accordance with the method prescribed in ISO 17493. It is preferred that the cloth has a water absorbing time of 30 seconds or less, as measured by the method prescribed in JIS L1907:2010 (dropping method) . It is preferred that the cloth has a bending resistance of 7.0 cm or less, as measured by the method prescribed in JIS L1096:2010 A method (cantilever). It is preferred that the cloth has an antistaticity of 7.0 ⁇ C or less, as measured by the method prescribed in JIS L1094:2014 (antistatic properties).
  • the fiber product of the invention is a fiber product using the above-described cloth, which is any one fiber product selected from the group consisting of protective clothing, fire-fighting fireproof clothing, fire fighting clothing, rescue clothing, workwear, a police uniform, Self-Defense Forces official clothing, and military clothing.
  • the fiber product uses the above-described cloth, and therefore has extremely excellent flame retardancy and has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties.
  • a weight per unit was measured in accordance with the method prescribed in JIS L1096:2010 A method.
  • Flammability was measured in accordance with the method prescribed in ISO 15025:2000 A method, or JIS L1091:1999 A-1 method.
  • a shrinkage rate was measured after subjected to washing 5 times in accordance with the method prescribed in ISO 5077. n (the number of samples) was 5 and the measurement was conducted with respect to the warp direction and the weft direction, and an average of the values measured in the both directions was determined.
  • a thermal shrinkage rate was measured after subjected to heat treatment at 180°C for 5 minutes in accordance with the method prescribed in ISO 17493. n (the number of samples) was 5 and the measurement was conducted with respect to the warp direction and the weft direction, and an average of the values measured in the both directions was determined.
  • a water absorption ability of a cloth to be tested was measured in accordance with the method prescribed in JIS L1907:2010.
  • a bending resistance of a cloth to be tested was measured in accordance with the method prescribed in JIS L1096:2010 A method (cantilever).
  • a bundle of the basic fiber having a diameter of about 1 mm was prepared and set on a holder for a fiber sample and subjected to measurement of a diffraction profile.
  • Conditions for the measurement were such that the source of an X-ray was Cu-K ⁇ (50 kV, 300 mA), the scanning angle range was 10 to 35°, the continuous measurement width was 0.1°, and the scanning speed was 1°/minute. From the actually measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain a total scattering profile.
  • Crystallinity % Crystal scattering intensity / Total scattering intensity ⁇ 100
  • a meta-type wholly aromatic polyamide fiber was produced by the method described below.
  • a 2-[2H-benzotriazol-2-yl]-4-6-bis(1-methyl-1-phenylethyl)ph enol powder (solubility in water: 0.01 mg/L) was mixed into and dissolved in the polymer solution in an amount of 3.0% by weight, based on the weight of the polymer, followed by deaeration under a reduced pressure, to obtain a spinning solution (spinning dope).
  • Spinning was performed by discharging the above-obtained spinning dope from a spinning nozzle having 500 holes and having a hole diameter of 0.07 mm into a coagulation bath at a bath temperature of 30°C.
  • the fiber after being washed was subjected to dry heat treatment using a heated roller having a surface temperature of 280°C to obtain a meta-type wholly aromatic polyamide fiber.
  • the obtained meta-type wholly aromatic polyamide fiber had physical properties such that the fineness was 1.7 dtex, the residual solvent content was 0.08% by weight, and the crystallinity was 19%.
  • crimping and cutting were performed to obtain a staple fiber having a length of 51 mm.
  • Post-processing was performed by conducting singeing, scouring, and final setting.
  • Procedure was performed in substantially the same manner as in Example 1 except that the conductive fiber was changed to an acrylic conductive fiber (AAS), and that the cloth was dyed with a cationic dye.
  • the fabric had 7.0 ⁇ C or less and was acceptable for the antistatic properties. Further, all the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the acrylic fiber were dyed deep color, and the whole of the cloth was uniformly dyed. The results are shown in Table 1.
  • Example 1 Example 2* Example 3* Example 4 Comparative Example 1 Comparative Example 2 MA/MD/AS MA/MD/AS MA/MD/AAS MA/MD/RY/PA MA/MD/RY/PA Mixing ratio % 18/80/2 28/70/2 38/60/2 18/80/2 25/30/40/5 35/30/15/20 Weight per unit g/m 2 200 200 200 200 200 200 200 200 200 Flammability Afterflame (second) 0 0 0 0 0 0 0 Washing shrinkage rate % 5 4 3 5 10 7 Dry heat shrinkage % 4 5 5 4 6 5 Hand and comfortability Cantilever (cm) 6.5 6.8 6.4 6.5 8.9 10.0 *Reference example
  • a cloth which is advantageous not only in that the cloth has extremely excellent flame retardancy, and further has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties, but also in that the whole of the cloth can be uniformly dyed, and a fiber product, and the invention is of extremely great industrial significance.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Woven Fabrics (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
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Claims (15)

  1. Tissu comprenant un filé qui comprend une fibre de polyamide entièrement aromatique de type méta, une fibre modacrylique, et une fibre électriquement conductrice ; caractérisé en ce que la fibre électriquement conductrice est une fibre acrylique.
  2. Tissu selon la revendication 1, le filé contenant la fibre de polyamide entièrement aromatique de type méta en une quantité de 5 % en poids ou plus, sur la base du poids du filé.
  3. Tissu selon la revendication 1 ou 2, le filé contenant la fibre modacrylique en une quantité de 30 % en poids ou plus, sur la base du poids du filé.
  4. Tissu selon l'une quelconque des revendications 1 à 3, le filé contenant la fibre électriquement conductrice en une quantité de 1 % en poids ou plus, sur la base du poids du filé.
  5. Tissu selon l'une quelconque des revendications 1 à 4, le filé comprenant seulement la fibre de polyamide entièrement aromatique de type méta, la fibre modacrylique, et la fibre électriquement conductrice.
  6. Tissu selon l'une quelconque des revendications 1 à 5, la fibre de polyamide entièrement aromatique de type méta possédant une teneur en solvant résiduel de 0,1 % en poids ou moins.
  7. Tissu selon l'une quelconque des revendications 1 à 6, la fibre de polyamide entièrement aromatique de type méta possédant une cristallinité dans la plage allant de 15 à 25 %.
  8. Tissu selon l'une quelconque des revendications 1 à 7, un polyamide entièrement aromatique de type méta formant la fibre de polyamide entièrement aromatique de type méta étant un polyamide aromatique possédant un squelette de polyamide aromatique comprenant des motifs structuraux répétitifs représentés par la formule (1) ci-dessous, un composant de type diamine aromatique différent des motifs constitutifs principaux de la structure répétitive, ou un composant de type halogénure d'acide dicarboxylique aromatique étant copolymérisé en tant que troisième composant avec le squelette de polyamide aromatique de sorte que la quantité du troisième composant devienne 1 à 10 % en moles, sur la base du nombre total de moles des motifs structuraux répétitifs du polyamide aromatique :

            -(NH-Ar1-NH-CO-Ar1-CO}-     Formule (1)

    Ar1 étant un groupe aromatique divalent possédant un groupe de liaison au niveau d'une position autre que la position méta ou la direction d'axe parallèle.
  9. Tissu selon la revendication 8, dans lequel, en tant que le troisième composant, la diamine aromatique est la formule suivante (2) ou (3), ou l'halogénure d'acide dicarboxylique aromatique est la formule suivante (4) ou (5) :

            H2N-Ar2-NH2     Formule (2)

            H2N-Ar2-Y-Ar2-NH2     Formule (3)

            XOC-Ar3-COX     Formule (4)

            XOC-Ar3-Y-Ar3-COX     Formule (5)

    Ar2 représentant un groupe aromatique divalent différent de Ar1, Ar3 représentant un groupe aromatique divalent différent de Ar1, Y représentant au moins un atome ou groupe fonctionnel choisi dans le groupe constitué par un atome d'oxygène, un atome de soufre et un groupe alkylène, et X représentant un atome d'halogène.
  10. Tissu selon l'une quelconque des revendications 1 à 9, la fibre de polyamide entièrement aromatique de type méta contenant en outre un colorant organique, un pigment organique ou un pigment inorganique.
  11. Tissu selon l'une quelconque des revendications 1 à 10, la fibre modacrylique et la fibre électriquement conductrice étant colorées avec le même colorant.
  12. Tissu selon l'une quelconque des revendications 1 à 11, lequel contient un absorbant de la lumière ultraviolette et/ou un agent réflecteur ; et/ou lequel possède un poids par unité dans la plage allant de 130 à 300 g/m2.
  13. Tissu selon l'une quelconque des revendications 1 à 12, lequel possède un temps de post-flamme de 2 secondes ou moins, tel que mesuré par le procédé fixé dans la norme ISO 15025:2000 procédé A ; et/ou
    lequel possède une aire carbonisée de 30 cm2 ou moins, telle que mesurée par le procédé fixé dans la norme JIS L1091:1999 procédé A-1 ; et/ou lequel possède un taux de rétrécissement de 5 % ou moins, tel que mesuré après avoir été soumis à 5 lavages conformément au procédé fixé dans la norme ISO 5077.
  14. Tissu selon l'une quelconque des revendications 1 à 13, lequel possède un taux de rétrécissement thermique de 10 % ou moins, tel que mesuré après avoir été soumis à un traitement thermique à 180 °C pendant 5 minutes conformément au procédé fixé dans la norme ISO 17493 ; et/ou lequel possède un temps d'absorption d'eau de 30 secondes ou moins, tel que mesuré par le procédé fixé dans la norme JIS L1907:2010 (procédé de déversement) ; et/ou
    lequel possède une résistance à la flexion de 7,0 cm ou moins, telle que mesurée par le procédé fixé dans la norme JIS L1906:2010 procédé A (en porte-à-faux) ; et/ou
    lequel possède un comportement antistatique de 7,0 µC ou moins, tel que mesuré par le procédé fixé dans la norme JIS L1094:2014 (propriétés antistatiques).
  15. Produit de fibre utilisant le tissu selon l'une quelconque des revendications 1 à 14, qui est un quelconque produit de fibre choisi dans le groupe constitué par un vêtement protecteur, un vêtement coupe-feu de lutte contre le feu, un vêtement de lutte contre le feu, un vêtement de sauvetage, un vêtement de travail, un uniforme de police, un vêtement d'officiel des Forces d'Auto-Défense, et un vêtement militaire.
EP19782317.2A 2018-04-03 2019-03-25 Tissu et produit textile Active EP3779004B1 (fr)

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JPH11250A (ja) * 1997-06-10 1999-01-06 Mitsubishi Rayon Co Ltd 制電性及び抗菌性を有する難燃毛布
US20050208855A1 (en) * 2004-03-18 2005-09-22 Reiyao Zhu Modacrylic/cotton/aramid fiber blends for arc and flame protection
JP2009221632A (ja) * 2008-03-17 2009-10-01 Mitsubishi Rayon Co Ltd 芯鞘複合アクリル系導電性フィラメント
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US20140026303A1 (en) * 2012-07-27 2014-01-30 E I Du Pont De Nemours And Company Fiber blends, yarns, fabrics, and garments for arc and flame protection
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