Fabrics and textile products

Abstract

To provide: a fabric which contains a meta-type wholly aromatic polyamide fiber, has extremely excellent flame retardancy, can reduce the amount of dyes to be used, and is excellent in appearance quality after washing; and a textile product thereof.SOLUTION: There is provided a fabric containing a meta-type wholly aromatic polyamide fiber, a para-type wholly aromatic polyamide fiber containing a pigment or a dye, and a conductive yarn, in which the meta-type wholly aromatic polyamide fiber is dyed.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a fabric containing meta-type wholly aromatic polyamide fibers, having extremely excellent flame retardancy, capable of reducing the amount of dye used, and having excellent appearance quality after washing, as well as fiber products.

Background Art

[0002] Conventionally, fabrics having flame retardancy have been used in applications such as protective clothing, fire-fighting and fire-prevention clothing, fire-fighting activity clothing, rescue clothing, flame-retardant workwear, police uniforms, self-defense force clothing, military uniforms, etc. (for example, Patent Documents 1 to 3). On the other hand, in recent years, there has been a demand for fabrics that are environmentally friendly and have excellent appearance quality.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention has been made in view of the above background, and its object is to provide a fabric containing meta-type wholly aromatic polyamide fibers, having extremely excellent flame retardancy, capable of reducing the amount of dye used, and having excellent appearance quality after washing, as well as fiber products.

Means for Solving the Problems

[0005] As a result of intensive studies to achieve the above problems, the present inventor has found that a desired fabric can be obtained, and has further completed the present invention through repeated intensive studies.

[0006] Thus, according to the present invention, there is provided "a fabric comprising meta-type wholly aromatic polyamide fibers, para-type wholly aromatic polyamide fibers containing a pigment or a dye, and conductive yarns, wherein the meta-type wholly aromatic polyamide fibers are dyed." At that time, it is preferable that the meta-type wholly aromatic polyamide fibers and the para-type wholly aromatic polyamide fibers are contained in the fabric at a mass ratio (meta-type wholly aromatic polyamide fibers / para-type wholly aromatic polyamide fibers) of 50 / 50 to 97 / 3. Also, it is preferable that the total mass of the meta-type wholly aromatic polyamide fibers and the para-type wholly aromatic polyamide fibers is 70% by mass or more based on the fabric mass. Further, in the meta-type wholly aromatic polyamide fibers, the residual solvent amount is preferably 0.1% by mass or less. Also, in the meta-type wholly aromatic polyamide fibers, the crystallinity is preferably in the range of 15 to 50%. Further, it is preferable that the para-type wholly aromatic polyamide fibers contain a black pigment or a black dye.

[0007] In the fabric of the present invention, the basis weight of the fabric is preferably in the range of 120 to 300 g / m 2 . Also, the L value of the fabric is preferably 40 or less. Also, when measuring the rubbing fastness (dry method) defined by the JIS L0849II method for the fabric, it is preferable that the staining is grade 3.5 or higher. Further, it is preferable that the meta-type wholly aromatic polyamide fibers are dyed with a cationic dye and / or a disperse dye, and the dye is unevenly distributed in the fiber surface layer part. Also, it is preferable that the color difference ΔE between after washing the fabric in accordance with ISO6330 6NF and before washing is 1 or less. Also, the afterflame time measured by the ISO15025:2000 A method is preferably 2 seconds or less. Also, the shrinkage rate after washing 5 times by the method defined in ISO5077 is preferably 5% or less. Also, the heat shrinkage rate when performing the heat treatment at 180° C. for 5 minutes defined in ISO17493 is preferably 5% or less.

[0008] Also, according to the present invention, there is provided a fabric-made fiber product selected from the group consisting of protective clothing, fireproof and fire-fighting clothing, fire-fighting activity clothing, rescue clothing, workwear, police uniforms, Self-Defense Force clothing, and military uniforms, which uses the above-mentioned fabric.

Advantages of the Invention

[0009] According to the present invention, there are provided a fabric and a fiber product which contain meta-type wholly aromatic polyamide fibers, have extremely excellent flame retardancy, can reduce the amount of dye used, and have excellent appearance quality after washing.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present invention will be described in detail. First, the meta-type wholly aromatic polyamide fiber used in the present invention is a fiber composed of a polymer in which 85 mol% or more of its repeating units are 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%.

[0011] Such a meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method, and as the degree of polymerization of the polymer, the intrinsic viscosity (I.V.) measured in an N-methyl-2-pyrrolidone solution having a concentration of 0.5 g / 100 ml is preferably in the range of 1.3 to 1.9 dl / g.

[0012] The above-mentioned meta-type wholly aromatic polyamide may contain an alkylbenzene sulfonic acid onium salt. Examples of the alkylbenzene sulfonic acid onium salt preferably include compounds such as tetrabutylphosphonium hexylbenzene sulfonate, tributylbenzylphosphonium hexylbenzene sulfonate, tetraphenylphosphonium dodecylbenzene sulfonate, tributyltetradecylphosphonium dodecylbenzene sulfonate, tetrabutylphosphonium dodecylbenzene sulfonate, tributylbenzylammonium dodecylbenzene sulfonate, etc. Among them, tetrabutylphosphonium dodecylbenzene sulfonate or tributylbenzylammonium dodecylbenzene sulfonate is particularly preferably exemplified because it is easily available, has good thermal stability, and high solubility in N-methyl-2-pyrrolidone.

[0013] In order to obtain a sufficient effect of improving dyeability, the content ratio of the above-mentioned alkylbenzene sulfonic acid onium salt is preferably in the range of 2.5 mol% or more, preferably 3.0 to 7.0 mol%, based on poly-m-phenylene isophthalamide.

[0014] Also, as a method of mixing poly-m-phenylene isophthalamide and an alkylbenzene sulfonic acid onium salt, a method of mixing and dissolving poly-m-phenylene isophthalamide in a solvent and then dissolving the alkylbenzene sulfonic acid onium salt in the solvent can be used, and any of them may be used. The dope thus obtained is formed into fibers by a conventionally known method.

[0015] For the purpose of improving dyeability and resistance to color change and fading, etc., the polymer used for meta-type wholly aromatic polyamide fibers can also copolymerize an aromatic diamine component or an aromatic dicarboxylic acid halide component 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) as a third component so that it accounts for 1 to 10 mol% of the total amount of the repeating structural units of the aromatic polyamide. -(NH-Ar1-NH-CO-Ar1-CO)- ··· Formula (1) Here, Ar1 is a divalent aromatic group having a bonding group other than the meta coordination or the parallel axis direction.

[0016] Also, it can be copolymerized as a third component. Specific examples of the aromatic diamines shown in Formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylene diamine, methylphenylene diamine, acetylphenylene diamine, aminoanisidine, benzidine, bis(aminophenyl) ether, bis(aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene, and the like. Specific examples of the aromatic dicarboxylic acid dichlorides shown in Formulas (4) and (5) include, for example, terephthalic acid chloride, 1,4-naphthalene dicarboxylic acid chloride, 2,6-naphthalene dicarboxylic acid chloride, 4,4'-biphenyl dicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis(chlorocarbonylphenyl) ether, and the like.

[0017] H2N-Ar2-NH2··· Formula (2) H2N-Ar2-Y-Ar2-NH2··· 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 or functional group selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group, and X represents a halogen atom.

[0018] Also, the crystallinity of the meta-type wholly aromatic polyamide fiber is preferably 5 to 35% in that the exhaustion property of the dye is good and it is easy to adjust to the target color with less dye or under weaker dyeing conditions. Further, it is more preferably 15 to 25% in that the surface uneven distribution of the dye hardly occurs, the fastness to change and fading is high, and the dimensional stability required in practice can be ensured.

[0019] It is also essential to include meta-type wholly aromatic polyamide fibers and as-received para-type wholly aromatic polyamide fibers. Further, the residual solvent content of the meta-type wholly aromatic polyamide fibers is preferably 0.1% by mass or less (preferably 0.001 to 0.1% by mass) so as not to impair the excellent flame retardant performance of the meta-type wholly aromatic polyamide fibers.

[0020] The meta-type wholly aromatic polyamide fibers can be produced by the following method, and in particular, by the method described later, the crystallinity and the residual solvent content can be within the above ranges. There is no particular need to limit the polymerization method of the meta-type wholly aromatic polyamide polymer. For example, a solution polymerization method or an interfacial polymerization method described in Japanese Patent Publication No. 35-14399, U.S. Patent No. 3360595, Japanese Patent Publication No. 47-10863, etc. may be used.

[0021] The spinning solution is not particularly limited, but an amide-based solvent solution containing an aromatic copolyamide polymer obtained by the above solution polymerization or interfacial polymerization may be used, or the polymer may be isolated from the above polymerization solution and dissolved in an amide-based solvent for use.

[0022] Examples of the amide-based solvent used here include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc., but N,N-dimethylacetamide is particularly preferred.

[0023] The copolymerized aromatic polyamide polymer solution obtained as described above is stabilized by further containing an alkali metal salt or an alkaline earth metal salt, and it is preferable because it can be used at a higher concentration and lower temperature. Preferably, the alkali metal salt and the alkaline earth metal salt are 1% by mass or less, more preferably 0.1% by mass or less, based on the total weight of the polymer solution. In the spinning and coagulation step, the spinning solution (meta-type wholly aromatic polyamide polymer solution) obtained above is spun into a coagulation liquid for coagulation.

[0024] The spinning device is not particularly limited, and a conventionally known wet spinning device can be used. Also, as long as wet spinning can be stably performed, the number of spinning holes, arrangement state, hole shape, etc. of the spinneret do not need to be particularly restricted. For example, a multi-hole spinneret for staple fibers with 1000 to 30000 holes and a spinning hole diameter of 0.05 to 0.2 mm may be used. Moreover, 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.

[0025] As the coagulation bath used to obtain the fibers, an aqueous solution containing substantially no inorganic salts and having an amide solvent, preferably NMP, with a concentration of 45 to 60% by mass is used in the range of 10 to 50°C for the bath solution temperature. When the concentration of the amide solvent (preferably NMP) is less than 45% by mass, the skin becomes thick, the washing efficiency in the washing process decreases, and it becomes difficult to reduce the residual solvent amount in the fibers. On the other hand, when the concentration of the amide solvent (preferably NMP) exceeds 60% by mass, uniform coagulation cannot be performed up to the inside of the fibers, and thus it also becomes difficult to reduce the residual solvent amount in the fibers. The immersion time of the fibers in the coagulation bath is suitably in the range of 0.1 to 30 seconds.

[0026] Subsequently, stretching is performed at a stretching ratio of 3 to 4 times in a plasticizing and stretching bath, which is an aqueous solution containing an amide solvent, preferably NMP, with a concentration of 45 to 60% by mass and having a bath solution temperature in the range of 10 to 50°C. After stretching, thorough washing is performed through an aqueous solution of NMP with a concentration of 20 to 40% by mass at 10 to 30°C, followed by a warm water bath at 50 to 70°C. The washed fibers are subjected to dry heat treatment at a temperature of 270 to 290°C to obtain meta-type wholly aromatic polyamide fibers satisfying the above ranges of crystallinity and residual solvent amount.

[0027] In the meta-type wholly aromatic polyamide fibers, the fibers may be long fibers (multifilaments) or short fibers. In particular, short fibers with a fiber length of 25 to 200 mm are preferable for blending with other fibers. Also, the single fiber fineness is preferably in the range of 1 to 5 dtex.

[0028] In the fabric of the present invention, meta-type wholly aromatic polyamide fibers, para-type wholly aromatic polyamide fibers containing a pigment or a dye, and conductive yarns are included. At this time, the meta-type wholly aromatic polyamide fibers and the para-type wholly aromatic polyamide fibers containing a pigment or a dye are preferably included at a mass ratio (the meta-type wholly aromatic polyamide fibers / the para-type wholly aromatic polyamide fibers) of 50 / 50 to 97 / 3. More preferably, the mass ratio (the meta-type wholly aromatic polyamide fibers / the para-type wholly aromatic polyamide fibers) is 60 / 40 to 97 / 3, and particularly preferably, the mass ratio (the meta-type wholly aromatic polyamide fibers / the para-type wholly aromatic polyamide fibers) is 70 / 30 to 97 / 3. The para-type wholly aromatic polyamide fibers may be known para-aramid fibers, and examples thereof include Twaron Black (trade name) and Technora Super Black (trade name).

[0029] Here, when the para-type wholly aromatic polyamide fibers containing the pigment or the dye include black pigment or black dye in the fabric, the amount of the dye used can be reduced when the fabric is dyed to a dark color (that is, the L value is small), which is environmentally friendly. Also, it is preferable that whitening is prevented even if fibrillation occurs during washing. At this time, it is preferable that the black pigment or the black dye is contained in an amount of 0.1 to 10% by mass based on the fiber mass of the para-type wholly aromatic polyamide fibers. Further, it is preferable that the para-type wholly aromatic polyamide fibers containing such black pigment or black dye are contained in the fabric in an amount of 1 to 50% by mass based on the mass of the fabric in terms of improving the appearance quality, rubbing fastness, and L value.

[0030] Here, if the fiber content of the black pigment or the black dye is less than 0.1% by mass, there is a possibility that improvement in appearance quality, rubbing fastness, and L value cannot be obtained. Conversely, if the fiber content of the black pigment or the black dye is more than 10% by mass, there is a possibility that the mechanical properties of the fiber may deteriorate.

[0031] As the black pigment or black dye, carbon black is preferred because it does not attack the matrix polymer itself and is easy to obtain and handle. As the carbon black, known ones can be used, for example, acetylene black, oil furnace black, thermal black, channel black, ketjen black, and the like. These can usually be used by being dispersed in the matrix polymer as fine powder.

[0032] Also, the primary particle size of the carbon black is preferably 10 to 100 nm. Here, the primary particle size refers to the particle size before the particles aggregate to form secondary particles. As a method for producing a para-type wholly aromatic polyamide fiber containing carbon black, carbon black can be added to a para-type wholly aromatic polyamide-containing dope, and this can be produced by a conventional method such as wet spinning and drawing.

[0033] Also, it is preferable that the conductive yarn is contained in the fabric in an amount of 1% by mass or more (preferably 1 to 10% by mass, more preferably 1 to 5% by mass) based on the fabric mass ratio. It is described in the standard ISO11612 that the conductive yarn is essential, and the inclusion of the conductive yarn in the fabric makes it possible to prevent static electricity in the fabric.

[0034] As such a conductive yarn, a conductive yarn made of a conductive acrylic fiber is preferred. When the meta-type wholly aromatic polyamide fiber and the conductive acrylic fiber are contained in the fabric, by dyeing with a cationic dye, both the meta-type wholly aromatic polyamide fiber and the conductive acrylic fiber are dyed dark and uniformly as a whole fabric. At that time, it is preferable that the meta-type wholly aromatic polyamide fiber and the conductive fiber are colored in the same color. Here, as the color difference between the meta-type wholly aromatic polyamide fiber and the conductive fiber, ΔE is preferably 3 or less.

[0035] As the conductive acrylic fiber, a fiber obtained by kneading conductive carbon into acrylic fiber, a core-sheath type composite fiber composed of a core part containing conductive fine particles and a sheath part not containing conductive fine particles, etc. are preferable. In particular, a core-sheath type composite fiber (or eccentric core-sheath type composite fiber) in which the sheath part is made of acrylic not containing conductive fine particles and the core part is made of a conductive carbon-containing polymer is preferable. By incorporating such conductive acrylic fiber into a fabric, the static electricity generated by the friction of the fabric can be reduced, and as a result, problems such as dust adhesion, adverse effects due to discharge, and ignition in an explosion-proof environment can be reduced.

[0036] As the conductive acrylic fiber, for example, those described in JP-A-2009-221632 are preferable. That is, it is composed of a core part containing conductive fine particles and a sheath part not containing conductive fine particles, the core-sheath ratio is 15 / 85 to 50 / 50, the content of conductive fine particles in the core part is 20 to 60% by mass, and the single fiber specific resistance value is 10 1 ~10 6 Ω·cm core-sheath type conductive acrylic fiber.

[0037] In the conductive fiber, the form of the fiber may be a long fiber (multifilament) or a short fiber. In particular, short fibers with a fiber length of 25 to 200 mm (more preferably 30 to 150 mm) are preferable for blending with other fibers. Also, the single fiber fineness is preferably in the range of 1 to 5 dtex.

[0038] In the fabric of the present invention, the fabric may be composed only of the above-mentioned fibers, but other fibers may also be included. In that case, examples of other fibers include polyester fibers, para-type wholly aromatic polyamide fibers not containing pigments or dyes, wholly aromatic polyester fibers, polybenzoxazole (PBO) fibers, polybenzimidazole (PBI) fibers, polybenzothiazole (PBTZ) fibers, polyimide (PI) fibers, polysulfonamide (PSA) fibers, polyetheretherketone (PEEK) fibers, polyetherimide (PEI) fibers, polyarylate (PAr) fibers, melamine fibers, phenol fibers, fluorine-based fibers, polyphenylene sulfide (PPS) fibers, cellulose fibers, polyolefin fibers, acrylic fibers, cotton fibers, animal hair fibers, polyurethane fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, acetate fibers, polycarbonate fibers, and the like.

[0039] Here, it is preferable that these fibers are blended and contained in the fabric as spun yarns. In that case, in order to exhibit the excellent heat resistance and flame retardancy of the meta-type wholly aromatic polyamide fibers, it is first preferable that the meta-type wholly aromatic polyamide fibers are 50% by mass or more based on the weight of the spun yarn. As a more specific example, the mixing ratio can be such that the meta-type wholly aromatic polyamide fibers are 30 to 98% by mass based on the weight of the spun yarn, the para-type wholly aromatic polyamide fibers are 2 to 10% by mass based on the weight of the spun yarn, and the conductive yarn is 0 to 5% by mass based on the weight of the spun yarn, so as to have both dyeability and high quality and high friction fastness. Further, the fibers constituting the fabric may contain a flame retardant, an ultraviolet absorber, a reflector, or the like.

[0040] In the present invention, the method for manufacturing the fabric is not particularly limited, and any known method can be used. For example, after mixing and spinning the above-mentioned fibers to obtain a spun yarn, it is preferable to weave the spun yarn into a texture such as twill weave or plain weave using a rapier loom or the like with single yarn or double yarn. Next, the fabric is subjected to a dyeing process. As the dye used in that case, cationic dyes and / or disperse dyes are preferable. The meta-type wholly aromatic polyamide fibers are dyed by such a dyeing process.

[0041] At this time, when the meta-type wholly aromatic polyamide fiber is dyed with a cationic dye and / or a disperse dye and the dye is unevenly distributed (ring dye) in the fiber surface layer part, it is preferable that the fabric can be dyed dark with a small amount of dye. As a method for dyeing the meta-type wholly aromatic polyamide fiber by ring dyeing, for example, the method described in JP-A-2019-81968 may be used. The fabric thus obtained is a fabric having extremely excellent flame retardancy, can reduce the amount of dye used, and has excellent appearance quality after washing.

[0042] Here, the basis weight of the fabric is preferably in the range of 120 to 300 g / m 2 Further, the L value of the fabric is preferably 40 or less (more preferably 5 to 31). Further, the rubbing fastness (dry method) defined by the JIS L0849II method is measured for the fabric, and it is preferable that the contamination is 3.5 or higher. Further, it is preferable that the color difference ΔE between after washing the fabric in accordance with ISO6330 6NF and before washing is 1 or less. Further, it is preferable that the afterflame time measured by the ISO15025:2000 A method is 2 seconds or less. Further, it is preferable that the shrinkage rate after washing 5 times by the method defined in ISO5077 is 5% or less. Further, it is preferable that the heat shrinkage rate when performing the heat treatment at 180° C. for 5 minutes defined in ISO17493 is 5% or less.

[0043] Next, the fiber product of the present invention is any fiber product selected from the group consisting of protective clothing, fireproof clothing, fire fighting clothing, rescue clothing, workwear, police uniforms, Self-Defense Forces clothing, and military uniforms, which is made using the above-mentioned fabric. Since such a fiber product uses the above-mentioned fabric, it has extremely excellent flame retardancy, can reduce the amount of dye used, and has excellent appearance quality after washing.

Examples

[0044] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Each physical property in the examples was measured by the following methods.

[0045] (1) Areal density It was measured by the method specified in JIS L 1096 A method.

[0046] (2) Flammability It was measured by the methods specified in ISO15025:2000 A method and JISL1091A-1 method.

[0047] (3) Washing shrinkage rate The shrinkage rate after washing 5 times by the method specified in ISO5077 was measured. It was measured for warp and weft with n = 5, and the average of the two was taken.

[0048] (4) Dry heat shrinkage rate The heat shrinkage rate when performing heat treatment at 180 °C for 5 minutes specified in ISO17493 was measured. It was measured for warp and weft with n = 5, and the average of the two was taken.

[0049] (5) Ring dye observation Meta-type wholly aromatic polyamide fibers were collected from the fabric, the fiber cross-section was cut, and surface observation was carried out using an optical microscope to confirm the diffusibility of the dye into the fiber. When the outer peripheral part was darker than the central part in the single fiber cross-section and dyed in a core-sheath type, it was regarded as a ring dye.

[0050] (6) Residual solvent amount Approximately 8.0 g of meta-type wholly aromatic polyamide fibers were collected from the fabric, dried at 105 °C for 120 minutes, then allowed to cool in a desiccator, and the fiber mass (M1) was weighed. Subsequently, for this fiber, reflux extraction was carried out using a Soxhlet extractor in methanol for 1.5 hours to extract the amide-based solvent contained in the fiber. The extracted fiber was taken out, vacuum dried at 150 °C for 60 minutes, then allowed to cool in a desiccator, and the fiber mass (M2) was weighed. The amount of solvent remaining in the fiber (amide-based solvent mass) was calculated by the following formula using the obtained M1 and M2. Residual solvent amount (%) = [(M1 - M2) / M1] × 100

[0051] (7) Crystallinity Using an X-ray diffractometer (RINT TTRIII manufactured by Rigaku Corporation), fibrils were aligned into fiber bundles with a diameter of approximately 1 mm, attached to a fiber sample stage, and the diffraction profile was measured. The measurement conditions were as follows: Cu-Kα radiation source (50 kV, 300 mA), scanning angle range of 10 to 35°, continuous measurement with a step width of 0.1°, and scanning speed of 1° / min. From the actually measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain the total scattering profile. Next, the amorphous scattering profile was subtracted from the total scattering profile to obtain the crystalline scattering profile. The crystallinity was determined from the area intensity of the crystalline scattering profile (crystalline scattering intensity) and the area intensity of the total scattering profile (total scattering intensity) using the following formula. Crystallinity (%) = [crystalline scattering intensity / total scattering intensity] × 100

[0052] (8) Shade (L value) The L value was measured using a Macbeth spectrophotometer Color-Eye3100.

[0053] (9) Rub fastness (dry method) It was measured by the method specified in JIS L 0849 II method.

[0054] (10) Color difference (ΔE) The fabric was washed under the conditions specified in ISO6330 6NF, and the color difference ΔE between after washing and before washing was measured. The measurement method was to measure the L value (L*), a value (a*), and b value (b*) using a Macbeth spectrophotometer Color-Eye3100, and calculate ΔE (ΔE*) using the following formula. The smaller ΔE is, the better the appearance quality after washing. ΔE* = 〔(ΔL*) 2 + (Δa*) 2 + (Δb*) 2 〕 1 / 2

[0055] [Manufacture of meta-type wholly aromatic polyamide fiber] The meta-type wholly aromatic polyamide fiber was produced by the following method. 20.0 parts by mass of polymetaphenylene isophthalamide powder having an intrinsic viscosity (I.V.) of 1.9, produced by the interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863, was suspended in 80.0 parts by mass of N-methyl-2-pyrrolidone (NMP) cooled to -10°C to form a slurry. Subsequently, the suspension was heated to 60°C to dissolve it, obtaining a transparent polymer solution. To this polymer solution, 3.0 parts by mass of 2-[2H-benzotriazol-2-yl]-4,6-bis(1-methyl-1-phenylethyl)phenol powder (solubility in water: 0.01 mg / L) and a phosphorus-based flame retardant were mixed and dissolved, and then degassed under reduced pressure to obtain a spinning solution (spinning dope).

[0056] [Spinning and Coagulation Process] The above spinning dope was extruded from a spinneret having a pore diameter of 0.07 mm and 500 holes into a coagulation bath at a bath temperature of 30°C for spinning. The composition of the coagulating liquid was water / NMP = 45 / 55 (parts by mass), and it was extruded into the coagulation bath at a yarn speed of 7 m / min for spinning.

[0057] [Plasticizing and Drawing Bath Drawing Process] Subsequently, drawing was performed at a draw ratio of 3.7 times in a plasticizing and drawing bath at a temperature of 40°C with a composition of water / NMP = 45 / 55.

[0058] [Washing Process] After drawing, it was washed in a bath of water / NMP = 70 / 30 at 20°C (immersion length 1.8 m), followed by a water bath at 20°C (immersion length 3.6 m), and further passed through a warm water bath at 60°C (immersion length 5.4 m) for sufficient washing.

[0059] [Dry Heat Treatment Process] The washed fibers were subjected to dry heat treatment using a hot roller with a surface temperature of 280°C to obtain meta-type wholly aromatic polyamide fibers.

[0060] [Physical Properties of Staple Fibers] The physical properties of the obtained meta-type wholly aromatic polyamide fibers were as follows: single fiber fineness 1.7 dtex, residual solvent content 0.08% by mass, and crystallinity 19%. Using the obtained staple fibers, crimping and cutting were performed to obtain staple fibers (raw cotton) with a length of 51 mm.

[0061] Other fiber raw materials used were as follows. As the para-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber with a single fiber fineness of 1.7 dtex was used, and was subjected to crimping and cutting to obtain staple fibers (raw cotton) with a length of 50 mm. Also, as the conductive yarn, acrylic conductive fiber with a single fiber fineness of 3.3 dtex was used, and was subjected to crimping and cutting to obtain staple fibers (raw cotton) with a length of 38 mm.

[0062] (Post-processing) The woven fabric was subjected to singeing, scouring, and setting (temperature 160 °C × time 30 seconds) by a conventional method, and then dyed with a cationic dye (manufactured by Nippon Kayaku Co., Ltd.: Kayacryl Blue GSL ED 3% owf, Kayacryl Red GL-ED 0.5% owf, carrier agent 10 g / l, acetic acid 3 g / l, sodium nitrate 20 g / l, dispersant (manufactured by Meisei Chemical Co., Ltd.: Disper VG) 1 g / l) in a dyeing solution (bath ratio 1:20) by heating from room temperature to 120 °C and dyeing for 90 minutes. After reduction washing, soaping, and hot water washing, final setting (at 160 °C for 30 seconds) and drying were carried out to obtain a dyed fabric.

[0063] [Example 1] Staple fibers of meta-type wholly aromatic polyamide fiber (MA) (length 51 mm), conductive yarn (AS) (length 38 mm), and carbon black-containing para-type wholly aromatic polyamide fiber (PA: Twaron Black 4072) (length 51 mm) were blended into a 40-count / 2-ply spun yarn at a ratio of MA / AS / PA = 93 / 2 / 5 and woven with a fabric density of 63 ends / 25.4 mm in the warp direction and 52 picks / 25.4 mm in the weft direction to obtain a plain fabric with a weight per unit area of 160 g / m 2 This was processed by the above method. The meta-type wholly aromatic polyamide fiber was dyed in a core-sheath type and was a ring dye. The results are shown in Table 1.

[0064] [Example 2] Meta-type wholly aromatic polyamide fiber (MA) (length 51 mm), conductive yarn (AS) (length 38 mm), and para-type wholly aromatic polyamide fiber containing carbon black (PA: Twaron Black 4072) (length 51 mm) were spun together at a ratio of MA / AS / PA = 83 / 2 / 15 to form a 40s / 2 ply yarn. The fabric was woven with a warp density of 63 threads / 25.4 mm and a weft density of 52 threads / 25.4 mm, and had a basis weight of 160 g / m 2 A plain weave fabric was obtained. It was processed by the above method. The meta-type wholly aromatic polyamide fiber was core-sheath dyed and was a ring dye. The results are shown in Table 1.

[0065] [Example 3] Meta-type wholly aromatic polyamide fiber (MA) (length 51 mm), conductive yarn (AS) (length 38 mm), and para-type wholly aromatic polyamide fiber containing carbon black (PA: Twaron Black 4072) (length 51 mm) were spun together at a ratio of MA / AS / PA = 73 / 2 / 25 to form a 40s / 2 ply yarn. The fabric was woven with a warp density of 63 threads / 25.4 mm and a weft density of 52 threads / 25.4 mm, and had a basis weight of 160 g / m 2 A plain weave fabric was obtained. It was processed by the above method. The meta-type wholly aromatic polyamide fiber was core-sheath dyed and was a ring dye. The results are shown in Table 1.

[0066] [Example 4] Meta-type wholly aromatic polyamide fiber (MA) (length 51 mm), conductive yarn (AS) (length 38 mm), and para-type wholly aromatic polyamide fiber containing carbon black (PA: Technora T331SB, manufactured by Teijin) (length 51 mm) were spun together at a ratio of MA / AS / PA = 93 / 2 / 5 to form a 40s / 2 ply yarn. The fabric was woven with a warp density of 63 threads / 25.4 mm and a weft density of 52 threads / 25.4 mm, and had a basis weight of 160 g / m 2 A plain weave fabric was obtained. It was processed by the above method. The meta-type wholly aromatic polyamide fiber was core-sheath dyed and was a ring dye. The results are shown in Table 1.

[0067] [Comparative Example 1] Meta-type wholly aromatic polyamide fiber (MA) (length 51 mm), conductive yarn (AS) (length 38 mm), and para-type wholly aromatic polyamide fiber (PA: Twaron 1072) (length 51 mm) staple fibers were blended at a ratio of MA / AS / PA = 93 / 2 / 5 to form a 40-count / 2-ply spun yarn, which was woven with a warp density of 63 threads / 25.4 mm and a weft density of 52 threads / 25.4 mm to obtain a plain weave fabric with a basis weight of 160 g / m 2 This was processed by the above method. Since the para-type wholly aromatic polyamide fiber does not contain a pigment or dye, whitening due to fibrillation during washing was observed with the same amount of dye as in the example during post-processing.

[0068] [Comparative Example 2] Meta-type wholly aromatic polyamide fiber (MA) (length 51 mm), conductive yarn (AS) (length 38 mm), and para-type wholly aromatic polyamide fiber (PA: Technora T330) (length 51 mm) staple fibers were blended at a ratio of MA / AS / PA = 93 / 2 / 5 to form a 40-count / 2-ply spun yarn, which was woven with a warp density of 63 threads / 25.4 mm and a weft density of 52 threads / 25.4 mm to obtain a plain weave fabric with a basis weight of 160 g / m 2 This was processed by the above method. Also in this comparative example, since the para-type wholly aromatic polyamide fiber does not contain a pigment or dye, whitening due to fibrillation during washing was observed with the same amount of dye as in the example during post-processing.

[0069]

Table 1

Industrial Applicability

[0070] According to the present invention, there are provided a fabric containing meta-type wholly aromatic polyamide fiber, having extremely excellent flame retardancy, capable of reducing the amount of dye used, and having excellent appearance quality after washing, and fiber products, and their industrial value is extremely great.

Claims

1. A fabric comprising a meta-type wholly aromatic polyamide fiber, a para-type wholly aromatic polyamide fiber containing a pigment or a dye, and a conductive yarn, wherein the meta-type wholly aromatic polyamide fiber is dyed, in the meta-type wholly aromatic polyamide fiber, the residual solvent amount is 0.1% by mass or less, the para-type wholly aromatic polyamide fiber contains a black pigment or a black dye, the color difference ΔE between the meta-type wholly aromatic polyamide fiber and the conductive fiber is 3 or less, the L value of the fabric is 40 or less, and the color difference ΔE between the fabric after washing in ISO6330 6NF and before washing is 1 or less, the meta-type wholly aromatic polyamide fiber is dyed with a cationic dye and / or a disperse dye, the dye is unevenly distributed in the fiber surface layer part, and the meta-type wholly aromatic polyamide fiber, the para-type wholly aromatic polyamide fiber, and the conductive yarn are included in the fabric as a spun yarn obtained by blending so that the content of the para-type wholly aromatic polyamide fiber is 5 to 25% by weight.

2. The fabric according to claim 1, wherein the meta-type wholly aromatic polyamide fiber and the para-type wholly aromatic polyamide fiber are contained in the fabric at a mass ratio (the meta-type wholly aromatic polyamide fiber / the para-type wholly aromatic polyamide fiber) of 50 / 50 to 97 / 3.

3. The fabric according to claim 1 or claim 2, wherein the total mass of the meta-type wholly aromatic polyamide fiber and the para-type wholly aromatic polyamide fiber is 70% by mass or more based on the fabric mass.

4. The fabric according to any one of claims 1 to 3, wherein the crystallinity of the meta-type wholly aromatic polyamide fiber is in the range of 15 to 50%.

5. The fabric having a basis weight in the range of 120 to 300 g / m ２ according to any one of claims 1 to 4.

6. The fabric according to any one of claims 1 to 5, wherein the rubbing fastness (dry method) defined by JIS L0849II method is measured, and the contamination is 3.5 grades or more.

7. The fabric according to any one of claims 1 to 6, wherein the afterflame time measured by ISO15025:2000 A method is 2 seconds or less.

8. The fabric according to any one of claims 1 to 7, wherein the shrinkage rate after washing 5 times by the method defined in ISO5077 is 5% or less.

9. The fabric according to any one of claims 1 to 8, wherein the heat shrinkage rate when heat treatment at 180°C for 5 minutes defined in ISO17493 is performed is 5% or less. A textile product made of the fabric according to any one of claims 1 to 9 and selected from the group consisting of protective clothing, fire-fighting and fire-prevention clothing, fire-fighting activity clothing, rescue clothing, workwear, police uniforms, Self-Defense Force clothing, and military uniforms.

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