Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/78—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
  • 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
  • D03D1/00—Woven fabrics designed to make specified articles
  • D03D1/0035—Protective fabrics
  • D03D1/0041—Cut or abrasion resistant
• • 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
  • D03D1/007—UV radiation protecting
• • 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
  • 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
  • D10B2401/04—Heat-responsive characteristics
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/22—Physical properties protective against sunlight or UV radiation

Definitions

• the present invention relates to a heat-resistant fabric made of a meta-type aromatic polyamide fiber.
• Patent Document 1 JP-A-2009-249758 discloses a method in which a high-strength, high-heat-resistance fiber is arranged as a core yarn, another dyeable fiber or spun-dyed yarn is arranged therearound in a substantially non-twisted state, and further they are covered with a dyeable fiber or spun-dyed yarn in a spiral fashion, thereby maintaining aesthetics.
• Patent Document 2 JP-A-2009-209488 discloses a composite spun yarn including a core component made of a para-aramid fiber and a meta-aramid fiber and a sheath component made of a cellulose fiber, with the composite ratio of core component/sheath component being within a range of 25/75 to 55/45, as well as a woven or knitted fabric using the composite spun yarn.
• Patent Document 3 JP-A-2003-147651 discloses a core-sheath-type composite spun yarn including a core component made of a heat-resistant, high-performance fiber and a sheath component made of staple fibers of a synthetic fiber, a chemical fiber, or a natural fiber, characterized in that the heat-resistant, high-performance fiber is a crimped yarn of a heat-resistant, high-performance fiber filament yarn.
• a fiber that is likely to adversely affect washing durability is used as the core part of a sheath-core structure yarn, thereby hiding the fiber itself so as to solve the problems.
• it is indispensable to use a sheath-core structure yarn.
• the invention has been accomplished in view of the problems mentioned above and is aimed at providing a heat-resistant fabric that can be dyed to a color chosen from a wide range of color options, is capable of maintaining high mechanical characteristics without degradation over time/age even after repeated uses or washes, etc., and has excellent pilling resistance.
• the heat-resistant fabric of the invention is a heat-resistant fabric containing a meta-type wholly aromatic polyamide fiber, characterized in that the abrasion resistance of the heat-resistant fabric in accordance with the JIS L1096 8.19.1 A-1 method (universal type method (plane method), abrasion tester press load: 4.45 N (0.454 kf), paper: #600) is 200 rubs or more, the tear strength of the heat-resistant fabric in accordance with the JIS L1096 8.17.4 D method (pendulum method) is 20 N or more, and the retention of the abrasion resistance and the retention of the tear strength after 100 washes in accordance with JIS L0844 No. A-1 are each 90% or more relative to before washing.
• the meta-type wholly aromatic polyamide fiber has a crystallinity of 15 to 27.
• the standard deviation of the single-fiber tensile strength of the meta-type wholly aromatic polyamide fiber is 0.60 or less.
• the meta-type wholly aromatic polyamide fiber has an average single-fiber tensile strength of 4.0 cN/dtex or less.
• the meta-type wholly aromatic polyamide fiber has an average single-fiber elongation of 35% or less.
• the meta-type wholly aromatic polyamide fiber has a single-fiber toughness of 130 or less.
• the heat-resistant fabric of the invention it is preferable that the heat-resistant fabric is dyed, and the color difference ⁇ E of the fabric before and after a light resistance test in accordance with JIS L0842 and the brightness L of the light resistance test fabric satisfy the following equation (1) : ⁇ E ⁇ 0.46 ⁇ L - 11.3
• the meta-type wholly aromatic polyamide fiber contains an organic dye.
• the heat-resistant fabric of the invention contains at least one member selected from a cellulose fiber, a polyester fiber, an acrylic fiber, and a polyamide fiber in an amount of 2 to 50 mass% based on the mass of the heat-resistant fabric.
• the cellulose fiber is rayon.
• the cellulose fiber, polyester fiber, acrylic fiber, or polyamide fiber contains a flame retarder.
• the pilling resistance of the heat-resistant fabric in accordance with the 11. JIS L1096 A method is Level 4 or higher.
• the heat-resistant fabric of the invention it is preferable that the heat-resistant fabric contains cellulose and is dyed with a fluorescent dye.
• the heat-resistant fabric of the invention is preferably the heat-resistant fabric according to any one of claims 1 to 12, wherein the meta-type wholly aromatic polyamide that forms the meta-type wholly aromatic polyamide fiber is an aromatic polyamide obtained by copolymerizing, into an aromatic polyamide backbone having a repeating structural unit represented by the following formula (1), an aromatic diamine component or aromatic dicarboxylic acid halide component that is different from a main unit of the repeating structure as a third component so that the proportion of the third component is 1 to 10 mol% based on the total repeating structural units of the aromatic polyamide: - (NH-Ar1-NH-CO-Ar1-CO) formula (1) wherein Ar1 is a divalent aromatic group having a linking group in a position other than the meta position or an axially parallel direction.
• the meta-type wholly aromatic polyamide that forms the meta-type wholly aromatic polyamide fiber is an aromatic polyamide obtained by copolymerizing, into an aromatic polyamide backbone having a repeating structural unit represented by the
• the third component is an aromatic diamine of formula (2) or (3) or an aromatic dicarboxylic acid halide of 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 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is 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 is a halogen atom.
• the meta-type aromatic polyamide fiber has a residual solvent content of 0.1 mass% or less.
• the heat-resistant fabric of the invention contains at least one member selected from a para-type wholly aromatic polyamide fiber, a polybenzobisoxazol fiber, and a wholly aromatic polyester fiber in an amount of 1 to 20 mass% based on the mass of the heat-resistant fabric.
• the para-type wholly aromatic polyamide fiber is a paraphenylene terephthalamide fiber or a co-paraphenylene/3,4'-oxydiphenylene terephthalamide fiber.
• a fiber that forms the heat-resistant fabric contains a UV absorber and/or UV reflector.
• the heat-resistant fabric of the invention it is preferable that the heat-resistant fabric has a UV absorber and/or UV reflector fixed to the surface thereof.
• a heat-resistant fabric that can be dyed to a color chosen from a wide range of options and is highly capable of retaining surface abrasion and tear strength over time/age even after repeated uses, washes, etc.
• the fabric can be suitably used for protective garments, such as firefighter garments, or for industrial materials, such as flexible heat-insulating materials.
• the heat-resistant fabric of the invention is a heat-resistant fabric containing a meta-type wholly aromatic polyamide fiber.
• the fabric indispensably contains a meta-type wholly aromatic polyamide fiber, but the presence of other kinds of fibers is also allowed, including flame-retardant fibers such as para-type wholly aromatic polyamide fibers, synthetic fibers such as polyester fibers, regenerated fibers such as rayon, and natural fibers such as cotton.
• flame-retardant fibers such as para-type wholly aromatic polyamide fibers
• synthetic fibers such as polyester fibers
• regenerated fibers such as rayon
• natural fibers such as cotton.
• the meta-type wholly aromatic polyamide fiber content is 50 mass% or more based on the total mass of the heat-resistant fabric.
• the meta-type wholly aromatic polyamide fiber for use in the invention is made of a polymer, wherein 85 mol% or more of the repeating unit is m-phenyleneisophthalamide.
• the meta-type wholly aromatic polyamide may also be a copolymer containing a third component in an amount within a range of less than 15 mol%.
• the abrasion resistance of the heat-resistant fabric in accordance with the JIS L1096 8.19.1 A-1 method (universal type method (plane method), abrasion tester press load: 4.45 N (0.454 kf), paper: #600) is 200 rubs or more
• the tear strength of the heat-resistant fabric in accordance with the JIS L1096 8.17.4 D method (pendulum method) is 20 N or more
• the retention of the abrasion resistance and the retention of the tear strength after 100 washes in accordance with JIS L0844 No. A-1 are each 90% or more relative to before washing.
• the above tear strength and retention thereof should be satisfied in at least one direction, but it is preferable that they are satisfied in both directions.
• the longitudinal direction and transverse direction herein may be arbitrarily determined.
• the length direction of the original fabric may be the longitudinal direction
• the direction perpendicular thereto may be the transverse direction.
• the above object can be achieved by using the below-mentioned fiber having improved dyeing affinity and discoloration/fading resistance as a meta-type wholly aromatic polyamide fiber to form the heat-resistant fabric.
• appropriate materials for the heat-resistant fabric are selected, and they are mixed in appropriate proportions.
• 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 a hexylbenzenesulfonic acid tetrabutylphosphonium salt, a hexylbenzenesulfonic acid tributylbenzylphosphonium salt, a dodecylbenzenesulfonic acid tetraphenylphosphonium salt, a dodecylbenzenesulfonic acid tributyltetradecylphosphonium salt, a dodecylbenzenesulfonic acid tetrabutylphosphonium salt, and a dodecylbenzenesulfonic acid tributylbenzylammonium salt.
• a dodecylbenzenesulfonic acid tetrabutylphosphonium salt and a dodecylbenzenesulfonic acid tributylbenzylammonium salt are particularly preferable because they are easily available, have excellent thermal stability, and also have high solubility in N-methyl-2-pyrrolidone.
• the content of the alkylbenzenesulfonic acid onium salt is preferably 2.5 mol% or more, more preferably 3.0 to 7.0 mol%, relative to poly-m-phenyleneisophthalamide.
• the polymer to form the meta-type wholly aromatic polyamide fiber may also be obtained by copolymerizing, into an aromatic polyamide backbone having a repeating structural unit represented by the following formula (1), an aromatic diamine component or aromatic dicarboxylic acid halide component that is different from a main unit of the repeating structure as a third component so that the proportion of the third component is 1 to 10 mol% based on the total repeating structural units of the aromatic polyamide: - (NH-Ar1-NH-CO-Ar1-CO) formula (1) wherein Ar1 is a divalent aromatic group having a linking group in a position other than the meta position or an axially parallel direction.
• Ar1 is a divalent aromatic group having a linking group in a position other than the meta position or an axially parallel direction.
• aromatic diamines represented by formulae (2) and (3) copolymerizable 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 formulae (4) and (5) include terephthaloyl chloride, 1,4-naphthalenedicarbonyl chloride, 2,6-naphthalenedicarbonyl chloride, 4,4'-biphenyldicarbonyl chloride, 5-chloroisophthaloyl chloride, 5-methoxyisophthaloyl chloride, and bis(chlorocarbonylphenyl)ether.
• Ar2 is a divalent aromatic group different from Ar1
• Ar3 is a divalent aromatic group different from Ar1
• Y is at least one atom or functional group selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group
• X is a halogen atom.
• the crystallinity of the meta-type aromatic polyamide fiber for use in the invention is 5 to 27%, more preferably 15 to 25%. It has been found that when the crystallinity is within such a range, the above initial abrasion resistance and retention after washing and also the above initial tear strength and retention after washing can be achieved at the same time. Such crystallinity also leads to excellent dye exhaustion properties. Accordingly, even when dying is performed with a small amount of dye or under weak dyeing conditions, the color can be easily adjusted as intended. Further, the dye is less likely to be unevenly distributed on the surface, discoloration/fading resistance is improved, and also the practically necessary dimensional stability can be ensured.
• the standard deviation of the single-fiber tensile strength of the meta-type wholly aromatic polyamide fiber in accordance with the JIS L 1015-99 method is 0.60 or less, more preferably 0.55 or less.
• the average single-fiber tensile strength of the meta-type wholly aromatic polyamide fiber in accordance with the JIS L 1015-99 method is 4.0 cN/dtex or less, more preferably 3.8 cN/dtex or less.
• the average single-fiber elongation of the meta-type wholly aromatic polyamide fiber in accordance with the JIS L 1015-99 method is 35% or less, more preferably 30% or less, and still more preferably 28% or less.
• the single-fiber toughness of the meta-type wholly aromatic polyamide fiber is 130 or less, more preferably 110 or less, and still more preferably 100 or less.
• the above initial abrasion resistance and retention after washing and also the above initial tear strength and retention after washing can be achieved at the same time. It is usually believed that tear strength is improved with an increase in the strength of the fiber.
• tear strength is improved with an increase in the strength of the fiber.
• the residual solvent content of the meta-type aromatic polyamide fiber is 0.1 mass% or less, more preferably 0.08 mass% or less, still more preferably 0.07 mass% or less, and yet more preferably 0.05 mass% or less. It has been found that also by controlling the residual solvent content like this, the above initial abrasion resistance and retention and also the above initial tear strength and retention can be achieved at the same time. In addition, the excellent flame retardancy of the meta-type aromatic polyamide fiber is not impaired. Further, the dye is less likely to be unevenly distributed on the surface, and the discoloration/fading resistance can be improved.
• the meta-type wholly aromatic polyamide fiber is a spun-dyed fiber containing a pigment having high light resistance over time as a coloring agent, the color of the fabric itself can be easily retained.
• the meta-type wholly aromatic polyamide fiber does not have to be a spun-dyed fiber. It is possible to perform yarn dyeing or fabric dyeing with an organic dye, that is, the fabric may be a so-called piece-dyed fabric. It is preferable that the meta-type wholly aromatic polyamide fiber can be piece-dyed for the following reasons: the fabric can be dyed to various colors to meet a wide variety of user needs, the fabric can be more brightly colored, the color can be changed, small lot production is possible, etc.
• the heat-resistant fabric of the invention may also contain other kinds of fibers, including flame-retardant fibers, synthetic fibers such as polyester fibers, regenerated fibers, and natural fibers.
• the flame-retardant fibers are fibers having a limiting oxygen index of 20 or more excluding meta-type wholly aromatic polyamide fibers.
• Preferred examples thereof include para-type wholly aromatic polyamide fibers, polybenzobisazole fibers, wholly aromatic polyester fibers, polysulfone amide fibers, polyimide fibers, and polyetheramide fibers.
• Preferred examples of para-type wholly aromatic polyamide fibers include paraphenylene terephthalamide fibers and co-paraphenylene/3,4'-oxydiphenylene terephthalamide fibers.
• polyester fibers are known synthetic fibers.
• polyester fibers such as polyethylene terephthalate fibers, polybutylene terephthalate fibers, polyethylene naphthalate fibers, and polylactic acid fibers
• preferred examples thereof include polyamide fibers, acrylic fibers, polyolefin fibers, and polycarbonate fibers.
• the regenerated fibers are known regenerated fibers.
• Preferred examples thereof include cellulose fibers, particularly rayon.
• the natural fibers are known natural fibers. Preferred examples thereof include cotton.
• the heat-resistant fabric contains at least one member selected from a cellulose fiber, a polyester fiber, an acrylic fiber, and a polyamide fiber in an amount of 2 to 50 mass%, more preferably 2 to 48 mass%, based on the mass of the heat-resistant fabric.
• the heat-resistant fabric contains at least one member selected from a para-type wholly aromatic polyamide fiber, a polybenzobisoxazol fiber, and a wholly aromatic polyester fiber in an amount of 1 to 20 mass%, more preferably 2 to 10 mass%, based on the mass of the heat-resistant fabric.
• the mixing proportions of these fibers are as follows. First, in order for excellent heat resistance and flame retardancy to be exerted, it is preferable that the proportion of the meta-type wholly aromatic polyamide fiber is 50 mass% or more.
• the above flame-retardant fibers, synthetic fibers, regenerated fibers, and natural fibers may be arbitrarily mixed.
• the mixing proportions may be as follows: meta-type wholly aromatic polyamide fiber: 50 to 98 mass%, polyester fiber: 2 to 50 mass%, cellulose fiber: 0 to 48 mass%. The proportions may be adjusted according to the performance to be emphasized.
• the fabric is capable of retaining excellent aesthetics over time/age even after repeated uses, washes, etc.
• "Excellent aesthetics” herein means that aesthetics are prevented from being lost due to any remaining or deposited soil; that is, it does not happen that due to the soil, the color/pattern looks different in some parts or the fabric has noticeable soiling.
• the color difference ⁇ E between a fabric after a light resistance test in accordance with JIS L0842 and a fabric before the light resistance test and the brightness L of the fabric before the light resistance test satisfy the following equation (1): ⁇ E ⁇ 0.46 ⁇ L - 11.3
• the ⁇ E value of the above equation (1) depending on the brightness L value of the original fabric before the light resistance test, even in the case where the fabric is repeatedly used, washed with a surfactant such as a detergent, etc., or dry-cleaned, for example, it does not happen that the fabric looks dirty due to the slightly remaining soil component or newly deposited soil component, or that due to such soil components, the color/pattern looks different in some parts or the fabric has noticeable soiling; as a result, excellent aesthetics can be achieved.
• the upper limit of the ⁇ E value can be set in direct proportion to the brightness L value of the original fabric.
• the meta-type wholly aromatic polyamide fiber used for the heat-resistant fabric of the invention is a spun-dyed fiber containing a pigment having high light resistance over time as a coloring agent, the color of the fabric itself can be easily retained.
• the meta-type wholly aromatic polyamide fiber does not have to be a spun-dyed fiber.
• the meta-type wholly aromatic polyamide fiber can be piece-dyed.
• a meta-type aromatic polyamide fiber that is suitable for use in the invention can be produced by the following method.
• the crystallinity and residual solvent content can be made within the above ranges.
• the polymerization method for a meta-type aromatic polyamide polymer does not have to be particularly limited, and it is possible to use, for example, the solution polymerization method or interfacial polymerization method described in JP-B-35-14399 , U.S. Pat. No. 3360595 , JP-B-47-10863 , etc.
• the spinning solution does not have to be particularly limited. It is possible to use an amide solvent solution containing an aromatic copolyamide polymer obtained by the above solution polymerization or interfacial polymerization, etc., or it is also possible that the polymer is isolated from the polymerization solution, dissolved in an amide solvent, and used.
• amide solvents used herein include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide, and N,N-dimethylacetamide is particularly preferable.
• the wholly aromatic polyamide polymer solution obtained as above further contains an alkali metal salt or an alkaline earth metal salt, as a result, the solution becomes more stable and thus can be used at higher concentrations and lower temperatures. It is preferable that the proportion of the alkali metal salt or alkaline earth metal salt is 1 mass% or less, more preferably 0.1 mass% or less, based on the total mass of the polymer solution.
• the spinning solution obtained above metal-type wholly aromatic polyamide polymer solution
• a coagulation liquid a coagulation liquid and coagulated.
• the spinning apparatus is not particularly limited and may be a conventionally known wet-spinning apparatus.
• the number of spinning holes of a spinneret there is no need to particularly limit the number of spinning holes of a spinneret, their arrangement, the hole shape, etc.
• the temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) upon extrusion from the spinneret is within a range of 20 to 90°C.
• an aqueous solution containing substantially no inorganic salt and having an amide solvent, preferably NMP, concentration of 45 to 60 mass% is used at a bath liquid temperature within a range of 10 to 50°C.
• An amide solvent (preferably NMP) concentration of less than 45 mass% leads to a structure with a thick skin.
• the washing efficiency in a washing step decreases, making it difficult to reduce the residual solvent content of the fiber.
• the amide solvent (preferably NMP) concentration is more than 60 mass%, uniform coagulation inside the fiber cannot be achieved, making it difficult to reduce the residual solvent content of the fiber.
• the time of fiber immersion in the coagulation bath is within a range of 0.1 to 30 seconds.
• the fiber is drawn to a draw ratio of 3 to 4 in a plastic drawing bath containing an aqueous solution having an amide solvent, preferably NMP, concentration of 45 to 60 mass% at a bath liquid temperature within a range of 10 to 50°C.
• an aqueous solution having an amide solvent, preferably NMP concentration of 45 to 60 mass% at a bath liquid temperature within a range of 10 to 50°C.
• the fiber is thoroughly washed with an aqueous solution at 10 to 30°C having an NMP concentration of 20 to 40 mass% and then through a hot water bath at 50 to 70°C.
• the fiber after washing is subjected to a dry heat treatment at a temperature of 270 to 290°C, whereby a meta-type wholly aromatic aramid fiber that satisfies the above crystallinity and residual solvent content ranges can be obtained.
• the obtained meta-type wholly aromatic aramid fiber is cut by a known method into staple fibers, further blend-spun into a spun yarn with the above flame-retardant fibers such as meta-type wholly aromatic aramid fibers, synthetic fibers such as polyester fibers and polyamide fibers, regenerated fibers, natural fibers, etc., and woven or knitted, whereby a heat-resistant fabric of the invention can be obtained.
• the method for preparing the heat-resistant fabric of the invention is not particularly limited, and any known methods may be employed.
• the above spun yarn is prepared and then, as a single yarn or a 2-ply yarn, woven into a twill weave, plain weave, or like structure using a rapier loom, etc., thereby giving the heat-resistant fabric.
• a UV absorber and/or UV reflector may be contained in any fiber that forms the heat-resistant fabric. It is preferable that the UV absorber is highly hydrophobic and has a solubility of less than 0.04 mg/L in water. When the solubility is 0.04 mg/L or more, such a UV absorber and/or UV reflector is likely to elute during carrier dyeing, and the light resistance after dyeing tends to easily decrease; therefore, this is undesirable.
• the UV absorber and/or UV reflector used in the invention is a compound that efficiently shields light near 360 nm, which is the photodegradation characteristic wavelength of a meta-wholly aromatic polyamide mainly used in the heat-resistant fabric of the invention, and has almost no absorption in the visible region.
• a specific substituted benzotriazole is preferable.
• Specific examples thereof include 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl) phenol, 2-[2H-benzotriazol-2-yl]-4-6-bis(1-methyl-1-phenylethyl)ph enol, and 2-[2H-benzotriazol-2-yl]-4-(1,1,3,3-tetramethylbutyl)pheno l.
• 2-[2H-benzotriazol-2-yl]-4-6-bis(1-methyl-1-phenylethyl)ph enol is particularly preferable because of its high hydrophobicity and low absorption in the visible region.
• UV reflectors include fine particles of metal oxides, such as titanium oxide, zinc oxide, selenium oxide, alumina, and silica, and calcium carbonate preferably having a particle size of 0.001 to 0.2 ⁇ m, more preferably 0.005 to 0.02 ⁇ m.
• the fiber to contain such a UV absorber and/or UV reflector is not limited.
• the content is 3.0 to 6. 5 mass%, more preferably 4.5 to 6.5 mass%, based on the total mass of the meta-type wholly aromatic polyamide fiber.
• the UV absorber and/or UV reflector may also be fixed to the fabric surface.
• the fixing method is not particularly limited.
• a water dispersion of the UV absorber and/or UV reflector is applied to the fabric by immersion/ squeezing or spraying, and then dried and cured.
• a binder such as resin or latex in order to increase the durability of fixing.
• resin or latex which is a binder component, may be previously mixed with the water dispersion as an aqueous product.
• the heat-resistant fabric obtained by the above method which is made of a meta-type wholly aromatic aramid fiber and preferably contains the above materials mixed therewith in the above mixing proportions, it is possible to achieve the excellent performance, that is, an abrasion resistance of 200 rubs or more and a tear strength of 20 N or more, with the retention of the abrasion resistance and the retention of the tear strength after 100 washes being each 90% or more relative to before washing.
• the above strength, elongation, standard deviations thereof, toughness, etc. can be easily achieved.
• the concentration of oxygen necessary to keep burning 50 mm or more was defined as a limiting oxygen index (LOI).
• the obtained raw fiber was crimped and cut into staple fibers 51 mm in length (raw stock).
• raw fibers were bundled into a fiber bundle of about 1 mm in diameter and mounted on a fiber sample table to measure the diffraction profile.
• the measurement conditions were as follows: Cu-K ⁇ radiation source (50 kV, 300 mA), scanning angle range: 10 to 35°, continuous measurement, measurement width: 0.1°, scanning at 1°/min. From the measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to give the total scattering profile. Next, the amorphous scattering profile was subtracted from the total scattering profile to give the crystal scattering profile.
• Artificial soil component a mixture of the following soil powder and artificial sebum in a ratio of 1:10
• Soil powder an intimate mixture of the following powders: JIS Z8901 Test Powder Class 12 (carbon black, particle size: 0. 03 to 0.2 ⁇ m), 25 mass%; and JIS Z8901 Test Powder Class 8 (the loamy layer of the Kanto Plain, particle size: 8 ⁇ m), 75 mass%
• a meta-type wholly aromatic aramid fiber was prepared by the following method.
• a polymetaphenylene isophthalamide powder having an intrinsic viscosity (I.V.) of 1.9 produced by interfacial polymerization in accordance with the method described in JP-B-47-10863 was suspended in 80.0 parts by mass of N-methyl-2-pyrrolidone (NMP) cooled to -10°C, thereby forming a slurry. Subsequently, the suspension was heated to 60°C for dissolution to give a transparent polymer solution.
• NMP N-methyl-2-pyrrolidone
• Example 1 a UV absorber 2-[2H-benzotriazol-2-yl]-4-6-bis(1-methyl-1-phenylethyl)ph enol was added to the spinning solution.
• the spinning dope was discharged and spun from a spinneret (hole diameter: 0.07 mm, the number of holes: 500) into a coagulation bath at a bath temperature of 30°C.
• the spinning dope was discharged and spun into the coagulation bath at a yarn speed of 7 m/min.
• the fiber after washing was subjected to a dry heat treatment using a hot roller having a surface temperature of 283°C to give a meta-type aromatic polyamide fiber.
• the obtained meta-type wholly aromatic aramid fiber had the following properties: fineness: 1.6dtex, residual solvent content: 0.08 mass%, crystallinity: 20%, LOI: 30.
• Polyester fiber polyethylene terephthalate fiber
• Tetoron® manufactured by Teijin
• the brightness L was adjusted with a dye so that fabrics after dyeing had an L value of 49 (neutral color) regardless of the foundation fabrics. Redyeing was performed as necessary to accurately control the L value.
• the conditions for dyeing and the conditions for washing a dyed product in a reducing bath (pH 5.5) were as follows.
• Cationic dye manufactured by Nippon Kayaku, trade name: Kayacryl Red GL-ED, 1% owf Bath ratio; 1:20 Temperature x Time; 120°C x 30 minutes (Reducing Bath Composition and Washing Conditions) Reducing bath; thiourea dioxide, 1 g/l Bath ratio; 1:20 Temperature x Time; 70°C x 15 minutes
• Staple fibers of a meta-type wholly aromatic polyamide fiber (MA), a para-type wholly aromatic polyamide fiber (PA), a polyester fiber (PE), and a flame-retardant rayon fiber (RY) were blend-spun in a mass ratio MA/PA/PE/RY of 55/5/15/25 into a spun yarn (36 count, 2-ply yarn), and woven at a weaving density of warp: 100 yarns/25.4 mm and weft: 56 yarns/25.4 mm, thereby giving a twill-woven fabric having an areal weight of 230 g/m 2 .
• the meta-type wholly aromatic polyamide fiber (MA) had an average strength of 3.7 cN/dtex with a standard deviation of 0.54, an average elongation of 25% with a standard deviation of 4.7, a toughness of 93, a crystallinity of 20%, and a residual solvent content of 0.08 mass%.
• the woven fabric was dyed by the above method to a neutral color (L value: 49).
• the abrasion resistance of the obtained fabric was measured. As a result, the resistance before washing (L0) was 215 rubs, while the resistance after 100 washes (L100) was 200 rubs. Thus, the retention of abrasion resistance (L100/L0 x 100) was 93%.
• the tear strength of the obtained fabric was measured. As a result, the strength before washing (L0) was 35.3 N in the longitudinal direction and 24.1 N in the transverse direction, while the strength after 100 washes (L100) was 31.9 N in the longitudinal direction and 23.2 N in the transverse direction. Thus, the retention of tear strength (L100/L0 x 100) was 90% in the longitudinal direction and 96% in the transverse direction. Further, pilling was Level 4 in the longitudinal direction and Level 4 in the transverse direction.
• MA meta-type wholly aromatic polyamide fiber
• PA para-type wholly aromatic polyamide fiber
• the meta-type wholly aromatic polyamide fiber (MA) had an average strength of 3.6 cN/dtex with a standard deviation of 0.55, an average elongation of 25% with a standard deviation of 4.8, a toughness of 90, a crystallinity of 20%, and a residual solvent content of 0.05 mass%.
• the abrasion resistance of the obtained fabric was measured. As a result, the resistance before washing (L0) was 209 rubs, while the resistance after 100 washes (L100) was 200 rubs. Thus, the retention of abrasion resistance (L100/L0 x 100) was 96%.
• the tear strength of the obtained fabric was measured. As a result, the strength before washing (L0) was 32.4 N in the longitudinal direction and 23.2 N in the transverse direction, while the strength after 100 washes (L100) was 29.8 N in the longitudinal direction and 22.5 N in the transverse direction. Thus, the retention of tear strength (L100/L0 x 100) was 92% in the longitudinal direction and 97% in the transverse direction. Further, pilling was Level 4 in the longitudinal direction and Level 4 in the transverse direction.
• the fabric had a brightness L of 49, with 0.45 x L - 11.3 being 11.25, a light-resistance color difference ⁇ E of 10.73, and a soil-resistance color difference ⁇ E* of 15.
• the meta-type wholly aromatic polyamide fiber (MA) had an average strength of 4.2 cN/dtex with a standard deviation of 0.61, an average elongation of 29% with a standard deviation of 4.8, a toughness of 121, a crystallinity of 20%, and a residual solvent content of 0.15 mass%.
• the abrasion resistance of the obtained fabric was measured. As a result, the resistance before washing (L0) was 211 rubs, while the resistance after 100 washes (L100) was 185 rubs. Thus, the retention of abrasion resistance (L100/L0 x 100) was 88%.
• the tear strength of the obtained fabric was measured. As a result, the strength before washing (L0) was 36.3 N in the longitudinal direction and 24.1 N in the transverse direction, while the strength after 100 washes (L100) was 30.4 N in the longitudinal direction and 23.0 N in the transverse direction. Thus, the retention of tear strength (L100/L0 x 100) was 84% in the longitudinal direction and 95% in the transverse direction. Further, pilling was Level 3 in the longitudinal direction and Level 3 in the transverse direction.
• Example 2 The same procedure as in Example 1 was performed, except that in the production of a meta-type wholly aromatic polyamide fiber (MA), the surface temperature of the hot roller in the dry heat treatment step was changed to 315°C.
• the meta-type wholly aromatic polyamide fiber (MA) had a crystallinity of 28% and a residual solvent content of 0.08 mass%.
• the abrasion resistance of the obtained fabric was measured. As a result, the resistance before washing (L0) was 250 rubs, while the resistance after 100 washes (L100) was 200 rubs. Thus, the retention of abrasion resistance (L100/L0 x 100) was 80%.
• the tear strength of the obtained fabric was measured. As a result, the strength before washing (L0) was 36.3 N in the longitudinal direction and 24.2 N in the transverse direction, while the strength after 100 washes (L100) was 31.8 N in the longitudinal direction and 23.1 N in the transverse direction. Thus, the retention of tear strength (L100/L0 x 100) was 86% in the longitudinal direction and 95% in the transverse direction. Further, pilling was Level 3 in the longitudinal direction and Level 3 in the transverse direction.
• Example 2 The same procedure as in Example 1 was performed, except that the spun yarn was changed to a spun yarn made only of a flame-retardant rayon fiber (RY).
• RY flame-retardant rayon fiber
• the abrasion resistance of the obtained fabric was measured. As a result, the resistance before washing (L0) was 57 rubs, while the resistance after 100 washes (L100) was 40 rubs. Thus, the retention of abrasion resistance (L100/L0 x 100) was 70%.
• the tear strength of the obtained fabric was measured. As a result, the strength before washing (L0) was 20 N in the longitudinal direction and 12 N in the transverse direction, while the strength after 100 washes (L100) was 10 N in the longitudinal direction and 7 N in the transverse direction. Thus, the retention of tear strength (L100/L0 x 100) was 50% in the longitudinal direction and 58% in the transverse direction. Further, pilling was Level 3 in the longitudinal direction and Level 3 in the transverse direction.
• Example 1 The same procedure as in Example 1 was performed, except that the spun yarn was changed to a spun yarn made only of a polyester fiber (PE). The results are shown in Table 1.
• the abrasion resistance of the obtained fabric was measured. As a result, the resistance before washing (L0) was 67 rubs, while the resistance after 100 washes (L100) was 41 rubs. Thus, the retention of abrasion resistance (L100/L0 x 100) was 61%.
• the tear strength of the obtained fabric was measured. As a result, the strength before washing (L0) was 21 N in the longitudinal direction and 10 N in the transverse direction, while the strength after 100 washes (L100) was 11 N in the longitudinal direction and 6 N in the transverse direction. Thus, the retention of tear strength (L100/L0 x 100) was 52% in the longitudinal direction and 60% in the transverse direction. Further, pilling was Level 3 in the longitudinal direction and Level 3 in the transverse direction.
• the heat-resistant fabric of the invention is excellent in terms of surface abrasion characteristics, tear characteristics, and the washing durability of these characteristics, and also has pilling resistance, a color tone that meets various user needs, and heat resistance. Therefore, the heat-resistant fabric of the invention is applicable to protective garments, such as firefighter garments, and industrial materials, such as flexible heat-insulating materials, and thus is industrially extremely useful.

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• 2013
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