WO2016060143A1 - Fabric, method for producing same, and textile product - Google Patents

Fabric, method for producing same, and textile product Download PDF

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Publication number
WO2016060143A1
WO2016060143A1 PCT/JP2015/078977 JP2015078977W WO2016060143A1 WO 2016060143 A1 WO2016060143 A1 WO 2016060143A1 JP 2015078977 W JP2015078977 W JP 2015078977W WO 2016060143 A1 WO2016060143 A1 WO 2016060143A1
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WIPO (PCT)
Prior art keywords
fiber
fabric
fabric according
aromatic polyamide
meta
Prior art date
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PCT/JP2015/078977
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French (fr)
Japanese (ja)
Inventor
博樹 島田
憲二 岩下
Original Assignee
帝人株式会社
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Application filed by 帝人株式会社 filed Critical 帝人株式会社
Priority to CN201580054738.9A priority Critical patent/CN106795666A/en
Priority to RU2017116828A priority patent/RU2017116828A/en
Priority to JP2016554092A priority patent/JPWO2016060143A1/en
Publication of WO2016060143A1 publication Critical patent/WO2016060143A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • 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
    • D03D15/20—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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes

Definitions

  • the present invention relates to a fabric that contains organic fibers and is colored by a textile printing process, and is excellent not only in sharpness and design but also in flame retardancy, a method for producing the same, and a textile product.
  • the present invention has been made in view of the above-described background, and an object of the present invention is a fabric containing organic fibers and colored by a printing process, which is excellent not only in sharpness and design but also in flame retardancy. It is in providing a fabric, its manufacturing method, and a textile product.
  • a fabric containing organic fibers and colored by a printing process characterized by having a carbonization length measured by JIS L1091-1998 A-4 (3-second flame contact) of 10 cm or less.
  • the organic fiber is a meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide ( PI) fiber, polysulfonamide (PSA), polyether ether ketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber
  • PPS polyphenylene sulfide
  • the fabric is further made of polyester fiber, cellulose fiber, polyamide fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, acetate fiber and polycarbonate fiber.
  • the fiber which comprises a fabric is only a fully aromatic polyamide fiber.
  • the meta-type wholly aromatic polyamide fiber is contained in an amount of 35% by weight or more relative to the weight of the fabric. At that time, the crystallinity of the meta-type wholly aromatic polyamide fiber is preferably in the range of 15 to 25%.
  • the meta type wholly aromatic polyamide forming the meta type wholly aromatic polyamide fiber is an aromatic polyamide skeleton including a repeating structural unit represented by the following formula (1):
  • Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
  • the aromatic diamine as the third component is represented by formulas (2) and (3), or the aromatic dicarboxylic acid halide is represented by formulas (4) and (5).
  • XOC-Ar3-COX Formula (4) XOC-Ar3-Y-Ar3-COX Formula (5)
  • Ar2 is a divalent aromatic group different from Ar1
  • Ar3 is a divalent aromatic group different from Ar1
  • Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
  • the residual solvent amount of the meta-type aromatic polyamide fiber is 0.1% by weight or less.
  • the fabric is preferably a woven fabric having a warp density of 40 to 100 pieces / 25.4 mm and a weft density of 40 to 100 pieces / 25.4 mm.
  • the fabric weight is preferably in the range of 140 to 300 g / m 2 .
  • the bending resistance of the fabric measured by JIS L1096-1998 A method is in the range of 4 to 12 mm.
  • the afterflame time is preferably 1 second or less in the vertical combustion test described in JIS L1091-1998 A-4 (12s flame contact).
  • the fabric is colored black or red.
  • a method for producing a fabric as described above wherein when a fabric is colored by a textile printing process, a textile processing agent containing a flame retardant is used.
  • a printing treatment agent containing a binder made of an acrylic resin or a urethane resin when printing. Further, it is preferable to perform a water repellent treatment on the fabric.
  • a textile product selected from the group consisting of fire fighting clothes, fire brigade clothes, work clothes, camouflage clothes, coats, and aprons using the fabric.
  • a fabric containing organic fibers and colored by a printing process which is excellent not only in sharpness and design but also in flame retardancy, a method for producing the same, and a textile product.
  • the type of organic fiber is not particularly limited.
  • meta-type wholly aromatic polyamide fiber para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) fiber, Polybenzimidazole (PBI) fiber, Polybenzthiazole (PBTZ) fiber, Polyimide (PI) fiber, Polysulfonamide (PSA), Polyetheretherketone (PEEK) fiber, Polyetherimide (PEI) fiber, Polyarylate (PAr) Fiber, melamine fiber, phenol fiber, fluorine fiber, polyphenylene sulfide (PPS) fiber and the like are preferable.
  • meta-type wholly aromatic polyamide fibers are preferable.
  • the meta-type wholly aromatic polyamide fiber is a fiber made of a polymer in which 85 mol% or more of the repeating units is m-phenylene isophthalamide.
  • Such a meta-type wholly aromatic polyamide may be a copolymer containing a third component within a range of less than 15 mol%.
  • Such a meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method.
  • the polymerization degree of the polymer is N-methyl-2-pyrrolidone solution having a concentration of 0.5 g / 100 ml.
  • Those having a measured intrinsic viscosity (IV) in the range of 1.3 to 1.9 dl / g are preferably used.
  • the meta-type wholly aromatic polyamide may contain an alkylbenzene sulfonic acid onium salt.
  • alkylbenzene sulfonic acid onium salt examples include tetrabutyl phosphonium salt of hexyl benzene sulfonate, tributyl benzyl phosphonium salt of hexyl benzene sulfonate, tetraphenyl phosphonium salt of dodecyl benzene sulfonate, tributyl tetradecyl phosphonate of dodecyl benzene sulfonate.
  • Preferred examples include compounds such as a nium salt, tetrabutylphosphonium salt of dodecylbenzenesulfonate, and tributylbenzylammonium salt of dodecylbenzenesulfonate.
  • dodecylbenzenesulfonic acid tetrabutylphosphonium salt or dodecylbenzenesulfonic acid tributylbenzylammonium salt is particularly easy to obtain and has good thermal stability and high solubility in N-methyl-2-pyrrolidone.
  • tributylbenzylammonium salt is particularly easy to obtain and has good thermal stability and high solubility in N-methyl-2-pyrrolidone.
  • the content ratio of the alkylbenzenesulfonic acid onium salt is 2.5 mol% or more, preferably 3.0 to 7.0 mol, relative to poly-m-phenyleneisophthalamide in order to obtain a sufficient dyeing effect. Those in the range of% are preferred.
  • poly-m-phenylene isophthalamide As a method of mixing poly-m-phenylene isophthalamide and alkylbenzene sulfonic acid onium salt, poly-m-phenylene isophthalamide is mixed and dissolved in a solvent, and alkylbenzene sulfonic acid onium salt is dissolved in the solvent. Any of these may be used.
  • the dope thus obtained is formed into fibers by a conventionally known method.
  • the polymer used for the meta-type wholly aromatic polyamide fiber has a repetitive structure in an aromatic polyamide skeleton containing a recurring structural unit represented by the following formula (1) for the purpose of improving dyeability and resistance to discoloration. It is also possible to copolymerize an aromatic diamine component or aromatic dicarboxylic acid halide component different from the main structural unit of 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide as the third component. It is.
  • Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
  • aromatic diamine represented by the formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, Examples include acetylphenylenediamine, aminoanisidine, benzidine, bis (aminophenyl) ether, bis (aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene, and the like.
  • aromatic dicarboxylic acid dichloride represented by the formulas (4) and (5) include, for example, terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4 Examples include '-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis (chlorocarbonylphenyl) ether, and the like.
  • Ar2 is a divalent aromatic group different from Ar1
  • Ar3 is a divalent aromatic group different from Ar1
  • Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
  • the crystallinity of the meta-type wholly aromatic polyamide fiber is 5 to 35% (more preferably 15 to 25%) in terms of high resistance to discoloration and securing dimensional stability necessary for practical use. It is preferable.
  • the residual solvent amount of the meta-type wholly aromatic polyamide fiber is preferably 0.1% by weight or less from the viewpoint that the excellent flame retardancy of the meta-type wholly aromatic polyamide fiber is not impaired.
  • the meta-type wholly aromatic polyamide fiber can be produced by the following method, and in particular, the crystallinity and the residual solvent amount can be within the above ranges by the method described later.
  • the polymerization method of the meta-type wholly aromatic polyamide polymer is not particularly limited.
  • the solution weight described in Japanese Patent Publication No. 35-14399, US Pat. No. 3,360,595, Japanese Patent Publication No. 47-10863, etc. A combination method or an interfacial polymerization method may be used.
  • the spinning solution is not particularly limited, but an amide solvent solution containing an aromatic copolyamide polymer obtained by the above solution polymerization or interfacial polymerization may be used, or the polymer may be removed from the polymerization solution. You may use what was isolated and melt
  • amide solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like, and in particular, N, N-dimethylacetamide. Is preferred.
  • the copolymerized aromatic polyamide polymer solution obtained as described above is preferably stabilized by containing an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and lower temperature.
  • the alkali metal salt and alkaline earth metal salt are 1% by weight or less, more preferably 0.1% by weight or less, based on the total weight of the polymer solution.
  • the spinning solution metal-type wholly aromatic polyamide polymer solution obtained above is spun into a coagulating solution and coagulated.
  • the spinning apparatus is not particularly limited, and a conventionally known wet spinning apparatus can be used.
  • the number of spinning holes, the arrangement state, the hole shape, etc. of the spinneret need not be particularly limited as long as they can be stably wet-spun.
  • the number of holes is 1,000 to 30,000, and the spinning hole diameter is 0.05.
  • a multi-hole spinneret for ⁇ 0.2 mm sufu may be used.
  • the temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) when spinning from the spinneret is suitably in the range of 20 to 90 ° C.
  • an amide solvent preferably an aqueous solution containing 45 to 60% by weight of NMP, which is substantially free of inorganic salts, is used at a bath temperature of 10 to 50 ° C. Use. If the concentration of the amide solvent (preferably NMP) is less than 45% by weight, the skin has a thick structure, the washing efficiency in the washing step is lowered, and it is difficult to reduce the residual solvent amount of the fiber. On the other hand, when the concentration of the amide solvent (preferably NMP) exceeds 60% by weight, uniform coagulation cannot be performed up to the inside of the fiber, and therefore, the residual solvent amount of the fiber can be reduced. It becomes difficult.
  • the fiber immersion time in the coagulation bath is suitably in the range of 0.1 to 30 seconds.
  • an amide solvent preferably an aqueous solution having a concentration of NMP of 45 to 60% by weight
  • a plastic stretching bath in which the temperature of the bath liquid is in the range of 10 to 50 ° C., at a stretching ratio of 3 to 4 times. Stretching is performed. After stretching, the film is thoroughly washed through an aqueous solution having an NMP concentration of 20 to 40% by weight at 10 to 30 ° C., followed by a hot water bath at 50 to 70 ° C.
  • the washed fiber is subjected to a dry heat treatment at a temperature of 270 to 290 ° C. to obtain a meta-type wholly aromatic aramid fiber satisfying the above-mentioned range of crystallinity and residual solvent amount.
  • the organic fiber may be a long fiber (multifilament) or a short fiber.
  • short fibers spun yarns
  • the single fiber fineness of the organic fiber is preferably in the range of 1 to 5 dtex.
  • the cotton count is preferably 10 to 50 (more preferably 15 to 25).
  • the fabric of the present invention may be composed only of the organic fibers described above, but further includes polyester fibers, cellulose fibers, polyamide fibers, polyolefin fibers, acrylic fibers, rayon fibers, cotton fibers, animal hair fibers, polyurethane fibers, polychlorinated fibers.
  • Other fibers such as vinyl fiber, polyvinylidene chloride fiber, acetate fiber, and polycarbonate fiber may be included.
  • the fibers constituting the fabric are only wholly aromatic polyamide fibers (meta-type wholly aromatic polyamide fibers and / or para-type wholly aromatic polyamide fibers).
  • the meta-type wholly aromatic polyamide fiber contained in the fabric is 35% by weight or more (more preferably 50% by weight or more) with respect to the mass of the fabric because excellent flame retardancy is obtained.
  • the flame retardant fiber, synthetic fiber, regenerated fiber, and natural fiber can be arbitrarily mixed according to the use and use needs.
  • the meta-type wholly aromatic polyamide fiber is 50 to 98% by weight
  • the polyester fiber is 2 to 50% by weight
  • the cellulosic fiber is 0 to 50% by weight. You can also The ratio can be adjusted according to the performance to be emphasized. It is also preferable to include a flame retardant in any of the fibers constituting the fabric.
  • the method for producing the fabric of the present invention is not particularly limited, and any known method can be used.
  • the organic fiber and other fibers as necessary may be blended to obtain a spun yarn, and then woven or knitted with a single yarn or twin yarn.
  • the fabric structure is preferably a woven fabric such as plain weave, twill weave, satin or double weave, but may be knitted fabric or non-woven fabric. Particularly preferred are woven fabrics having a warp density of 40-100 strands / 25.4 mm and a weft density of 40-100 strands / 25.4 mm.
  • the production method of the fabric is not particularly limited, and a known knitting machine such as a rapier loom or a gripper loom can be used.
  • the fabric of the present invention is obtained by coloring the fabric by a textile printing process.
  • the printing process includes a direct printing method, a discharging method, an anti-dyeing method, and the like.
  • Operation includes machine printing and hand printing.
  • a printing agent is made by kneading a pigment or an auxiliary agent with glue, and generally, the printing agent is printed (printed) on a cloth by a printing machine.
  • the mixture is heated (steamed) with water vapor so that the pigment penetrates and dyes the fibers well, and is treated with a soap solution or the like (soaping) to remove attached dyes, washed with water, and dried.
  • examples of pigments used in textile printing include insoluble azo faces typified by CI Pigment Yellow 93, CI Pigment Brown 23, CI Pigment Red 144, CI Vat Yellow 1 (CI 70700), CI Vat Orange 105 (I7), C 71 CI Vat Red 23 (CI 71130), CI Pigment Red 123 (CI 71140), CI Vat Violet 1 (CI 60010), CI Vat ⁇ Blue 4 (CI 69800), selenium pigment, CI Pimgmt blue 160m, ol-blue 160 Phthalocyanine pigments represented by CI, CI Pigment, Red1 2, quinacridone pigments represented by CI Pigment Violet 19 (CI46500), dioxazine pigments represented by CI Pigment Violet 23, CI pigments Yellow 110, CI Pigment Orange 42, CI Pigment and other red pigments such as CI Pigment As commercial products, Dixel series (Dainippon Ink Chemical Co., Ltd.), Imperon series (Dyl
  • pigments those that do not change color at a heat history of 300 ° C. for 15 minutes are particularly preferable, and selenium, phthalocyanine, quinacridone, dioxazine, and isoindolinone pigments are preferably used.
  • the amount of the pigment adhered to the cloth is preferably 0.05 to 30.0% by weight (more preferably 0.1 to 20.0% by weight).
  • the amount of the textile treating agent attached to the fabric is preferably 7 to 80 g / m 2 (more preferably 10 to 50 g / m 2 ) as the solid content weight after drying.
  • the adhesion amount to the fabric used in the present invention is set to% by weight relative to the solid content weight of the printing processing agent adhered per unit area.
  • the above-described pigment is used as a printing processing agent in which a binder is added thereto.
  • the binder is not particularly limited, but a polyurethane polymer, a polyacrylic polymer, a polyamide polymer, a polyester polymer, a polyethylene polymer, a polypropylene polymer, a polyvinyl chloride polymer, A water-based emulsion such as a polyvinylidene chloride polymer, a polyfluorine-based polymer, or a silicone-based polymer, or a combination of a water-based emulsion of a prepolymer of each polymer and a crosslinking agent may be used.
  • crosslinking agent examples include acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, methylol acrylamide, vinyl ethylene urea, acrolein, ketene dimer, vinyl isocyanate, divinyl sulfone.
  • a reactive compound having a functional group such as is used.
  • the amount of adhesion of the binder is preferably 10 to 70% by weight (more preferably 10 to 60% by weight).
  • a desirable ratio of the textile processing agent is 1:99 to 99: 1 in terms of pigment: binder (in terms of solid content, including a crosslinking agent).
  • a flame retardant (sometimes referred to as a flame retardant) is used in combination.
  • a flame retardant sometimes referred to as a flame retardant
  • phosphorus-based and / or halogen-based flame retardants are preferably exemplified.
  • phosphorus-based flame retardant examples include phosphate esters, phosphonate esters, and phosphazene oligomers.
  • halogen flame retardant an organic halogen flame retardant is preferable.
  • organic halogen flame retardant include halogenated carbonate oligomer, halogenated epoxy compound, halogenated polystyrene, halogenated triazine compound, halogenated diphenylalkane compound, halogenated indane compound, and halogenated aromatic phthalimide compound.
  • halogenated carbonate oligomers and halogenated epoxy compounds are preferred because of their excellent compatibility with polycarbonate and their good heat resistance and thermal stability.
  • the adhesion amount of the above flame retardant is preferably 1.0 to 50.0% by weight (more preferably 2.0 to 40.0% by weight) relative to the weight of the fabric.
  • An inorganic flame retardant such as barium, antimony trioxide, and aluminum hydroxide can be blended in an amount of about 5.0% by weight or less.
  • the printing treatment is carried out by blending a printing treatment agent mainly composed of the pigment and the binder (and, if necessary, the flame retardant) to a viscosity of about 2000 to 50000 cPs suitable for printing, for example, 300 to 2000.
  • Printing may be performed using a mesh screen. The screen at this time may adopt a flat or rotary method.
  • heat treatment may be performed at 170 to 220 ° C. for 0.5 to 5 minutes.
  • a water repellent treatment Surprisingly, the flame retardancy is maintained even when the water repellent treatment is applied.
  • water repellent treatment for example, methods described in Japanese Patent No. 3133227 and Japanese Patent Publication No. 4-5786 are suitable. That is, commercially available fluorine-based water repellents (preferably fluorine-based water repellents that do not contain perfluorooctanoic acid and perfluorooctane sulfonic acid) or silicone-based water repellents are used as the water repellent.
  • a melamine resin and a catalyst are mixed to form a processing agent having a water repellent concentration of about 3 to 15% by weight, and the surface of the fabric is treated with the processing agent at a pickup rate of about 50 to 90%.
  • the method for treating the surface of the fabric with the processing agent include a pad method (immersion, pressing), a spray method, and the like. Of these, the pad method is most preferable for allowing the processing agent to penetrate into the fabric.
  • the said pick-up rate is a weight ratio (%) with respect to the fabric (before processing agent provision) weight of a processing agent.
  • the fabric thus obtained has a carbonization length of 10 cm or less (preferably 5 cm or less, particularly preferably 0.1 to 3.0 cm) as measured by JIS L1091-1998 A-4 (3 second flame contact). It is. If the carbonization length is greater than 10 cm, it may not be used as protective clothing.
  • the afterflame time is preferably 1 second or less (more preferably 0 seconds) in the vertical combustion test described in JIS L1091-1998 A-4 (12-second flame contact).
  • the basis weight and the bending resistance of the fabric are appropriately selected depending on the application, but the basis weight of the fabric is preferably within a range of 140 to 300 g / m 2 .
  • the bending resistance of the fabric is preferably in the range of 4 to 12 mm.
  • the bending resistance is measured by JIS L1096-1998 A method (cantilever method).
  • the fabric is colored black or red.
  • the fabric preferably has a black colored portion and a red colored portion.
  • the textile product of the present invention is a textile product selected from the group consisting of fire fighting clothes, fire brigade clothes, work clothes, camouflage clothes, coats and aprons using the above-mentioned fabric.
  • a coat having a black colored portion and a red colored portion is preferable.
  • Residual solvent amount (%) [(M1-M2) / M1] ⁇ 100 (6) Crystallinity Using an X-ray diffractometer (RINT TTRIII, manufactured by Rigaku Corporation), the fibers were aligned in a fiber bundle having a diameter of about 1 mm and mounted on a fiber sample table to measure a diffraction profile. The measurement conditions were Cu—K ⁇ radiation source (50 kV, 300 mA), scanning angle range 10 to 35 °, continuous measurement 0.1 ° width measurement, 1 ° / min scanning. From the measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain a total scattering profile.
  • crystal scattering profile was obtained by subtracting the amorphous scattering profile from the total scattering profile.
  • the degree of crystallinity was determined by the following equation from the area intensity of the crystal scattering profile (crystal scattering intensity) and the area intensity of the total scattering profile (total scattering intensity).
  • Crystallinity (%) [crystal scattering intensity / total scattering intensity] ⁇ 100 [Example 1] Meta-type wholly aromatic polyamide fiber (Conex (registered trademark) manufactured by Teijin Limited) (fiber length 51 mm) staple fiber is placed on the 20th spun yarn / twist yarn as warp, and meta-type wholly aromatic polyamide fiber (Teijin) Conex (registered trademark) (fiber length 51 mm) staple fiber made by Co., Ltd., spun yarn 20 count / single yarn is arranged on the weft, and weave density is warp 65 / 25.4 mm, weft 56 / 25.4 mm After weaving, a woven fabric having a 3/1 twill structure was obtained. The fabric was then subjected to the following printing treatment and then the following water-repellent treatment.
  • HI-COLOR BLACK NB black pigment: 10 parts by weight and DYF30 (binder): 100 parts by weight, Higuard FR-100 (flame retardant): 10 parts by weight, Fixer (crosslinking agent): 3 parts by weight ⁇ all, Hayashi Chemical Industry Co., Ltd.> was mixed, and printing (printing process) was performed twice (the coating amount was 20% by weight of the dough weight) and dried at 40 ° C. for 2 hours.
  • the basis weight is 238 g / m 2
  • the pigment adhesion amount is 10% by weight
  • the flame retardant adhesion amount is 10% by weight
  • the binder adhesion amount is 100% by weight
  • the carbonization length is 2.0 cm
  • the afterflame time is 0 second.
  • the bending resistance was 6.2 cm.
  • Example 2 The same operation as in Example 1 was performed, except that the acrylic binder (DYF30) in the above printing formulation was changed to a urethane binder (Newplex AU-13).
  • the basis weight is 235 g / m 2
  • the pigment adhesion amount is 10% by weight
  • the flame retardant adhesion amount is 10% by weight
  • the binder adhesion amount is 100% by weight
  • the carbonization length is 1.5 cm
  • the afterflame time is 0 second.
  • the bending resistance was 4.5 cm.
  • Example 3 The same operation as in Example 1 was performed except that the black pigment used in Example 1 was changed to a red pigment (HI-COLOR RED N3B).
  • the basis weight was 239 g / m 2
  • the pigment adhesion amount was 10% by weight
  • the flame retardant adhesion amount was 10% by weight
  • the binder adhesion amount was 100% by weight
  • the carbonization length was 2.4 cm
  • the afterflame time was 0 seconds.
  • the bending resistance was 5.2 cm.
  • Example 1 The same operation as in Example 1 was performed, except that the flame retardant (Higuard FR-100) in the above printing recipe was changed to 5 parts by weight.
  • the basis weight is 231 g / m 2
  • the pigment adhesion amount is 10% by weight
  • the flame retardant adhesion amount is 5% by weight
  • the binder adhesion amount is 100% by weight
  • the carbonization length is 20 cm or more (burnt)
  • the bending resistance was 6.0 cm for 30 seconds or more (burnt completely).
  • Example 2 The same operation as in Example 1 was carried out except that the flame retardant (Higuard FR-100) in the textile printing formulation was changed to 0 parts by weight.
  • the basis weight is 230 g / m 2
  • the pigment adhesion amount is 10% by weight
  • the flame retardant adhesion amount is 0% by weight
  • the binder adhesion amount is 100% by weight
  • the carbonization length is 20 cm or more (total burning)
  • the bending resistance was 6.0 cm for 30 seconds or more (burnt completely).
  • Example 4 Example 1 was carried out in the same manner as Example 1 except that a meta-type wholly aromatic polyamide fiber was prepared by the following method.
  • polymetaphenylene isophthalamide powder produced by an interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863 and having an intrinsic viscosity (IV) of 1.9 is placed at ⁇ 10 ° C. It was suspended in 80.0 parts by weight of cooled N-methyl-2-pyrrolidone (NMP) to form a slurry. Subsequently, the suspension was heated to 60 ° C. and dissolved to obtain a transparent polymer solution.
  • NMP N-methyl-2-pyrrolidone
  • [Washing process] After stretching, the film was washed with a 20 ° C. water / NMP 70/30 bath (immersion length 1.8 m), followed by a 20 ° C. water bath (immersion length 3.6 m), and then a 60 ° C. hot water bath (immersion length 5).
  • the washed fiber was subjected to a dry heat treatment with a heat roller having a surface temperature of 280 ° C. to obtain a meta-type wholly aromatic polyamide fiber.
  • the physical properties of the obtained meta-type wholly aromatic polyamide fiber were a fineness of 1.7 dtex, a residual solvent amount of 0.08% by weight, and a crystallinity of 19%.
  • the weight per unit area was 235 g / m 2
  • the pigment adhesion amount was 10% by weight
  • the flame retardant adhesion amount was 10% by weight
  • the binder adhesion amount was 100% by weight
  • the carbonization length was 2.0 cm
  • the afterflame time was 0 second.
  • the bending resistance was 3.5 cm
  • a fabric containing organic fibers and colored by a textile printing process which is excellent not only in sharpness and design but also in flame retardancy, a method for producing the same, and a textile product, Its industrial value is extremely large.

Abstract

The present invention address the problem of providing: a fabric that includes an organic fiber and is colored by means of a printing treatment, said fabric not only having excellent clarity and design properties but also having excellent flame retardancy; a method for producing said fabric; and a textile product. The problem is solved by configuring the measured char length to be 10 cm or less by using a printing treatment agent including a flame retardant when coloring the fabric by means of the printing treatment.

Description

布帛およびその製造方法および繊維製品Fabric, manufacturing method thereof and textile product
　本発明は、有機繊維を含みかつ捺染処理により着色された布帛であって、鮮明性、意匠性に優れるだけでなく難燃性にも優れる布帛およびその製造方法および繊維製品に関する。 The present invention relates to a fabric that contains organic fibers and is colored by a textile printing process, and is excellent not only in sharpness and design but also in flame retardancy, a method for producing the same, and a textile product.
　従来、メタ型芳香族ポリアミド繊維などの有機繊維を主体とする布帛を着色する方法として、原着した繊維を用いる方法や助剤（膨潤剤）を用いて染色する方法などが知られている。さらには、捺染処理により着色された布帛も提案されている（例えば、特許文献１）。 Conventionally, as a method for coloring a fabric mainly composed of organic fibers such as a meta-type aromatic polyamide fiber, a method using an attached fiber or a method using an auxiliary agent (swelling agent) is known. Furthermore, a fabric colored by textile printing has also been proposed (for example, Patent Document 1).
　しかしながら、捺染処理により着色された布帛では難燃性の点で十分とはいえなかった。 However, a fabric colored by a textile printing process is not sufficient in terms of flame retardancy.
特開２００９－５７６５２号公報JP 2009-57652 A
　本発明は上記の背景に鑑みなされたものであり、その目的は、有機繊維を含みかつ捺染処理により着色された布帛であって、鮮明性、意匠性に優れるだけでなく難燃性にも優れる布帛およびその製造方法および繊維製品を提供することにある。 The present invention has been made in view of the above-described background, and an object of the present invention is a fabric containing organic fibers and colored by a printing process, which is excellent not only in sharpness and design but also in flame retardancy. It is in providing a fabric, its manufacturing method, and a textile product.
　本発明者らは上記の課題を達成するため鋭意検討した結果、捺染処理を工夫することにより難燃性が向上することを見出し、さらに鋭意検討を重ねることにより本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that flame retardancy is improved by devising a textile printing process, and have further completed the present invention by intensive studies.
　かくして、本発明によれば「有機繊維を含みかつ捺染処理により着色された布帛であって、ＪＩＳ　Ｌ１０９１－１９９８　Ａ－４（３秒接炎）により測定した炭化長が１０ｃｍ以下であることを特徴とする布帛。」が提供される。 Thus, according to the present invention, “a fabric containing organic fibers and colored by a printing process, characterized by having a carbonization length measured by JIS L1091-1998 A-4 (3-second flame contact) of 10 cm or less. Is provided.
　その際、前記有機繊維が、メタ型全芳香族ポリアミド繊維、パラ型全芳香族ポリアミド繊維、ポリベンズオキサゾール（ＰＢＯ）繊維、ポリベンズイミダゾール（ＰＢＩ）繊維、ポリベンズチアゾール（ＰＢＴＺ）繊維、ポリイミド（ＰＩ）繊維、ポリスルホンアミド（ＰＳＡ）、ポリエーテルエーテルケトン（ＰＥＥＫ）繊維、ポリエーテルイミド（ＰＥＩ）繊維、ポリアリレート（ＰＡｒ）繊維、メラミン繊維、フェノール繊維、フッ素系繊維、ポリフェニレンスルフィド（ＰＰＳ）繊維からなる群より選択されるいずれか１種であることが好ましい。また、布帛がさらに、ポリエステル繊維、セルロース繊維、ポリアミド繊維、ポリオレフィン繊維、アクリル繊維、レーヨン繊維、コットン繊維、獣毛繊維、ポリウレタン繊維、ポリ塩化ビニル繊維、ポリ塩化ビニリデン繊維、アセテート繊維およびポリカーボネート繊維からなる群より選択されるいずれか１種以上を含むことが好ましい。また、布帛を構成する繊維が全芳香族ポリアミド繊維のみであることが好ましい。また、メタ型全芳香族ポリアミド繊維が布帛重量対比３５重量％以上含まれることが好ましい。その際、前記メタ型全芳香族ポリアミド繊維の結晶化度が１５～２５％の範囲内であることが好ましい。また、前記メタ型全芳香族ポリアミド繊維を形成するメタ型全芳香族ポリアミドが、下記の式（１）で示される反復構造単位を含む芳香族ポリアミド骨格中に、反復構造の主たる構成単位とは異なる芳香族ジアミン成分、または芳香族ジカルボン酸ハライド成分を、第３成分として芳香族ポリアミドの反復構造単位の全量に対し１～１０ｍｏｌ％となるように共重合させたメタ型全芳香族ポリアミドであることが好ましい。
　－（ＮＨ－Ａｒ１－ＮＨ－ＣＯ－Ａｒ１－ＣＯ）－　・・・式（１）
ここで、Ａｒ１はメタ配位又は平行軸方向以外に結合基を有する２価の芳香族基である。 At that time, the organic fiber is a meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide ( PI) fiber, polysulfonamide (PSA), polyether ether ketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber It is preferably any one selected from the group consisting of The fabric is further made of polyester fiber, cellulose fiber, polyamide fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, acetate fiber and polycarbonate fiber. It is preferable to include any one or more selected from the group consisting of: Moreover, it is preferable that the fiber which comprises a fabric is only a fully aromatic polyamide fiber. Further, it is preferable that the meta-type wholly aromatic polyamide fiber is contained in an amount of 35% by weight or more relative to the weight of the fabric. At that time, the crystallinity of the meta-type wholly aromatic polyamide fiber is preferably in the range of 15 to 25%. In addition, the meta type wholly aromatic polyamide forming the meta type wholly aromatic polyamide fiber is an aromatic polyamide skeleton including a repeating structural unit represented by the following formula (1): A meta-type wholly aromatic polyamide obtained by copolymerizing different aromatic diamine components or aromatic dicarboxylic acid halide components as a third component so as to be 1 to 10 mol% based on the total amount of repeating structural units of the aromatic polyamide. It is preferable.
— (NH—Ar 1 —NH—CO—Ar 1 —CO) — (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
　その際、第３成分となる芳香族ジアミンが式（２）、（３）、または芳香族ジカルボン酸ハライドが、式（４）、（５）であることが好ましい。
　　Ｈ２Ｎ－Ａｒ２－ＮＨ２　・・・式（２）
　　Ｈ２Ｎ－Ａｒ２－Ｙ－Ａｒ２－ＮＨ２　・・・式（３）
　　ＸＯＣ－Ａｒ３－ＣＯＸ　・・・式（４）
　　ＸＯＣ－Ａｒ３－Ｙ－Ａｒ３－ＣＯＸ　・・・式（５）
ここで、Ａｒ２はＡｒ１とは異なる２価の芳香族基、Ａｒ３はＡｒ１とは異なる２価の芳香族基、Ｙは酸素原子、硫黄原子、アルキレン基からなる群から選ばれる少なくとも１種の原子又は官能基であり、Ｘはハロゲン原子を表す。 In that case, it is preferable that the aromatic diamine as the third component is represented by formulas (2) and (3), or the aromatic dicarboxylic acid halide is represented by formulas (4) and (5).
H 2 N—Ar 2 —NH 2 Formula (2)
H 2 N—Ar 2 —Y—Ar 2 —NH 2 Formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
　また、前記メタ型芳香族ポリアミド繊維の残存溶媒量が０．１重量％以下であることが好ましい。 Moreover, it is preferable that the residual solvent amount of the meta-type aromatic polyamide fiber is 0.1% by weight or less.
　また、布帛が、経密度４０～１００本／２５．４ｍｍ、および緯密度４０～１００本／２５．４ｍｍの織物であることが好ましい。また、布帛の目付けが１４０～３００ｇ／ｍ２の範囲内であることが好ましい。また、布帛において、ＪＩＳ　Ｌ１０９６－１９９８　Ａ法により測定した剛軟度が４～１２ｍｍの範囲内であることが好ましい。また、ＪＩＳ　Ｌ１０９１－１９９８　Ａ－４（１２ｓ接炎）に記載の垂直燃焼試験で残炎時間が１秒以下であることが好ましい。また、布帛が黒色または赤色に着色していることが好ましい。 Further, the fabric is preferably a woven fabric having a warp density of 40 to 100 pieces / 25.4 mm and a weft density of 40 to 100 pieces / 25.4 mm. The fabric weight is preferably in the range of 140 to 300 g / m 2 . Further, it is preferable that the bending resistance of the fabric measured by JIS L1096-1998 A method is in the range of 4 to 12 mm. In addition, the afterflame time is preferably 1 second or less in the vertical combustion test described in JIS L1091-1998 A-4 (12s flame contact). Moreover, it is preferable that the fabric is colored black or red.
　また、本発明によれば、前記の布帛の製造方法であって、捺染処理により布帛を着色する際、難燃剤を含む捺染処理剤を用いることを特徴とする布帛の製造方法が提供される。 Further, according to the present invention, there is provided a method for producing a fabric as described above, wherein when a fabric is colored by a textile printing process, a textile processing agent containing a flame retardant is used.
　ここで、捺染処理する際、アクリル樹脂またはウレタン樹脂からなるバインダーを含む捺染処理剤を用いることが好ましい。また、さらに布帛に撥水処理を施すことが好ましい。 Here, it is preferable to use a printing treatment agent containing a binder made of an acrylic resin or a urethane resin when printing. Further, it is preferable to perform a water repellent treatment on the fabric.
　また、本発明によれば、前記の布帛を用いてなる、消防服、消防団服、作業服、迷彩服、法被、およびエプロンからなる群より選択される繊維製品が提供される。 Further, according to the present invention, there is provided a textile product selected from the group consisting of fire fighting clothes, fire brigade clothes, work clothes, camouflage clothes, coats, and aprons using the fabric.
　本発明によれば、有機繊維を含みかつ捺染処理により着色された布帛であって、鮮明性、意匠性に優れるだけでなく難燃性にも優れる布帛およびその製造方法および繊維製品が得られる。 According to the present invention, it is possible to obtain a fabric containing organic fibers and colored by a printing process, which is excellent not only in sharpness and design but also in flame retardancy, a method for producing the same, and a textile product.
　以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　本発明の布帛において、有機繊維の種類は特に限定されないが、優れた難燃性を得る上で、メタ型全芳香族ポリアミド繊維、パラ型全芳香族ポリアミド繊維、ポリベンズオキサゾール（ＰＢＯ）繊維、ポリベンズイミダゾール（ＰＢＩ）繊維、ポリベンズチアゾール（ＰＢＴＺ）繊維、ポリイミド（ＰＩ）繊維、ポリスルホンアミド（ＰＳＡ）、ポリエーテルエーテルケトン（ＰＥＥＫ）繊維、ポリエーテルイミド（ＰＥＩ）繊維、ポリアリレート（ＰＡｒ）繊維、メラミン繊維、フェノール繊維、フッ素系繊維、ポリフェニレンスルフィド（ＰＰＳ）繊維などが好ましい。 In the fabric of the present invention, the type of organic fiber is not particularly limited. However, in order to obtain excellent flame retardancy, meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) fiber, Polybenzimidazole (PBI) fiber, Polybenzthiazole (PBTZ) fiber, Polyimide (PI) fiber, Polysulfonamide (PSA), Polyetheretherketone (PEEK) fiber, Polyetherimide (PEI) fiber, Polyarylate (PAr) Fiber, melamine fiber, phenol fiber, fluorine fiber, polyphenylene sulfide (PPS) fiber and the like are preferable.
　なかでも、メタ型全芳香族ポリアミド繊維が好ましい。メタ型全芳香族ポリアミド繊維とは、その繰返し単位の８５モル％以上がｍ－フェニレンイソフタルアミドであるポリマーからなる繊維である。かかるメタ型全芳香族ポリアミドは、１５モル％未満の範囲内で第３成分を含んだ共重合体であっても差しつかえない。 Of these, meta-type wholly aromatic polyamide fibers are preferable. The meta-type wholly aromatic polyamide fiber is a fiber made of a polymer in which 85 mol% or more of the repeating units is m-phenylene isophthalamide. Such a meta-type wholly aromatic polyamide may be a copolymer containing a third component within a range of less than 15 mol%.
　このようなメタ型全芳香族ポリアミドは、従来から公知の界面重合法により製造することができ、そのポリマーの重合度としては、０．５ｇ／１００ｍｌの濃度のＮ－メチル－２－ピロリドン溶液で測定した固有粘度（Ｉ．Ｖ．）が１．３～１．９ｄｌ／ｇの範囲のものが好ましく用いられる。 Such a meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method. The polymerization degree of the polymer is N-methyl-2-pyrrolidone solution having a concentration of 0.5 g / 100 ml. Those having a measured intrinsic viscosity (IV) in the range of 1.3 to 1.9 dl / g are preferably used.
　上記メタ型全芳香族ポリアミドにはアルキルベンゼンスルホン酸オニウム塩が含有されていてもよい。アルキルベンゼンスルホン酸オニウム塩としては、ヘキシルベンゼンスルホン酸テトラブチルフォスフォニウム塩、ヘキシルベンゼンスルホン酸トリブチルベンジルフォスフォニウム塩、ドデシルベンゼンスルホン酸テトラフェニルフォスフォニウム塩、ドデシルベンゼンスルホン酸トリブチルテトラデシルフォスフォニウム塩、ドデシルベンゼンスルホン酸テトラブチルフォスフォニウム塩、ドデシルベンゼンスルホン酸トリブチルベンジルアンモニウム塩等の化合物が好ましく例示される。なかでもドデシルベンゼンスルホン酸テトラブチルフォスフォニウム塩、又はドデシルベンゼンスルホン酸トリブチルベンジルアンモニウム塩は、入手しやすく、熱的安定性も良好なうえ、Ｎ－メチル－２－ピロリドンに対する溶解度も高いため特に好ましく例示される。 The meta-type wholly aromatic polyamide may contain an alkylbenzene sulfonic acid onium salt. Examples of the onium salt of alkylbenzene sulfonate include tetrabutyl phosphonium salt of hexyl benzene sulfonate, tributyl benzyl phosphonium salt of hexyl benzene sulfonate, tetraphenyl phosphonium salt of dodecyl benzene sulfonate, tributyl tetradecyl phosphonate of dodecyl benzene sulfonate. Preferred examples include compounds such as a nium salt, tetrabutylphosphonium salt of dodecylbenzenesulfonate, and tributylbenzylammonium salt of dodecylbenzenesulfonate. Among them, dodecylbenzenesulfonic acid tetrabutylphosphonium salt or dodecylbenzenesulfonic acid tributylbenzylammonium salt is particularly easy to obtain and has good thermal stability and high solubility in N-methyl-2-pyrrolidone. Preferably exemplified.
　上記アルキルベンゼンスルホン酸オニウム塩の含有割合は、十分な染色性の改良効果を得るために、ポリ－ｍ－フェニレンイソフタルアミドに対して２．５モル％以上、好ましくは３．０～７．０モル％の範囲にあるものが好ましい。 The content ratio of the alkylbenzenesulfonic acid onium salt is 2.5 mol% or more, preferably 3.0 to 7.0 mol, relative to poly-m-phenyleneisophthalamide in order to obtain a sufficient dyeing effect. Those in the range of% are preferred.
　また、ポリ－ｍ－フェニレンイソフタルアミドとアルキルベンゼンスルホン酸オニウム塩を混合する方法としては、溶媒中にポリ－ｍ－フェニレンイソフタルアミドを混合、溶解し、それにアルキルベンゼンスルホン酸オニウム塩を溶媒に溶解する方法などが用いられそのいずれを用いてもよい。このようにして得られたドープは、従来から公知の方法により繊維に形成される。 As a method of mixing poly-m-phenylene isophthalamide and alkylbenzene sulfonic acid onium salt, poly-m-phenylene isophthalamide is mixed and dissolved in a solvent, and alkylbenzene sulfonic acid onium salt is dissolved in the solvent. Any of these may be used. The dope thus obtained is formed into fibers by a conventionally known method.
　メタ型全芳香族ポリアミド繊維に用いるポリマーは、染着性や耐変褪色性を向上させる等目的で、下記の式（１）で示される反復構造単位を含む芳香族ポリアミド骨格中に、反復構造の主たる構成単位とは異なる芳香族ジアミン成分、または芳香族ジカルボン酸ハライド成分を、第３成分として芳香族ポリアミドの反復構造単位の全量に対し１～１０ｍｏｌ％となるように共重合させることも可能である。 The polymer used for the meta-type wholly aromatic polyamide fiber has a repetitive structure in an aromatic polyamide skeleton containing a recurring structural unit represented by the following formula (1) for the purpose of improving dyeability and resistance to discoloration. It is also possible to copolymerize an aromatic diamine component or aromatic dicarboxylic acid halide component different from the main structural unit of 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide as the third component. It is.
　　－（ＮＨ－Ａｒ１－ＮＨ－ＣＯ－Ａｒ１－ＣＯ）－　・・・式（１）
ここで、Ａｒ１はメタ配位又は平行軸方向以外に結合基を有する２価の芳香族基である。 — (NH—Ar 1 —NH—CO—Ar 1 —CO) — (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
　また、第３成分として共重合させることも可能であり、式（２）、（３）に示した芳香族ジアミンの具体例としては、例えば、ｐ－フェニレンジアミン、クロロフェニレンジアミン、メチルフェニレンジアミン、アセチルフェニレンジアミン、アミノアニシジン、ベンジジン、ビス（アミノフェニル）エーテル、ビス（アミノフェニル）スルホン、ジアミノベンズアニリド、ジアミノアゾベンゼン等が挙げられる。式（４）、（５）に示すような芳香族ジカルボン酸ジクロライドの具体例としては、例えば、テレフタル酸クロライド、１，４－ナフタレンジカルボン酸クロライド、２，６－ナフタレンジカルボン酸クロライド、４，４’－ビフェニルジカルボン酸クロライド、５－クロルイソフタル酸クロライド、５－メトキシイソフタル酸クロライド、ビス（クロロカルボニルフェニル）エーテルなどが挙げられる。 Further, it is possible to copolymerize as the third component. Specific examples of the aromatic diamine represented by the formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, Examples include acetylphenylenediamine, aminoanisidine, benzidine, bis (aminophenyl) ether, bis (aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene, and the like. Specific examples of the aromatic dicarboxylic acid dichloride represented by the formulas (4) and (5) include, for example, terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4 Examples include '-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis (chlorocarbonylphenyl) ether, and the like.
　　Ｈ２Ｎ－Ａｒ２－ＮＨ２　・・・式（２）
　　Ｈ２Ｎ－Ａｒ２－Ｙ－Ａｒ２－ＮＨ２　・・・式（３）
　　ＸＯＣ－Ａｒ３－ＣＯＸ　・・・式（４）
　　ＸＯＣ－Ａｒ３－Ｙ－Ａｒ３－ＣＯＸ　・・・式（５）
　ここで、Ａｒ２はＡｒ１とは異なる２価の芳香族基、Ａｒ３はＡｒ１とは異なる２価の芳香族基、Ｙは酸素原子、硫黄原子、アルキレン基からなる群から選ばれる少なくとも１種の原子又は官能基であり、Ｘはハロゲン原子を表す。 H 2 N—Ar 2 —NH 2 Formula (2)
H 2 N—Ar 2 —Y—Ar 2 —NH 2 Formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
　また、メタ型全芳香族ポリアミド繊維の結晶化度は、耐変褪色性も高い点および実用上必要な寸法安定性も確保できる点で５～３５％（より好ましくは１５～２５％）であることが好ましい。 The crystallinity of the meta-type wholly aromatic polyamide fiber is 5 to 35% (more preferably 15 to 25%) in terms of high resistance to discoloration and securing dimensional stability necessary for practical use. It is preferable.
　また、メタ型全芳香族ポリアミド繊維の残存溶媒量は、メタ型全芳香族ポリアミド繊維の優れた難燃性能を損なわない点で、０．１重量％以下であることが好ましい。 The residual solvent amount of the meta-type wholly aromatic polyamide fiber is preferably 0.1% by weight or less from the viewpoint that the excellent flame retardancy of the meta-type wholly aromatic polyamide fiber is not impaired.
　前記メタ型全芳香族ポリアミド繊維は以下の方法により製造することができ、特に後述する方法により、結晶化度や残存溶媒量を上記範囲とすることができる。 The meta-type wholly aromatic polyamide fiber can be produced by the following method, and in particular, the crystallinity and the residual solvent amount can be within the above ranges by the method described later.
　メタ型全芳香族ポリアミドポリマーの重合方法としては、特に限定する必要はなく、例えば特公昭３５－１４３９９号公報、米国特許第３３６０５９５号公報、特公昭４７－１０８６３号公報などに記載された溶液重合法、界面重合法を用いてもよい。 The polymerization method of the meta-type wholly aromatic polyamide polymer is not particularly limited. For example, the solution weight described in Japanese Patent Publication No. 35-14399, US Pat. No. 3,360,595, Japanese Patent Publication No. 47-10863, etc. A combination method or an interfacial polymerization method may be used.
　紡糸溶液としては、とくに限定する必要はないが、上記溶液重合や界面重合などで得られた、芳香族コポリアミドポリマーを含むアミド系溶媒溶液を用いても良いし、上記重合溶液から該ポリマーを単離し、これをアミド系溶媒に溶解したものを用いても良い。 The spinning solution is not particularly limited, but an amide solvent solution containing an aromatic copolyamide polymer obtained by the above solution polymerization or interfacial polymerization may be used, or the polymer may be removed from the polymerization solution. You may use what was isolated and melt | dissolved in the amide-type solvent.
　ここで用いられるアミド系溶媒としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、ジメチルスルホキシドなどを例示することができるが、とくにＮ，Ｎ－ジメチルアセトアミドが好ましい。 Examples of the amide solvent used here include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like, and in particular, N, N-dimethylacetamide. Is preferred.
　上記の通り得られた共重合芳香族ポリアミドポリマー溶液は、さらにアルカリ金属塩又はアルカリ土類金属塩を含むことにより安定化され、より高濃度、低温での使用が可能となり好ましい。好ましくはアルカリ金属塩及びアルカリ土類金属塩がポリマー溶液の全重量に対して１重量％以下、より好ましくは０．１重量％以下である。 The copolymerized aromatic polyamide polymer solution obtained as described above is preferably stabilized by containing an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and lower temperature. Preferably, the alkali metal salt and alkaline earth metal salt are 1% by weight or less, more preferably 0.1% by weight or less, based on the total weight of the polymer solution.
　紡糸・凝固工程においては、上記で得られた紡糸液（メタ型全芳香族ポリアミド重合体溶液）を凝固液中に紡出して凝固させる。 In the spinning / coagulation step, the spinning solution (meta-type wholly aromatic polyamide polymer solution) obtained above is spun into a coagulating solution and coagulated.
　紡糸装置としては特に限定されるものではなく、従来公知の湿式紡糸装置を使用することができる。また、安定して湿式紡糸できるものであれば、紡糸口金の紡糸孔数、配列状態、孔形状等は特に制限する必要はなく、例えば、孔数が１０００～３００００個、紡糸孔径が０．０５～０．２ｍｍのスフ用の多ホール紡糸口金等を用いてもよい。 The spinning apparatus is not particularly limited, and a conventionally known wet spinning apparatus can be used. In addition, the number of spinning holes, the arrangement state, the hole shape, etc. of the spinneret need not be particularly limited as long as they can be stably wet-spun. For example, the number of holes is 1,000 to 30,000, and the spinning hole diameter is 0.05. A multi-hole spinneret for ˜0.2 mm sufu may be used.
　また、紡糸口金から紡出する際の紡糸液（メタ型全芳香族ポリアミド重合体溶液）の温度は、２０～９０℃の範囲が適当である。 Further, the temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) when spinning from the spinneret is suitably in the range of 20 to 90 ° C.
　繊維を得るために用いる凝固浴としては、実質的に無機塩を含まない、アミド系溶媒、好ましくはＮＭＰの濃度が４５～６０重量％の水溶液を、浴液の温度１０～５０℃の範囲で用いる。アミド系溶媒（好ましくはＮＭＰ）の濃度が４５重量％未満ではスキンが厚い構造となってしまい、洗浄工程における洗浄効率が低下し、繊維の残存溶媒量を低減させることが困難となる。一方、アミド系溶媒（好ましくはＮＭＰ）の濃度が６０重量％を超える場合には、繊維内部に至るまで均一な凝固を行うことができず、このためやはり、繊維の残存溶媒量を低減させることが困難となる。なお、凝固浴中への繊維の浸漬時間は、０．１～３０秒の範囲が適当である。 As a coagulation bath used to obtain fibers, an amide solvent, preferably an aqueous solution containing 45 to 60% by weight of NMP, which is substantially free of inorganic salts, is used at a bath temperature of 10 to 50 ° C. Use. If the concentration of the amide solvent (preferably NMP) is less than 45% by weight, the skin has a thick structure, the washing efficiency in the washing step is lowered, and it is difficult to reduce the residual solvent amount of the fiber. On the other hand, when the concentration of the amide solvent (preferably NMP) exceeds 60% by weight, uniform coagulation cannot be performed up to the inside of the fiber, and therefore, the residual solvent amount of the fiber can be reduced. It becomes difficult. The fiber immersion time in the coagulation bath is suitably in the range of 0.1 to 30 seconds.
　引続き、アミド系溶媒、好ましくはＮＭＰの濃度が４５～６０重量％の水溶液であり、浴液の温度を１０～５０℃の範囲とした可塑延伸浴中にて、３～４倍の延伸倍率で延伸を行う。延伸後、１０～３０℃のＮＭＰの濃度が２０～４０重量％の水溶液、続いて５０～７０℃の温水浴を通して十分に洗浄を行う。 Subsequently, an amide solvent, preferably an aqueous solution having a concentration of NMP of 45 to 60% by weight, in a plastic stretching bath in which the temperature of the bath liquid is in the range of 10 to 50 ° C., at a stretching ratio of 3 to 4 times. Stretching is performed. After stretching, the film is thoroughly washed through an aqueous solution having an NMP concentration of 20 to 40% by weight at 10 to 30 ° C., followed by a hot water bath at 50 to 70 ° C.
　洗浄後の繊維は、温度２７０～２９０℃にて乾熱処理を施し、上記の結晶化度および残存溶媒量の範囲を満たすメタ型全芳香族アラミド繊維を得ることができる。 The washed fiber is subjected to a dry heat treatment at a temperature of 270 to 290 ° C. to obtain a meta-type wholly aromatic aramid fiber satisfying the above-mentioned range of crystallinity and residual solvent amount.
　前記有機繊維は、長繊維(マルチフィラメント)でもよいし短繊維でもよい。特に、他の繊維と混紡する上で繊維長２５～２００ｍｍの短繊維(紡績糸)が好ましい。また、有機繊維の単繊維繊度としては１～５ｄｔｅｘの範囲が好ましい。また、綿番手としては１０～５０番手（より好ましくは１５～２５番手）であることが好ましい。 The organic fiber may be a long fiber (multifilament) or a short fiber. In particular, short fibers (spun yarns) having a fiber length of 25 to 200 mm are preferred in blending with other fibers. The single fiber fineness of the organic fiber is preferably in the range of 1 to 5 dtex. The cotton count is preferably 10 to 50 (more preferably 15 to 25).
　本発明の布帛は前記の有機繊維だけで構成されていてもよいが、さらにポリエステル繊維、セルロース繊維、ポリアミド繊維、ポリオレフィン繊維、アクリル繊維、レーヨン繊維、コットン繊維、獣毛繊維、ポリウレタン繊維、ポリ塩化ビニル繊維、ポリ塩化ビニリデン繊維、アセテート繊維、ポリカーボネート繊維などの他の繊維が含まれていてもよい。 The fabric of the present invention may be composed only of the organic fibers described above, but further includes polyester fibers, cellulose fibers, polyamide fibers, polyolefin fibers, acrylic fibers, rayon fibers, cotton fibers, animal hair fibers, polyurethane fibers, polychlorinated fibers. Other fibers such as vinyl fiber, polyvinylidene chloride fiber, acetate fiber, and polycarbonate fiber may be included.
　その際、布帛を構成する繊維が全芳香族ポリアミド繊維（メタ型全芳香族ポリアミド繊維および／またはパラ型全芳香族ポリアミド繊維）のみであると優れた難燃性が得られ好ましい。特に、布帛に含まれるメタ型全芳香族ポリアミド繊維を布帛質量に対して３５重量％以上（より好ましくは５０重量％以上）であると優れた難燃性が得られ好ましい。用途や使用やのニーズに応じて、上記の難燃繊維、合成繊維、再生繊維、天然繊維を任意に混合できる。より具体的な例としては、メタ型全芳香族ポリアミド繊維が５０～９８重量％、ポリエステル繊維が２～５０重量％、セルロース系繊維が０～５０重量％の混率として快適性を併せ持つようにすることもできる。重視する性能に応じて比率を調整することができる。布帛を構成するいずれかの繊維に難燃剤を含ませることも好ましい。 At that time, it is preferable that excellent flame retardancy is obtained when the fibers constituting the fabric are only wholly aromatic polyamide fibers (meta-type wholly aromatic polyamide fibers and / or para-type wholly aromatic polyamide fibers). In particular, it is preferable that the meta-type wholly aromatic polyamide fiber contained in the fabric is 35% by weight or more (more preferably 50% by weight or more) with respect to the mass of the fabric because excellent flame retardancy is obtained. The flame retardant fiber, synthetic fiber, regenerated fiber, and natural fiber can be arbitrarily mixed according to the use and use needs. As a more specific example, the meta-type wholly aromatic polyamide fiber is 50 to 98% by weight, the polyester fiber is 2 to 50% by weight, and the cellulosic fiber is 0 to 50% by weight. You can also The ratio can be adjusted according to the performance to be emphasized. It is also preferable to include a flame retardant in any of the fibers constituting the fabric.
　本発明の布帛を製造する方法は、特に限定するものではなく、公知のいかなる方法でも用いる可能である。例えば前記の有機繊維と必要に応じて他の繊維とを混綿して紡績糸を得た後、単糸または双糸にて製織または製編するとよい。布帛の組織としては、平織、綾織、サテン、二重織などの織物が好ましいが、編物や不織布でもよい。特に、経密度４０～１００本／２５．４ｍｍ、および緯密度４０～１００本／２５．４ｍｍである織物が好ましい。布帛の製造方法は特に限定されず、レピア織機やグリッパー織機など公知の織編機を用いることができる。 The method for producing the fabric of the present invention is not particularly limited, and any known method can be used. For example, the organic fiber and other fibers as necessary may be blended to obtain a spun yarn, and then woven or knitted with a single yarn or twin yarn. The fabric structure is preferably a woven fabric such as plain weave, twill weave, satin or double weave, but may be knitted fabric or non-woven fabric. Particularly preferred are woven fabrics having a warp density of 40-100 strands / 25.4 mm and a weft density of 40-100 strands / 25.4 mm. The production method of the fabric is not particularly limited, and a known knitting machine such as a rapier loom or a gripper loom can be used.
　次いで、捺染処理により布帛を着色すると本発明の布帛が得られる。ここで、捺染処理は直接捺染法、抜染法、防染法などを含む。操作的には機械捺染、手捺染を含む。まず、顔料や助剤を糊と練り合わせて捺染処理剤をつくり、一般的には、捺染機で布帛に捺染処理剤を印捺(プリント)する。次いで水蒸気で加熱(スチーミング)し顔料を繊維によく浸透、染着させ、セッケン液等で処理(ソーピング)して付着染料などを除去し、水洗した後、乾燥する。 Subsequently, the fabric of the present invention is obtained by coloring the fabric by a textile printing process. Here, the printing process includes a direct printing method, a discharging method, an anti-dyeing method, and the like. Operation includes machine printing and hand printing. First, a printing agent is made by kneading a pigment or an auxiliary agent with glue, and generally, the printing agent is printed (printed) on a cloth by a printing machine. Next, the mixture is heated (steamed) with water vapor so that the pigment penetrates and dyes the fibers well, and is treated with a soap solution or the like (soaping) to remove attached dyes, washed with water, and dried.
　ここで、布帛を捺染処理する際に用いられる顔料としては、例えばＣＩＰｉｇｍｅｎｔ Ｙｅｌｌｏｗ９３、ＣＩ Ｐｉｇｍｅｎｔ Ｂｒｏｗｎ２３、ＣＩ Ｐｉｇｍｅｎｔ Ｒｅｄ１４４に代表される不溶性アゾ顔、ＣＩ ＶａｔＹｅｌｌｏｗ１（ＣＩ ７０６００）、ＣＩ Ｖａｔ Ｏｒａｎｇｅ７（ＣＩ ７１１０５）、ＣＩ Ｖａｔ Ｒｅｄ２３（ＣＩ ７１１３０）、ＣＩ Ｐｉｇｍｅｎｔ Ｒｅｄ１２３（ＣＩ７１１４０）、ＣＩ Ｖａｔ Ｖｉｏｌｅｔ１（ＣＩ ６００１０）、ＣＩ Ｖａｔ Ｂｌｕｅ４（ＣＩ ６９８００）に代表されるスレン系顔料 、ＣＩ Ｐｉｍｇｍｔ Ｂｌｕｅ１５（ＣＩ７４１６０）、Ｐｏｌｙ－ｂｒｏｍｏ－ｐｈｔａｌｏｃｙａｎｉｎｅに代表されるフタロシアニン系顔料 、ＣＩ Ｐｉｇｍｅｎｔ Ｒｅｄ１２２、ＣＩ Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ１９（ＣＩ４６５００）に代表されるキナクリドン系顔料 、ＣＩ Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ２３に代表されるジオキサジン系顔料 、ＣＩ Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １１０、ＣＩＰｉｇｍｅｎｔ Ｏｒａｎｇｅ４２、ＣＩ Ｐｉｇｍｅｎｔ Ｒｅｄ１８０で代表されるイソインドリノン系顔料などのほか、市販品として、ディクセルシリーズ（大日本インキ化学工業（株）製）、インペロンシリーズ（Ｄｙｓｔａｒ　Ｌｔｄ製）、リューダイシリーズ（大日本インキ化学工業（株）製）、ＨＩ－ＣＯＬＯＲ　ＢＬＡＣＫ　ＮＢ（林化学工業(株)製）、ＨＩ－ＣＯＬＯＲ　ＲＥＤ　Ｎ３Ｂ（林化学工(株)製）などが使用できる。 Here, examples of pigments used in textile printing include insoluble azo faces typified by CI Pigment Yellow 93, CI Pigment Brown 23, CI Pigment Red 144, CI Vat Yellow 1 (CI 70700), CI Vat Orange 105 (I7), C 71 CI Vat Red 23 (CI 71130), CI Pigment Red 123 (CI 71140), CI Vat Violet 1 (CI 60010), CI Vat ス Blue 4 (CI 69800), selenium pigment, CI Pimgmt blue 160m, ol-blue 160 Phthalocyanine pigments represented by CI, CI Pigment, Red1 2, quinacridone pigments represented by CI Pigment Violet 19 (CI46500), dioxazine pigments represented by CI Pigment Violet 23, CI pigments Yellow 110, CI Pigment Orange 42, CI Pigment and other red pigments such as CI Pigment As commercial products, Dixel series (Dainippon Ink Chemical Co., Ltd.), Imperon series (Dystar Ltd.), Ryudai series (Dainippon Ink Chemical Co., Ltd.), HI-COLOR BLACK NB (Hayashi) Chemical Industry Co., Ltd.), HI-COLOR RED N3B (manufactured by Hayashi Chemical Industry Co., Ltd.), etc. can be used.
　これらの顔料の中では、３００℃、１５分の熱履歴で変色しないものが特に好ましく、スレン系、フタロシアニン系、キナクリドン系、ジオキサジン系、イソインドリノン系顔料が好ましく用いられる。 Among these pigments, those that do not change color at a heat history of 300 ° C. for 15 minutes are particularly preferable, and selenium, phthalocyanine, quinacridone, dioxazine, and isoindolinone pigments are preferably used.
　顔料の布帛への付着量は、０．０５～３０．０重量％（より好ましくは０．１～２０．０重量％）であることが好ましい。 The amount of the pigment adhered to the cloth is preferably 0.05 to 30.0% by weight (more preferably 0.1 to 20.0% by weight).
　捺染処理において、捺染処理剤の布帛への付着量は、乾燥後の固形分重量として、７～８０ｇ／ｍ２（より好ましくは１０～５０ｇ／ｍ２）であることが好ましい。なお、本発明において用いる布帛への付着量は、単位面積当たりに付着した捺染処理剤の固形分重量に対する重量％とする。 In the textile printing treatment, the amount of the textile treating agent attached to the fabric is preferably 7 to 80 g / m 2 (more preferably 10 to 50 g / m 2 ) as the solid content weight after drying. In addition, the adhesion amount to the fabric used in the present invention is set to% by weight relative to the solid content weight of the printing processing agent adhered per unit area.
　本発明の布帛では、上記の顔料は、これらにバインダーを加えた捺染処理剤として用いられる。 In the fabric of the present invention, the above-described pigment is used as a printing processing agent in which a binder is added thereto.
　ここで、バインダーとしては、特に限定されないが、ポリウレタン系重合体、ポリアクリル系重合体、ポリアミド系重合体、ポリエステル系重合体、ポリエチレン系重合体、ポリプロピレン系重合体、ポリ塩化ビニル系重合体、ポリ塩化ビニリデン系重合体、ポリフッ素系重合体、あるいはシリコーン系重合体などの水系エマルジョン、さらにあるいは上記各重合体のプレポリマーの水系エマルジョンと架橋剤の組合せを用いればよい。特に、柔軟性、洗濯耐久性、耐加水分解性、コストなどの点からポリウレタン系重合体、ポリアクリル系重合体、ポリアミド系重合体、ポリエステル系重合体からなる群から選ばれる一種または二種以上の水系エマルジョンの組合せで用いるものがより好ましい。 Here, the binder is not particularly limited, but a polyurethane polymer, a polyacrylic polymer, a polyamide polymer, a polyester polymer, a polyethylene polymer, a polypropylene polymer, a polyvinyl chloride polymer, A water-based emulsion such as a polyvinylidene chloride polymer, a polyfluorine-based polymer, or a silicone-based polymer, or a combination of a water-based emulsion of a prepolymer of each polymer and a crosslinking agent may be used. In particular, one or more selected from the group consisting of a polyurethane polymer, a polyacrylic polymer, a polyamide polymer, and a polyester polymer in terms of flexibility, washing durability, hydrolysis resistance, cost, etc. Those used in combination with water-based emulsions are more preferred.
　なお、上記架橋剤としては、アクリル酸、メタクリル酸、ヒドロキシアルキルアクリレート、ヒドロキシアルキルメタクリレート、グリシジルアクリレート、グリシジルメタクリレート、アクリルアミド、メタクリルアミド、メチロールアクリルアミド、ビニルエチレン尿素、アクロレイン、ケテンダイマー、ビニルイソシアネート、ジビニルスルホン等の官能基を有する反応性化合物などが用いられる。 Examples of the crosslinking agent include acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, methylol acrylamide, vinyl ethylene urea, acrolein, ketene dimer, vinyl isocyanate, divinyl sulfone. A reactive compound having a functional group such as is used.
　バインダー（必要に応じて用いられる架橋剤を含む）の付着量は、１０～７０重量％（より好ましくは１０～６０重量％）であることが好ましい。 The amount of adhesion of the binder (including a crosslinking agent used as necessary) is preferably 10 to 70% by weight (more preferably 10 to 60% by weight).
　なお、捺染処理剤の好ましい割合は、顔料：バインダー（固形分換算、架橋剤を含む）で１：９９～９９：１である。 A desirable ratio of the textile processing agent is 1:99 to 99: 1 in terms of pigment: binder (in terms of solid content, including a crosslinking agent).
　さらに、本発明の布帛では、難燃性をさらに向上させるために、難燃剤（防炎剤ということもある。）が併用されていることが好ましい。例えば、リン系および／またはハロゲン系難燃剤が好適に例示される。 Furthermore, in the fabric of the present invention, in order to further improve the flame retardancy, it is preferable that a flame retardant (sometimes referred to as a flame retardant) is used in combination. For example, phosphorus-based and / or halogen-based flame retardants are preferably exemplified.
　リン系難燃剤としては、リン酸エステル、ホスホン酸エステル、およびホスファゼンオリゴマーなどが好適に例示される。 Favorable examples of the phosphorus-based flame retardant include phosphate esters, phosphonate esters, and phosphazene oligomers.
　ハロゲン系難燃剤としては、有機ハロゲン系難燃剤が好ましい。かかる有機ハロゲン系難燃剤としては、ハロゲン化カーボネートオリゴマー、ハロゲン化エポキシ化合物、ハロゲン化ポリスチレン、ハロゲン化トリアジン化合物、ハロゲン化ジフェニルアルカン系化合物、ハロゲン化インダン系化合物、およびハロゲン化芳香族フタルイミド系化合物などが挙げられ、中でもポリカーボネートとの相溶性に優れ、その耐熱性および熱安定性が良好であることからハロゲン化カーボネートオリゴマー、ハロゲン化エポキシ化合物が好ましい。 As the halogen flame retardant, an organic halogen flame retardant is preferable. Examples of the organic halogen flame retardant include halogenated carbonate oligomer, halogenated epoxy compound, halogenated polystyrene, halogenated triazine compound, halogenated diphenylalkane compound, halogenated indane compound, and halogenated aromatic phthalimide compound. Among these, halogenated carbonate oligomers and halogenated epoxy compounds are preferred because of their excellent compatibility with polycarbonate and their good heat resistance and thermal stability.
　以上の難燃剤の付着量は、布帛重量対比１．０～５０．０重量％（より好ましくは２．０～４０．０重量％）であることが好ましい。 The adhesion amount of the above flame retardant is preferably 1.0 to 50.0% by weight (more preferably 2.0 to 40.0% by weight) relative to the weight of the fabric.
　なお、上記難燃剤中には、酸化チタン、二酸化ケイ素、酸化亜鉛、塩基性炭酸亜鉛や白鉛、塩基性硫酸亜鉛、硫酸鉛、硫化亜鉛、酸化セリウム、酸化ジルコニウム、酸化タングステン、酸化スズ、硫酸バリウム、三酸化アンチモン、水酸化アルミニウムなどの無機系難燃剤を５．０重量％以下程度、配合することもできる。 In the above flame retardant, titanium oxide, silicon dioxide, zinc oxide, basic zinc carbonate and white lead, basic zinc sulfate, lead sulfate, zinc sulfide, cerium oxide, zirconium oxide, tungsten oxide, tin oxide, sulfuric acid An inorganic flame retardant such as barium, antimony trioxide, and aluminum hydroxide can be blended in an amount of about 5.0% by weight or less.
　本発明において捺染処理は、上記顔料およびバインダー（さらに、必要に応じて上記難燃剤）を主成分とする捺染処理剤を、例えば捺染に適した２０００～５００００ｃＰｓ程度の粘度に調合し、３００～２０００メッシュのスクリーンを用いて捺染すればよい。このときのスクリーンはフラットまたはロータリー方式を採用すればよい。プリント捺染後、１２０～１８０℃で１～５分間乾燥したのち、１７０～２２０℃で０．５～５分熱処理すればよい。 In the present invention, the printing treatment is carried out by blending a printing treatment agent mainly composed of the pigment and the binder (and, if necessary, the flame retardant) to a viscosity of about 2000 to 50000 cPs suitable for printing, for example, 300 to 2000. Printing may be performed using a mesh screen. The screen at this time may adopt a flat or rotary method. After printing, after drying at 120 to 180 ° C. for 1 to 5 minutes, heat treatment may be performed at 170 to 220 ° C. for 0.5 to 5 minutes.
　さらには、撥水処理を施すことが好ましい。驚くべきことに撥水処理が施されても難燃性が維持される。かかる撥水処理としては、例えば、特許第３１３３２２７号公報や特公平４－５７８６号公報に記載された方法が好適である。すなわち、撥水剤として市販のふっ素系撥水剤（パーフルオロオクタン酸およびパーフルオロオクタンスルホン酸を含有しないふっ素系撥水剤が好ましい。）やシリコーン系撥水剤などを使用し、必要に応じてメラミン樹脂、触媒を混合して撥水剤の濃度が３～１５重量％程度の加工剤とし、ピックアップ率５０～９０％程度で、該加工剤を用いて布帛の表面を処理する方法である。加工剤で布帛の表面を処理する方法としては、パッド法（浸漬、圧搾）、スプレー法などが例示される。なかでも、加工剤を布帛内部まで浸透させる上でパッド法が最も好ましい。なお、前記ピックアップ率とは、加工剤の布帛（加工剤付与前）重量に対する重量割合（％）である。 Furthermore, it is preferable to perform a water repellent treatment. Surprisingly, the flame retardancy is maintained even when the water repellent treatment is applied. As such water repellent treatment, for example, methods described in Japanese Patent No. 3133227 and Japanese Patent Publication No. 4-5786 are suitable. That is, commercially available fluorine-based water repellents (preferably fluorine-based water repellents that do not contain perfluorooctanoic acid and perfluorooctane sulfonic acid) or silicone-based water repellents are used as the water repellent. In this method, a melamine resin and a catalyst are mixed to form a processing agent having a water repellent concentration of about 3 to 15% by weight, and the surface of the fabric is treated with the processing agent at a pickup rate of about 50 to 90%. . Examples of the method for treating the surface of the fabric with the processing agent include a pad method (immersion, pressing), a spray method, and the like. Of these, the pad method is most preferable for allowing the processing agent to penetrate into the fabric. In addition, the said pick-up rate is a weight ratio (%) with respect to the fabric (before processing agent provision) weight of a processing agent.
　かくして得られた布帛において、ＪＩＳ　Ｌ１０９１－１９９８　Ａ－４（３秒接炎）により測定した炭化長が１０ｃｍ以下(好ましくは５ｃｍ以下、特に好ましくは０．１～３．０ｃｍ)であることが肝要である。該炭化長が１０ｃｍよりも大きいと防護服などとして使えないおそれがある。また、ＪＩＳ　Ｌ１０９１－１９９８　Ａ－４（１２秒接炎）に記載の垂直燃焼試験で残炎時間が１秒以下（より好ましくは０秒）であることが好ましい。 It is essential that the fabric thus obtained has a carbonization length of 10 cm or less (preferably 5 cm or less, particularly preferably 0.1 to 3.0 cm) as measured by JIS L1091-1998 A-4 (3 second flame contact). It is. If the carbonization length is greater than 10 cm, it may not be used as protective clothing. In addition, the afterflame time is preferably 1 second or less (more preferably 0 seconds) in the vertical combustion test described in JIS L1091-1998 A-4 (12-second flame contact).
　かかる布帛の目付けや剛軟度は用途により適宜選定されるが、布帛の目付けとしては１４０～３００ｇ／ｍ２の範囲内であることが好ましい。 The basis weight and the bending resistance of the fabric are appropriately selected depending on the application, but the basis weight of the fabric is preferably within a range of 140 to 300 g / m 2 .
　また、布帛の剛軟度としては４～１２ｍｍの範囲内であることが好ましい。なお、剛軟度はＪＩＳ　Ｌ１０９６－１９９８　Ａ法（カンチレバー法）により測定するものとする。 Further, the bending resistance of the fabric is preferably in the range of 4 to 12 mm. The bending resistance is measured by JIS L1096-1998 A method (cantilever method).
　また、布帛が黒色または赤色に着色していることが好ましい。特に、布帛において、黒色に着色した箇所と赤色に着色した箇所を有することが好ましい。 Further, it is preferable that the fabric is colored black or red. In particular, the fabric preferably has a black colored portion and a red colored portion.
　次に、本発明の繊維製品は、前記の布帛を用いてなる、消防服、消防団服、作業服、迷彩服、法被、およびエプロンからなる群より選択される繊維製品である。例えば、黒色に着色した箇所と赤色に着色した箇所を有する法被が好ましい。 Next, the textile product of the present invention is a textile product selected from the group consisting of fire fighting clothes, fire brigade clothes, work clothes, camouflage clothes, coats and aprons using the above-mentioned fabric. For example, a coat having a black colored portion and a red colored portion is preferable.
　かかる繊維製品は前記の布帛を用いているので、捺染固有の鮮明性、意匠性に優れるだけでなく難燃性にも優れる。 Since such a textile product uses the above-mentioned fabric, it is excellent not only in the sharpness and design characteristic inherent to textile printing, but also in flame retardancy.
　以下、実施例をあげて本発明を詳細に説明するが、本発明はこれらによって何ら限定されるものではない。なお、実施例中の各物性は下記の方法により測定したものである。
（１）目付け
　ＪＩＳ Ｌ １０９６－１９９８により測定した。
（２）炭化長
　ＪＩＳ　Ｌ１０９１－１９９８　Ａ－４（３秒接炎）に記載の燃焼試験により測定した。
（３）残炎時間
　ＪＩＳ　Ｌ１０９１－１９９８　Ａ－４（１２秒接炎）に記載の垂直燃焼試験により測定した。
（４）剛軟度
　ＪＩＳ　Ｌ１０９６－１９９８　Ａ法（カンチレバー法）により測定した。
（５）残存溶媒量
　繊維を約８．０ｇ採取し、１０５℃で１２０分間乾燥させた後にデシケーター内で放冷し、繊維重量（Ｍ１）を秤量した。続いて、この繊維について、メタノール中で１．５時間、ソックスレー抽出器を用いて還流抽出を行い、繊維中に含まれるアミド系溶媒の抽を行った。抽出を終えた繊維を取り出して、１５０℃で６０分間真空乾燥させた後にデシケーター内で放冷し、繊維重量（Ｍ２）を秤量した。繊維中に残存する溶媒量（アミド系溶媒重量）は、得られるＭ１およびＭ２を用いて、下記式により算出した。
残存溶媒量（％）＝［（Ｍ１－Ｍ２）／Ｍ１］×１００
（６）結晶化度
　Ｘ線回折測定装置（リガク社製  ＲＩＮＴ  ＴＴＲIII）を用い、繊維を約１ｍｍ径の繊維束に引きそろえて繊維試料台に装着して回折プロファイルを測定した。測定条件は、Ｃｕ－Ｋα線源（５０ｋＶ、３００ｍＡ）、走査角度範囲１０～３５°、連続測定０．１°幅計測、１°／分走査でおこなった。実測した回折プロファイルから空気散乱、非干渉性散乱を直線近似で補正して全散乱プロファイルを得た。次に、全散乱プロファイルから非晶質散乱プロファイルを差し引いて結晶散乱プロファイルを得た。結晶化度は、結晶散乱プロファイルの面積強度（結晶散乱強度）と全散乱プロファイルの面積強度（全散乱強度）から、次式により求めた。
結晶化度（％）＝［結晶散乱強度／全散乱強度］×１００
　　［実施例１］
　メタ型全芳香族ポリアミド繊維（帝人(株)製コーネックス(登録商標）（繊維長５１ｍｍ）のステープルファイバーを紡績糸２０番手／双糸を経糸に配し、メタ型全芳香族ポリアミド繊維（帝人(株)製コーネックス(登録商標）（繊維長５１ｍｍ）のステープルファイバーを紡績糸２０番手／単糸を緯糸に配し、織密度　経６５本／２５．４ｍｍ、緯５６本／２５．４ｍｍで製織し、３／１綾組織の織物を得た。次いで、該織物に以下の捺染処理を施した後、以下の撥水処理を施した。
（捺染処理）
　ＨＩ－ＣＯＬＯＲ　ＢＬＡＣＫ　ＮＢ(黒色の顔料)：１０重量部とＤＹＦ３０（バインダー）：１００重量部、ハイガードＦＲ－１００（難燃剤）：１０重量部、フィクサー（架橋剤）：３重量部＜全て、林化学工業（株）製＞を混合し、捺染（プリント処理）を２往復実施し（塗布量は、生地重量の２０重量％）、４０℃で２時間乾燥した。
（撥水処理）
　ＡＧ－Ｅ０８２（明成化学工業(株)製）：７５ｇ／ＬとＮＫガードＳ－２２（日華化学製）：５０ｇ／ＬとメーカネートＢＸ（明成化学工業(株)製）：２０ｇ／Ｌを混合し、浸漬、圧搾（ピックアップ率：６５％以上）、乾燥（１６０℃×９０秒）、熱処理（１９０℃×６０秒）を実施した。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited at all by these. In addition, each physical property in an Example is measured with the following method.
(1) Weight per unit area Measured according to JIS L 1096-1998.
(2) Carbonization length It was measured by a combustion test described in JIS L1091-1998 A-4 (3 second flame contact).
(3) Afterflame time It was measured by the vertical combustion test described in JIS L1091-1998 A-4 (12 second flame contact).
(4) Bending softness Measured by JIS L1096-1998 A method (cantilever method).
(5) Amount of residual solvent About 8.0 g of fiber was collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and the fiber weight (M1) was weighed. Subsequently, this fiber was subjected to reflux extraction using a Soxhlet extractor in methanol for 1.5 hours to extract an amide solvent contained in the fiber. The extracted fiber was taken out, vacuum-dried at 150 ° C. for 60 minutes, allowed to cool in a desiccator, and the fiber weight (M2) was weighed. The amount of solvent remaining in the fiber (amide solvent weight) was calculated by the following formula using M1 and M2 obtained.
Residual solvent amount (%) = [(M1-M2) / M1] × 100
(6) Crystallinity Using an X-ray diffractometer (RINT TTRIII, manufactured by Rigaku Corporation), the fibers were aligned in a fiber bundle having a diameter of about 1 mm and mounted on a fiber sample table to measure a diffraction profile. The measurement conditions were Cu—Kα radiation source (50 kV, 300 mA), scanning angle range 10 to 35 °, continuous measurement 0.1 ° width measurement, 1 ° / min scanning. From the measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain a total scattering profile. Next, a crystal scattering profile was obtained by subtracting the amorphous scattering profile from the total scattering profile. The degree of crystallinity was determined by the following equation from the area intensity of the crystal scattering profile (crystal scattering intensity) and the area intensity of the total scattering profile (total scattering intensity).
Crystallinity (%) = [crystal scattering intensity / total scattering intensity] × 100
[Example 1]
Meta-type wholly aromatic polyamide fiber (Conex (registered trademark) manufactured by Teijin Limited) (fiber length 51 mm) staple fiber is placed on the 20th spun yarn / twist yarn as warp, and meta-type wholly aromatic polyamide fiber (Teijin) Conex (registered trademark) (fiber length 51 mm) staple fiber made by Co., Ltd., spun yarn 20 count / single yarn is arranged on the weft, and weave density is warp 65 / 25.4 mm, weft 56 / 25.4 mm After weaving, a woven fabric having a 3/1 twill structure was obtained.The fabric was then subjected to the following printing treatment and then the following water-repellent treatment.
(Printing process)
HI-COLOR BLACK NB (black pigment): 10 parts by weight and DYF30 (binder): 100 parts by weight, Higuard FR-100 (flame retardant): 10 parts by weight, Fixer (crosslinking agent): 3 parts by weight <all, Hayashi Chemical Industry Co., Ltd.> was mixed, and printing (printing process) was performed twice (the coating amount was 20% by weight of the dough weight) and dried at 40 ° C. for 2 hours.
(Water repellent treatment)
AG-E082 (manufactured by Meisei Chemical Co., Ltd.): 75 g / L and NK guard S-22 (manufactured by Nikka Chemical): 50 g / L and Makernate BX (manufactured by Meisei Chemical Industry Co., Ltd.): 20 g / L Mixing, immersion, pressing (pickup rate: 65% or more), drying (160 ° C. × 90 seconds), and heat treatment (190 ° C. × 60 seconds) were performed.
　得られた織物において、目付け２３８ｇ／ｍ２、顔料の付着量１０重量％、難燃剤の付着量１０重量％、バインダーの付着量１００重量％、炭化長が２．０ｃｍ、残炎時間が０秒、剛軟度が６．２ｃｍであった。 In the obtained woven fabric, the basis weight is 238 g / m 2 , the pigment adhesion amount is 10% by weight, the flame retardant adhesion amount is 10% by weight, the binder adhesion amount is 100% by weight, the carbonization length is 2.0 cm, and the afterflame time is 0 second. The bending resistance was 6.2 cm.
　次いで、該布帛を用いて消防団服(法被)を得たところ、鮮明性、意匠性に優れるだけでなく難燃性にも優れるものであった。 Next, when the fire brigade uniform was obtained using the fabric, it was not only excellent in sharpness and design, but also excellent in flame retardancy.
　　［実施例２］
　上記捺染処方のアクリルバインダー（ＤＹＦ３０）をウレタンバインダー（ニュープレックスＡＵ－１３）に変更した以外は、実施例１と同様の操作を行った。 [Example 2]
The same operation as in Example 1 was performed, except that the acrylic binder (DYF30) in the above printing formulation was changed to a urethane binder (Newplex AU-13).
　得られた織物において、目付け２３５ｇ／ｍ２、顔料の付着量１０重量％、難燃剤の付着量１０重量％、バインダーの付着量１００重量％、炭化長が１．５ｃｍ、残炎時間が０秒、剛軟度が４．５ｃｍであった。 In the obtained woven fabric, the basis weight is 235 g / m 2 , the pigment adhesion amount is 10% by weight, the flame retardant adhesion amount is 10% by weight, the binder adhesion amount is 100% by weight, the carbonization length is 1.5 cm, and the afterflame time is 0 second. The bending resistance was 4.5 cm.
　　［実施例３］
　実施例１で用いた黒色の顔料を赤色の顔料（ＨＩ－ＣＯＬＯＲ　ＲＥＤ　Ｎ３Ｂ）に変更した以外は、実施例１と同様の操作を行った。 [Example 3]
The same operation as in Example 1 was performed except that the black pigment used in Example 1 was changed to a red pigment (HI-COLOR RED N3B).
　得られた織物において、目付け２３９ｇ／ｍ２、顔料の付着量１０重量％、難燃剤の付着量１０重量％、バインダーの付着量１００重量％、炭化長が２．４ｃｍ、残炎時間が０秒、剛軟度が５．２ｃｍであった。 In the obtained woven fabric, the basis weight was 239 g / m 2 , the pigment adhesion amount was 10% by weight, the flame retardant adhesion amount was 10% by weight, the binder adhesion amount was 100% by weight, the carbonization length was 2.4 cm, and the afterflame time was 0 seconds. The bending resistance was 5.2 cm.
　　［比較例１］
　上記捺染処方の難燃剤（ハイガードＦＲ－１００）を５重量部に変更した以外は、実施例１と同様の操作を行った。 [Comparative Example 1]
The same operation as in Example 1 was performed, except that the flame retardant (Higuard FR-100) in the above printing recipe was changed to 5 parts by weight.
　得られた織物において、目付け２３１ｇ／ｍ２、顔料の付着量１０重量％、難燃剤の付着量５重量％、バインダーの付着量１００重量％、炭化長が２０ｃｍ以上(全焼)、残炎時間が３０秒以上（全焼)、剛軟度が６．０ｃｍであった。 In the obtained woven fabric, the basis weight is 231 g / m 2 , the pigment adhesion amount is 10% by weight, the flame retardant adhesion amount is 5% by weight, the binder adhesion amount is 100% by weight, the carbonization length is 20 cm or more (burnt), and the after flame time. The bending resistance was 6.0 cm for 30 seconds or more (burnt completely).
　　［比較例２］
　上記捺染処方の難燃剤（ハイガードＦＲ－１００）を０重量部に変更した以外は、実施例１と同様の操作を行った。 [Comparative Example 2]
The same operation as in Example 1 was carried out except that the flame retardant (Higuard FR-100) in the textile printing formulation was changed to 0 parts by weight.
　得られた織物において、目付け２３０ｇ／ｍ２、顔料の付着量１０重量％、難燃剤の付着量０重量％、バインダーの付着量１００重量％、炭化長が２０ｃｍ以上(全焼)、残炎時間が３０秒以上（全焼)、剛軟度が６．０ｃｍであった。 In the obtained woven fabric, the basis weight is 230 g / m 2 , the pigment adhesion amount is 10% by weight, the flame retardant adhesion amount is 0% by weight, the binder adhesion amount is 100% by weight, the carbonization length is 20 cm or more (total burning), and the after flame time. The bending resistance was 6.0 cm for 30 seconds or more (burnt completely).
　　［実施例４］
　実施例１においてメタ型全芳香族ポリアミド繊維として以下の方法で作製した物を用いること以外は実施例１と同様にした。 [Example 4]
Example 1 was carried out in the same manner as Example 1 except that a meta-type wholly aromatic polyamide fiber was prepared by the following method.
　特公昭４７－１０８６３号公報記載の方法に準じた界面重合法により製造した、固有粘度（Ｉ．Ｖ．）が１．９のポリメタフェニレンイソフタルアミド粉末２０．０重量部を、－１０℃に冷却したＮ－メチル－２－ピロリドン（ＮＭＰ）８０．０重量部中に懸濁させ、スラリー状にした。引き続き、懸濁液を６０℃まで昇温して溶解させ、透明なポリマー溶液を得た。該ポリマー溶液に、ポリマー対比３．０重量％の２－［２Ｈ－ベンゾトリアゾール－２－イル］－４－６－ビス（１－メチル－１－フェニルエチル）フェノール粉末（水への溶解度：０．０１ｍｇ／Ｌ）を混合溶解させ、減圧脱法して紡糸液（紡糸ドープ）とした。

［紡糸・凝固工程］
　上記紡糸ドープを、孔径０．０７ｍｍ、孔数５００の紡糸口金から、浴温度３０℃の凝固浴中に吐出して紡糸した。凝固液の組成は、水／ＮＭＰ＝４５／５５（重量部）であり、凝固浴中に糸速７ｍ／分で吐出して紡糸した。
［可塑延伸浴延伸工程］
　引き続き、温度４０℃の水／ＮＭＰ＝４５／５５の組成の可塑延伸浴中にて、３．７倍の延伸倍率で延伸を行った。
［洗浄工程］
　延伸後、２０℃の水／ＮＭＰ＝７０／３０の浴（浸漬長１．８ｍ）、続いて２０℃の水浴（浸漬長３．６ｍ）で洗浄し、さらに６０℃の温水浴（浸漬長５．４ｍ）に通して十分に洗浄を行った。
［乾熱処理工程］
　洗浄後の繊維について、表面温度２８０℃の熱ローラーにて乾熱処理を施し、メタ型全芳香族ポリアミド繊維を得た。
［繊維の物性］
　得られたメタ型全芳香族ポリアミド繊維の物性は、繊度１．７ｄｔｅｘ、残存溶媒量０．０８重量％、結晶化度は１９％であった。　得られた織物において、目付け２３５ｇ／ｍ２、顔料の付着量１０重量％、難燃剤の付着量１０重量％、バインダーの付着量１００重量％、炭化長が２．０ｃｍ、残炎時間が０秒、剛軟度が３．５ｃｍであった 20.0 parts by weight of polymetaphenylene isophthalamide powder produced by an interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863 and having an intrinsic viscosity (IV) of 1.9 is placed at −10 ° C. It was suspended in 80.0 parts by weight of cooled N-methyl-2-pyrrolidone (NMP) to form a slurry. Subsequently, the suspension was heated to 60 ° C. and dissolved to obtain a transparent polymer solution. To the polymer solution, 3.0% by weight of 2- [2H-benzotriazol-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol powder (solubility in water: 0) .01 mg / L) was mixed and dissolved, and depressurized under reduced pressure to obtain a spinning solution (spinning dope).

[Spinning and coagulation process]
The spinning dope was spun from a spinning nozzle having a hole diameter of 0.07 mm and a hole number of 500 into a coagulation bath having a bath temperature of 30 ° C. The composition of the coagulation liquid was water / NMP = 45/55 (parts by weight), and was spun by discharging into the coagulation bath at a yarn speed of 7 m / min.
[Plastic stretching bath stretching process]
Subsequently, the film was stretched at a stretching ratio of 3.7 times in a plastic stretching bath having a composition of water / NMP = 45/55 at a temperature of 40 ° C.
[Washing process]
After stretching, the film was washed with a 20 ° C. water / NMP = 70/30 bath (immersion length 1.8 m), followed by a 20 ° C. water bath (immersion length 3.6 m), and then a 60 ° C. hot water bath (immersion length 5). 4m) and thoroughly washed.
[Dry heat treatment process]
The washed fiber was subjected to a dry heat treatment with a heat roller having a surface temperature of 280 ° C. to obtain a meta-type wholly aromatic polyamide fiber.
[Fiber properties]
The physical properties of the obtained meta-type wholly aromatic polyamide fiber were a fineness of 1.7 dtex, a residual solvent amount of 0.08% by weight, and a crystallinity of 19%. In the obtained woven fabric, the weight per unit area was 235 g / m 2 , the pigment adhesion amount was 10% by weight, the flame retardant adhesion amount was 10% by weight, the binder adhesion amount was 100% by weight, the carbonization length was 2.0 cm, and the afterflame time was 0 second. The bending resistance was 3.5 cm
　本発明によれば、有機繊維を含みかつ捺染処理により着色された布帛であって、鮮明性、意匠性に優れるだけでなく難燃性にも優れる布帛およびその製造方法および繊維製品が提供され、その工業的価値は極めて大である。 According to the present invention, there are provided a fabric containing organic fibers and colored by a textile printing process, which is excellent not only in sharpness and design but also in flame retardancy, a method for producing the same, and a textile product, Its industrial value is extremely large.

Claims (18)

  1. 　有機繊維を含みかつ捺染処理により着色された布帛であって、ＪＩＳ　Ｌ１０９１－１９９８　Ａ－４（３秒接炎）により測定した炭化長が１０ｃｍ以下であることを特徴とする布帛。 A fabric containing organic fibers and colored by a printing process, wherein the carbonization length measured by JIS L1091-1998 A-4 (3-second flame contact) is 10 cm or less.
  2. 　前記有機繊維が、メタ型全芳香族ポリアミド繊維、パラ型全芳香族ポリアミド繊維、ポリベンズオキサゾール（ＰＢＯ）繊維、ポリベンズイミダゾール（ＰＢＩ）繊維、ポリベンズチアゾール（ＰＢＴＺ）繊維、ポリイミド（ＰＩ）繊維、ポリスルホンアミド（ＰＳＡ）、ポリエーテルエーテルケトン（ＰＥＥＫ）繊維、ポリエーテルイミド（ＰＥＩ）繊維、ポリアリレート（ＰＡｒ）繊維、メラミン繊維、フェノール繊維、フッ素系繊維、ポリフェニレンスルフィド（ＰＰＳ）繊維からなる群より選択されるいずれか１種である、請求項１に記載の布帛。 The organic fiber is a meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide (PI) fiber. , Polysulfonamide (PSA), polyether ether ketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber The fabric according to claim 1, wherein the fabric is any one selected from more.
  3. 　布帛がさらに、ポリエステル繊維、セルロース繊維、ポリアミド繊維、ポリオレフィン繊維、アクリル繊維、レーヨン繊維、コットン繊維、獣毛繊維、ポリウレタン繊維、ポリ塩化ビニル繊維、ポリ塩化ビニリデン繊維、アセテート繊維およびポリカーボネート繊維からなる群より選択されるいずれか１種以上を含む、請求項１に記載の布帛。 The fabric further comprises polyester fiber, cellulose fiber, polyamide fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, acetate fiber and polycarbonate fiber. The fabric according to claim 1, comprising any one or more selected from the above.
  4. 　布帛を構成する繊維が全芳香族ポリアミド繊維のみである、請求項１に記載の布帛。 The fabric according to claim 1, wherein the fibers constituting the fabric are only wholly aromatic polyamide fibers.
  5. 　メタ型全芳香族ポリアミド繊維が布帛重量対比３５重量％以上含まれる、請求項１に記載の布帛。 The fabric according to claim 1, wherein the meta-type wholly aromatic polyamide fiber is contained in an amount of 35% by weight or more relative to the weight of the fabric.
  6. 　前記メタ型全芳香族ポリアミド繊維の結晶化度が１５～２５％の範囲内である、請求項５に記載の布帛。 The fabric according to claim 5, wherein the crystallinity of the meta-type wholly aromatic polyamide fiber is in the range of 15 to 25%.
  7. 　前記メタ型全芳香族ポリアミド繊維を形成するメタ型全芳香族ポリアミドが、下記の式（１）で示される反復構造単位を含む芳香族ポリアミド骨格中に、反復構造の主たる構成単位とは異なる芳香族ジアミン成分、または芳香族ジカルボン酸ハライド成分を、第３成分として芳香族ポリアミドの反復構造単位の全量に対し１～１０ｍｏｌ％となるように共重合させたメタ型全芳香族ポリアミドである、請求項５に記載の布帛。
    　－（ＮＨ－Ａｒ１－ＮＨ－ＣＯ－Ａｒ１－ＣＯ）－　・・・式（１）
    ここで、Ａｒ１はメタ配位又は平行軸方向以外に結合基を有する２価の芳香族基である。     The meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber has an aromatic different from the main constituent unit of the repeating structure in the aromatic polyamide skeleton containing the repeating structural unit represented by the following formula (1). A meta-type wholly aromatic polyamide obtained by copolymerizing an aromatic diamine component or an aromatic dicarboxylic acid halide component as a third component so as to be 1 to 10 mol% based on the total amount of repeating structural units of the aromatic polyamide. Item 6. The fabric according to Item 5.
    — (NH—Ar 1 —NH—CO—Ar 1 —CO) — (1)
    Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
  8. 　第３成分となる芳香族ジアミンが式（２）、（３）、または芳香族ジカルボン酸ハライドが、式（４）、（５）である請求項７に記載の布帛。
    　　Ｈ２Ｎ－Ａｒ２－ＮＨ２　・・・式（２）
    　　Ｈ２Ｎ－Ａｒ２－Ｙ－Ａｒ２－ＮＨ２　・・・式（３）
    　　ＸＯＣ－Ａｒ３－ＣＯＸ　・・・式（４）
    　　ＸＯＣ－Ａｒ３－Ｙ－Ａｒ３－ＣＯＸ　・・・式（５）
    ここで、Ａｒ２はＡｒ１とは異なる２価の芳香族基、Ａｒ３はＡｒ１とは異なる２価の芳香族基、Ｙは酸素原子、硫黄原子、アルキレン基からなる群から選ばれる少なくとも１種の原子又は官能基であり、Ｘはハロゲン原子を表す。     The fabric according to claim 7, wherein the aromatic diamine as the third component is represented by formulas (2) and (3), or the aromatic dicarboxylic acid halide is represented by formulas (4) and (5).
    H 2 N—Ar 2 —NH 2 Formula (2)
    H 2 N—Ar 2 —Y—Ar 2 —NH 2 Formula (3)
    XOC-Ar3-COX Formula (4)
    XOC-Ar3-Y-Ar3-COX Formula (5)
    Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
  9. 　前記メタ型芳香族ポリアミド繊維の残存溶媒量が０．１重量％以下である、請求項５に記載の布帛。 The fabric according to claim 5, wherein the residual solvent amount of the meta-type aromatic polyamide fiber is 0.1% by weight or less.
  10. 　布帛が、経密度４０～１００本／２５．４ｍｍ、および緯密度４０～１００本／２５．４ｍｍの織物である、請求項１に記載の布帛。 The fabric according to claim 1, wherein the fabric is a woven fabric having a warp density of 40 to 100 pieces / 25.4 mm and a weft density of 40 to 100 pieces / 25.4 mm.
  11. 　布帛の目付けが１４０～３００ｇ／ｍ２の範囲内である、請求項１に記載の布帛。 The fabric according to claim 1, wherein the fabric weight is within a range of 140 to 300 g / m 2 .
  12. 　布帛において、ＪＩＳ　Ｌ１０９６－１９９８　Ａ法により測定した剛軟度が４～１２ｍｍの範囲内である、請求項１に記載の布帛。 The fabric according to claim 1, wherein the fabric has a bending resistance measured by JIS L1096-1998 A method in a range of 4 to 12 mm.
  13. 　ＪＩＳ　Ｌ１０９１　Ａ－４（１２ｓ接炎）に記載の垂直燃焼試験で残炎時間が１秒以下である、請求項１に記載の布帛。 The fabric according to claim 1, wherein the afterflame time is 1 second or less in the vertical combustion test described in JIS L1091 A-4 (12s flame contact).
  14. 　布帛が黒色または赤色に着色してなる、請求項１に記載の布帛。 The fabric according to claim 1, wherein the fabric is colored black or red.
  15. 　請求項１に記載の布帛の製造方法であって、捺染処理により布帛を着色する際、難燃剤を含む捺染処理剤を用いることを特徴とする布帛の製造方法。 2. The method for producing a fabric according to claim 1, wherein when the fabric is colored by a textile printing treatment, a textile treating agent containing a flame retardant is used.
  16. 　捺染処理する際、アクリル樹脂またはウレタン樹脂からなるバインダーを含む捺染処理剤を用いる、請求項１５に記載の布帛の製造方法。 The method for producing a fabric according to claim 15, wherein a printing agent containing a binder made of an acrylic resin or a urethane resin is used in the printing process.
  17. 　さらに布帛に撥水処理を施す、請求項１５に記載の布帛の製造方法。 The method for producing a fabric according to claim 15, wherein the fabric is further subjected to a water repellent treatment.
  18. 　請求項１～１４のいずれかに記載の布帛を用いてなる、消防服、消防団服、作業服、迷彩服、法被、およびエプロンからなる群より選択される繊維製品。 A textile product selected from the group consisting of fire clothes, fire brigade clothes, work clothes, camouflage clothes, coats, and an apron, using the fabric according to any one of claims 1 to 14.
PCT/JP2015/078977 2014-10-16 2015-10-14 Fabric, method for producing same, and textile product WO2016060143A1 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017197852A (en) * 2016-04-25 2017-11-02 帝人株式会社 Flame-retardant fabric and fiber product
JP2017197882A (en) * 2016-04-28 2017-11-02 帝人株式会社 Flame-retardant fabric and fiber product
JP2019014994A (en) * 2017-07-06 2019-01-31 帝人株式会社 Fabric and textile product
CN109837780A (en) * 2019-02-28 2019-06-04 江苏工程职业技术学院 A kind of colouring method of high fire-retardance tooling fabric
EP4036294A4 (en) * 2019-09-24 2022-11-09 Teijin Limited Fireproof fabric and seat
KR102583789B1 (en) * 2023-01-03 2023-10-04 (주)보광아이엔티 Materials for inner and outer of protective product and respective manufacturing methods

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* Cited by examiner, † Cited by third party
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CN109930270B (en) * 2019-03-08 2020-06-12 东华大学 Production method of blended yarn containing flame-retardant polyester fibers and polyarylate fibers
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CN111155224A (en) * 2020-02-17 2020-05-15 上海市纺织科学研究院有限公司 Preparation method of polyarylester fiber-based self-lubricating fabric

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62268876A (en) * 1986-05-14 1987-11-21 バ−リントン・インダストリ−ズ・インコ−ポレイテツド Method and paste composition for printing molded product of aramide fiber
JPS6366385A (en) * 1986-09-08 1988-03-25 帝人株式会社 Cloth for camouflage
JP2007298199A (en) * 2006-04-28 2007-11-15 Toray Ind Inc Multicolor camouflage cloth and multicolor camouflage clothes
JP2009057652A (en) * 2007-08-31 2009-03-19 Teijin Techno Products Ltd Wholly aromatic polyamide fiber fabric
JP2012052249A (en) * 2010-08-31 2012-03-15 Teijin Techno Products Ltd Composite spun yarn
WO2012102090A1 (en) * 2011-01-27 2012-08-02 日本毛織株式会社 Fabric for protective clothing, and spun yarn for same
JP2013510250A (en) * 2009-11-05 2013-03-21 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Printable aramid blended fabric
WO2013166086A1 (en) * 2012-05-03 2013-11-07 E. I. Du Pont De Nemours And Company Process for obtaining low residual aramid materials

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5773170A (en) * 1980-10-24 1982-05-07 Daido Steel Co Ltd Tool steel
CN102505531B (en) * 2011-11-10 2014-05-07 北京中纺化工股份有限公司 Complex functional polyester fabric for automobiles and preparation method of complex functional polyester fabric
CN102634908B (en) * 2012-04-28 2014-05-07 江苏省纺织研究所有限公司 Oil and water resistant, fire resistant, anti-static and silicon removing multifunctional shell fabric
CN103046316A (en) * 2012-12-07 2013-04-17 浙江理工大学 Method for finishing environment-friendly flame-retardant waterproof coating fabric
JP6072538B2 (en) * 2012-12-28 2017-02-01 帝人株式会社 High pilling heat resistant fabric

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62268876A (en) * 1986-05-14 1987-11-21 バ−リントン・インダストリ−ズ・インコ−ポレイテツド Method and paste composition for printing molded product of aramide fiber
JPS6366385A (en) * 1986-09-08 1988-03-25 帝人株式会社 Cloth for camouflage
JP2007298199A (en) * 2006-04-28 2007-11-15 Toray Ind Inc Multicolor camouflage cloth and multicolor camouflage clothes
JP2009057652A (en) * 2007-08-31 2009-03-19 Teijin Techno Products Ltd Wholly aromatic polyamide fiber fabric
JP2013510250A (en) * 2009-11-05 2013-03-21 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Printable aramid blended fabric
JP2012052249A (en) * 2010-08-31 2012-03-15 Teijin Techno Products Ltd Composite spun yarn
WO2012102090A1 (en) * 2011-01-27 2012-08-02 日本毛織株式会社 Fabric for protective clothing, and spun yarn for same
WO2013166086A1 (en) * 2012-05-03 2013-11-07 E. I. Du Pont De Nemours And Company Process for obtaining low residual aramid materials

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017197852A (en) * 2016-04-25 2017-11-02 帝人株式会社 Flame-retardant fabric and fiber product
JP2017197882A (en) * 2016-04-28 2017-11-02 帝人株式会社 Flame-retardant fabric and fiber product
JP2019014994A (en) * 2017-07-06 2019-01-31 帝人株式会社 Fabric and textile product
CN109837780A (en) * 2019-02-28 2019-06-04 江苏工程职业技术学院 A kind of colouring method of high fire-retardance tooling fabric
EP4036294A4 (en) * 2019-09-24 2022-11-09 Teijin Limited Fireproof fabric and seat
KR102583789B1 (en) * 2023-01-03 2023-10-04 (주)보광아이엔티 Materials for inner and outer of protective product and respective manufacturing methods

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