The present invention relates to fabrics and textile products having extremely excellent flame retardancy and excellent washing shrinkage resistance, texture and antistatic properties.
Background technology
[0002]
　Conventionally, flame-retardant fabrics have been used for protective clothing, fire-fighting fire-retardant clothing, activity clothing for fire brigade members, rescue clothing, flame-retardant workwear, police uniforms, self-defense force clothing, military clothing, etc. (for example, patents). Refer to Documents 1 to 4).
[0003]
　On the other hand, in recent years, there has been a demand for fabrics that are not only flame-retardant but also comfortable to wear. Has not been proposed so far.
Prior art literature
Patent documents
[0004]
Patent Document 1: Japanese Patent Application Laid-Open No. 2014-221955
Patent Document 2: Japanese Patent Application Laid-Open No. 2015-94043
Patent Document 3: Japanese Patent Application Laid-Open No. 8-325934
Patent Document 4: Japanese Patent Application Laid-Open No. 2014-528690
Outline of the invention
Problems to be solved by the invention
[0005]
　The present invention has been made in view of the above background, and an object of the present invention is to have extremely excellent flame retardancy, excellent washing shrinkage resistance, texture and antistatic properties, and preferably uniform dyeing of the entire fabric. The purpose is to provide various fabrics and textile products.
Means to solve problems
[0006]
　As a result of diligent studies to achieve the above problems, the present inventors have extremely excellent flame retardancy by skillfully devising the types of fibers constituting the fabric, and also have excellent washing shrinkage resistance and texture. Furthermore, it has been found that a fabric that can be dyed uniformly as a whole fabric can be obtained, and further diligent studies have led to the completion of the present invention.
[0007]
　Thus, according to the present invention, "a fabric characterized by containing a spun yarn containing a meta-type total aromatic polyamide fiber, a modacrylic fiber, and a conductive fiber" is provided.
[0008]
　At that time, it is preferable that the spun yarn contains 5% by weight or more of the meta-type total aromatic polyamide fiber with respect to the weight of the spun yarn. Further, in the spun yarn, it is preferable that the modacrylic fiber is contained in an amount of 30% by weight or more based on the weight of the spun yarn. Further, it is preferable that the spun yarn contains conductive fibers in an amount of 1% by weight or more based on the weight of the spun yarn. Further, it is preferable that the spun yarn is composed of only meta-type total aromatic polyamide fibers, modacrylic fibers and conductive fibers. Further, in the meta-type total aromatic polyamide fiber, the residual solvent amount is preferably 0.1% by weight or less. Further, in the meta-type total aromatic polyamide fiber, the crystallinity is preferably in the range of 15 to 25%. In particular, in the meta-type total aromatic polyamide fiber, the meta-type total aromatic polyamide forming the meta-type total aromatic polyamide fiber is contained in the aromatic polyamide skeleton containing the repeating structural unit represented by the following formula (1). , An aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main structural unit of the repeating structure is copolymerized as a third component so as to be 1 to 10 mol% with respect to the total amount of the repeating structural unit of the aromatic polyamide. It is preferably an aromatic polyamide.
[0009]
　-(NH-Ar1-NH-CO-Ar1-CO)-... Formula (1)
Here, Ar1 is a divalent aromatic group having a binding group other than the meta-coordination or the parallel axis direction.
[0010]
　At that time, it is preferable that the aromatic diamine as the third component is of the formulas (2) and (3), or the aromatic dicarboxylic acid halide is of the formulas (4) and (5).
[0011]
　　H 2 N-Ar2-NH 2　... Equation (2)
　　H 2 N-Ar2-Y-Ar2-NH 2　... Equation (3)
　　XOC-Ar3-COX ... Equation (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 an oxygen atom, a sulfur atom, and an alkylene. It is at least one atom or functional group selected from the group consisting of groups, where X represents a halogen atom.
[0012]
　Further, it is preferable that the meta-type total aromatic polyamide fiber further contains an organic dye or an organic pigment or an inorganic pigment. Further, it is preferable that the conductive fiber is an acrylic fiber. It is preferable that the modacrylic fiber and the conductive fiber are dyed with the same dye.
[0013]
　In the fabric of the present invention, it is preferable that the fabric contains an ultraviolet absorber and / or a reflector. Further, it is preferable that the basis weight of the fabric is in the range of 130 to 300 g / m 2 . Further, it is preferable that the residual flame time is 2 seconds or less as measured by the method specified by the ISO 15025: 2000 A method. Further, it is preferable that the carbonized area is 30 cm 2 or less as measured by the method specified by JIS L1091: 1999 A-1 method . Further, it is preferable that the shrinkage rate after washing 5 times by the method specified in ISO5077 is 5% or less. Further, it is preferable that the heat shrinkage rate after heat treatment at 180 ° C. for 5 minutes specified in ISO 17493 is 10% or less. Further, it is preferable that the water absorption time is 30 seconds or less as measured by the method specified in JIS L1907: 2010 (dropping method). Further, it is preferable that the rigidity and softness are measured by the method specified in JIS L1096: 2010 A method (cantilever) and are 7.0 cm or less. Further, it is preferable that the antistatic property is measured by the method specified in JIS L1094: 2014 (antistatic property) and is 7.0 μC or less.
[0014]
　Further, according to the present invention, the cloth described above is used, and is composed of a group consisting of protective clothing, fire-fighting fire-retardant clothing, fire-fighting personnel activity clothing, rescue clothing, work wear, police uniform, self-defense force clothing, and military clothing. Any textile product of choice is provided.
The invention's effect
[0015]
　According to the present invention, it is possible to obtain a fabric and a textile product which has extremely excellent flame retardancy, is also excellent in washing shrinkage resistance and texture, and can be dyed uniformly as a whole fabric.
Mode for carrying out the invention
[0016]
　Hereinafter, embodiments of the present invention will be described in detail. First, the fabric of the present invention includes a spun yarn containing meta-type total aromatic polyamide fibers, modacrylic fibers and conductive fibers.
[0017]
　Here, the meta-type total aromatic polyamide fiber used in the present invention is a fiber made of a polymer in which 85 mol% or more of the repeating unit is m-phenylene isophthalamide. The meta-type total aromatic polyamide may be a copolymer containing a third component in the range of less than 15 mol%.
[0018]
　Such a meta-type total aromatic polyamide can be produced by a conventionally known interfacial polymerization method, and the degree of polymerization of the polymer is 0.5 g / 100 ml in an N-methyl-2-pyrrolidone solution. Those having a measured intrinsic viscosity (IV) in the range of 1.3 to 1.9 dl / g are preferably used.
[0019]
　The meta-type total aromatic polyamide may contain an onium salt of alkylbenzene sulfonic acid. Examples of the alkylbenzene sulfonic acid onium salt include hexylbenzene sulfonic acid tetrabutylphosphonium salt, hexylbenzene sulfonic acid tributylbenzylphosphonium salt, dodecylbenzenesulfonic acid tetraphenylphosphonium salt, and dodecylbenzenesulfonic acid tributyltetradecylphosphonium salt. Compounds such as nium salt, tetrabutylphosphonium salt of dodecylbenzene sulfonic acid, and tributylbenzylammonium salt of dodecylbenzene sulfonic acid are preferably exemplified. Among them, the tetrabutylphosphonium salt of dodecylbenzene sulfonic acid or the tributylbenzylammonium salt of dodecylbenzene sulfonic acid is particularly easy to obtain, has good thermal stability, and has high solubility in N-methyl-2-pyrrolidone. Preferably exemplified.
[0020]
　The content ratio of the alkylbenzene sulfonic acid onium salt is 2.5 mol% or more, preferably 3.0 to 7.0 mol, based on poly-m-phenylene isophthalamide in order to obtain a sufficient effect of improving the stainability. Those in the range of% are preferable.
[0021]
　Further, 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 dissolving the alkylbenzene sulfonic acid onium salt in the solvent. Etc. are used, and any of them may be used. The dope thus obtained is formed into fibers by a conventionally known method.
[0022]
　The polymer used for the meta-type total aromatic polyamide fiber has a repeating structure in an aromatic polyamide skeleton containing a repeating structural unit represented by the following formula (1) for the purpose of improving dyeability and discoloration resistance. It is also possible to copolymerize an aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main constituent unit of the above as a third component so as to be 1 to 10 mol% with respect to the total amount of the repeating structural unit of the aromatic polyamide. Is.
[0023]
　　-(NH-Ar1-NH-CO-Ar1-CO)-... Formula (1)
Here, Ar1 is a divalent aromatic group having a binding group other than the meta-coordination or the parallel axis direction.
[0024]
　Further, it can be copolymerized as a third component, and specific examples of the aromatic diamines represented by the formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylenediamine, and methylphenylenediamine. Examples thereof include acetylphenylenediamine, aminoanisidine, benzidine, bis (aminophenyl) ether, bis (aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene and the like. Specific examples of the aromatic dicarboxylic acid dichloride shown in the formulas (4) and (5) include, for example, terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4. '-Biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis (chlorocarbonylphenyl) ether and the like can be mentioned.
[0025]
　　H 2 N-Ar2-NH 2　... Equation (2)
　　H 2 N-Ar2-Y-Ar2-NH 2　... Equation (3)
　　XOC-Ar3-COX ... Equation (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 an oxygen atom, a sulfur atom, and an alkylene. It is at least one atom or functional group selected from the group consisting of groups, where X represents a halogen atom.
[0026]
　In addition, the crystallinity of the meta-type total aromatic polyamide fiber is 5 to 35% in that the dye absorbency is good and it is easy to adjust to the target color with less dye or even if the dyeing conditions are weak. It is preferable to have. Further, it is more preferably 15 to 25% in that the surface of the dye is less likely to be unevenly distributed, the discoloration resistance is high, and the dimensional stability required for practical use can be ensured.
[0027]
　Further, the residual solvent amount of the meta-type total aromatic polyamide fiber is 0.1% by weight or less (preferably 0.001 to 0.1) in that the excellent flame retardant performance of the meta-type total aromatic polyamide fiber is not impaired. Weight%) is preferable.
[0028]
　The meta-type total aromatic polyamide fiber can be produced by the following method, and in particular, the crystallinity and the amount of residual solvent can be set in the above range by the method described later.
[0029]
　The method for polymerizing the meta-type total aromatic polyamide polymer is not particularly limited, and for example, the solution weights described in Japanese Patent Publication No. 35-14399, US Pat. No. 3,360,595, and Japanese Patent Publication No. 47-10863. A legal or interfacial polymerization method may be used.
[0030]
　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 used from the above polymerization solution. It may be isolated and dissolved in an amide-based solvent.
[0031]
　Examples of the amide-based 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 preferable.
[0032]
　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 can be used at a higher concentration and a lower temperature, which is preferable. The alkali metal salt and the alkaline earth metal salt are preferably 1% by weight or less, more preferably 0.1% by weight or less, based on the total mass of the polymer solution.
[0033]
　In the spinning / coagulation step, the spinning liquid (meta-type total aromatic polyamide polymer solution) obtained above is spun into the coagulating liquid and coagulated.
[0034]
　The spinning device is not particularly limited, and a conventionally known wet spinning device can be used. Further, the number of spinning holes, the arrangement state, the hole shape, etc. of the spinneret need not be particularly limited as long as it can be stably wet-spun. A multi-hole spinneret or the like for a rayon having a thickness of about 0.2 mm may be used.
[0035]
　The temperature of the spinning liquid (meta-type total aromatic polyamide polymer solution) when spinning from the spinneret is appropriately in the range of 20 to 90 ° C.
[0036]
　As the coagulation bath used to obtain the fibers, an amide-based solvent, preferably an aqueous solution having an NMP concentration of 45 to 60% by weight, which is substantially free of inorganic salts, is used in a bath solution temperature range of 10 to 50 ° C. Use. If the concentration of the amide solvent (preferably NMP) is less than 45% by weight, the skin becomes thick, the cleaning efficiency in the cleaning step is lowered, and it becomes difficult to reduce the amount of residual solvent in the fibers. 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 amount of residual solvent in the fiber is also reduced. Becomes difficult. The time for immersing the fibers in the coagulation bath is appropriately in the range of 0.1 to 30 seconds.
[0037]
　Subsequently, in an aqueous solution having an amide solvent, preferably an NMP concentration of 45 to 60% by weight, in a plastic stretching bath in which the temperature of the bath liquid was in the range of 10 to 50 ° C., at a stretching ratio of 3 to 4 times. Perform stretching. After stretching, thorough washing is carried out through an aqueous solution having an NMP concentration of 10 to 30 ° C. of 20 to 40% by weight, followed by a warm water bath at 50 to 70 ° C.
[0038]
　The washed fibers are subjected to dry heat treatment at a temperature of 270 to 290 ° C. to obtain meta-type total aromatic aramid fibers that satisfy the above ranges of crystallinity and residual solvent amount.
[0039]
　In the meta-type total aromatic aramid fiber, the form of the fiber is preferably a short fiber having a fiber length of 25 to 200 mm for blending with other fibers. The single fiber fineness is preferably in the range of 1 to 5 dtex.
[0040]
　In the present invention, it is preferable that the meta-type total aromatic polyamide fiber is contained in the spun yarn in an amount of 5% by weight or more (more preferably 5 to 50% by weight) based on the weight of the spun yarn. If the content of the meta-type total aromatic polyamide fiber is less than this range, the flame retardancy of the fabric may decrease.
[0041]
　Further, the modacrylic fiber refers to a fiber made of a linear synthetic polymer containing 35% or more and less than 85% by weight of a repeating unit of an acrylonitrile group in JIS L0204-2 (2001). Modacrylic fiber has less wrinkles as a woven fabric, and is excellent in fire resistance, chemical resistance, aesthetics, texture, washing shrinkage resistance, and the like.
[0042]
　In the present invention, it is preferable that the modacrylic fiber is contained in the spun yarn in an amount of 30% by weight or more (more preferably 50 to 90% by weight, particularly preferably 60 to 80% by weight) based on the weight of the spun yarn. If the content of the modacrylic fiber is less than this range, the texture of the fabric, the washing shrinkage resistance, and the like may be lowered.
[0043]
　Further, in the present invention, the spun yarn includes not only meta-type total aromatic polyamide fibers and modacrylic fibers but also conductive fibers.
[0044]
　As such conductive fibers, nylon conductive threads or acrylic fibers in which conductive carbon fine particles are kneaded are preferable. When the fabric contains meta-type total aromatic polyamide fibers and acrylic fibers, dyeing with a cationic dye makes the meta-type total aromatic polyamide fibers, modacryl fibers, and acrylic fibers all darker and darker. The entire fabric is dyed uniformly. At that time, it is preferable that the meta-type total aromatic polyamide fiber and the conductive fiber are colored in the same color. Here, the hue difference between the meta-type total aromatic polyamide fiber and the conductive fiber is preferably ΔE of 3 or less.
[0045]
　As the acrylic fiber, a fiber in which conductive carbon is kneaded into an acrylic fiber, a core-sheath type composite fiber composed of a core portion containing conductive fine particles and a sheath portion not containing conductive fine particles, and the like are preferable. .. In particular, a core-sheath type composite fiber (or an eccentric core-sheath type composite fiber) in which the sheath portion is made of acrylic containing no conductive fine particles and the core portion is made of a conductive carbon-containing polymer is preferable. By incorporating such acrylic fibers in the fabric, it is possible to reduce the static electricity generated by the friction of the fabric, and as a result, it is possible to reduce problems such as adhesion of dust, harmful effects due to electric discharge, and ignition in an explosion-proof environment. can.
[0046]
　As the acrylic fiber, for example, those described in JP-A-2009-221632 are preferable. That is, it is composed of a core portion containing conductive fine particles and a sheath portion not containing conductive fine particles, the core-sheath ratio is 15/85 to 50/50, and the conductive fine particle content of the core portion is 20 to 60. is the mass%, monofilament resistivity of 10 1 ~ 10 6 is a core-sheath type conductive acrylic fiber of Omega · cm.
[0047]
　In the conductive fibers, the form of the fibers may be long fibers (multifilaments) or short fibers. In particular, short fibers having a fiber length of 25 to 200 mm (more preferably 30 to 150 mm) are preferable for blending with other fibers. The single fiber fineness is preferably in the range of 1 to 5 dtex.
[0048]
　In the fabric of the present invention, it is preferable that conductive fibers are contained in an amount of 1% by weight or more (more preferably 1 to 5% by weight) based on the weight of the spun yarn. If the weight ratio of the conductive fibers is smaller than this range, the antistatic property of the fabric may decrease.
[0049]
　In the fabric of the present invention, the spun yarn is preferably composed of only meta-type total aromatic polyamide fibers, modacrylic fibers and conductive fibers, but may further contain other fibers. Examples of such other fibers include para-type total aromatic polyamide fibers, total aromatic polyester fibers, polybenzoxazole (PBO) fibers, polybenzimidazole (PBI) fibers, polybenzthiazole (PBTZ) fibers, and polyimide (PI) fibers. , Polysulfonamide (PSA) fiber, polyether ether ketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorofiber, polyphenylene sulfide (PPS) fiber, etc. Flame-retardant fibers may be included.
[0050]
　In addition, if cellulose fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, acetate fiber, polycarbonate fiber, etc. are contained, water absorption, Dyeability, wearing comfort and the like are added, which is preferable.
[0051]
　In the present invention, the method for producing the fabric is not particularly limited, and any known method can be used. For example, it is preferable to mix the spun yarns of the above fibers to obtain a spun yarn, and then weave a single yarn or a twin yarn into a structure such as a twill weave or a plain weave using a rapier loom or the like. At that time, it is preferable that the fabric is composed of only the spun yarn, but it may be interwoven or interwoven with other fibers as described above.
[0052]
　It is then preferable to perform post-processing. Specific post-processing steps include processes such as smelting, drying, relaxing, hair burning, dyeing and functionalization.
[0053]
　Here, as the dyeing process, it is preferable to perform the dyeing process in a dyeing bath containing the above-mentioned cationic dye. At that time, preferably, a method of dyeing at 115 to 135 ° C., performing a reduction treatment, and drying can be adopted, but the method is not limited thereto.
[0054]
　Further, in the dyeing process, it is preferable to use a carrier agent, and it is preferable to perform a dyeing treatment in the same bath of the cationic dye and the carrier agent. In addition, by treating the fabric with a special surfactant before cation dyeing, it is possible to deepen the dyeing by spreading dyeing.
[0055]
　Examples of the carrier agent include DL-β-ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol and 2-methyl. Be at least one selected from phenethyl alcohol, 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, silica skin alcohol, p-anisyl alcohol and benzhydrol. Is preferable. As specific products, benzyl alcohol, Downol PPH manufactured by Dow Chemical Co., Ltd., and CINDYE DNK manufactured by BOZZETTO are preferable. Further, from the viewpoint of further improving the dyeability, it is preferable to use benzyl alcohol, particularly 2,5-dimethylbenzyl alcohol or 2-nitrobenzyl alcohol.
[0056]
　The amount of the carrier agent is preferably 1 to 10 parts by weight (more preferably 1 to 5 parts by weight) with respect to 100 parts by weight of the meta-type total aromatic polyamide fiber.
[0057]
　The smelting and relaxing treatment may be a spreading treatment or a liquid flow smelting / relaxing treatment. Specifically, it is a method of processing with a spread non-tension machine in continuous refining and continuous drying. For example, it is a method using a softener smelter, a dryer, a shrink surfer, a short loop, a Luciol dryer, or the like. In some cases, it is possible to omit the refining and relaxing steps.
[0058]
　In addition, hair shearing and / or hair burning may be performed to improve other properties. Furthermore, various other processes that impart functions such as sweat absorbers, water repellents, heat storage agents, UV shielding agents, antistatic agents, antibacterial agents, deodorants, insect repellents, mosquito repellents, phosphorescent agents, and retroreflective agents. May be additionally applied. The woven or knitted fabric to be used may be a raw material, a yarn-dyed product, or a post-dyed product.
[0059]
　As the sweat absorbent, polyethylene glycol diacrylate, a derivative of polyethylene glycol diacrylate, polyethylene terephthalate-polyethylene glycol copolymer, or water-soluble polyurethane is preferable.
[0060]
　Examples of the method of applying the sweat absorbing agent to the fabric include a method of padding and a method of treating the fabric in the same bath as the dyeing solution at the time of dyeing.
[0061]
　Since the fabric thus obtained contains the spun yarn, it has extremely excellent flame retardancy, and is also excellent in washing shrinkage resistance, texture and antistatic property. When acrylic fibers are used as conductive fibers, the meta-type total aromatic polyamide fibers, modacrylic fibers, and acrylic fibers are all dyed in a dark color and uniformly as a whole fabric by dyeing with a cationic dye. Will be done.
[0062]
　Here, it is preferable that the basis weight of the fabric is in the range of 130 to 300 g / m 2 . Further, it is preferable that the residual flame time is 2 seconds or less as measured by the method specified by the ISO 15025: 2000 A method. Further, it is preferable that the carbonized area is 30 cm 2 or less as measured by the method specified by JIS L1091: 1999 A-1 method . Further, it is preferable that the shrinkage rate after washing 5 times by the method specified in ISO 5077 is 5% or less. Further, it is preferable that the heat shrinkage rate when the heat treatment is performed at 180 ° C. for 5 minutes specified in ISO 17493 is 10% or less. Further, it is preferable that the water absorption time is 30 seconds or less as measured by the method specified in JIS L1907: 2010 (dropping method). Further, it is preferable that the rigidity and softness are measured by the method specified in JIS L1096: 2010 A method (cantilever) and are 7.0 cm or less. Further, it is preferable that the antistatic property is measured by the method specified in JIS L1094: 2014 (antistatic property) and is 7.0 μC or less.
[0063]
　The textile product of the present invention is made of the above-mentioned cloth and is selected from the group consisting of protective clothing, fire-fighting fire-retardant clothing, fire-fighting personnel activity clothing, rescue clothing, workwear, police uniforms, self-defense force clothing, and military clothing. It is a textile product. Since such a textile product uses the above-mentioned fabric, it has extremely excellent flame retardancy, and is also excellent in washing shrinkage resistance, texture, and antistatic property.
Example
[0064]
　Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In addition, each physical property in an Example was measured by the following method.
(1) Metsuke
　JIS L1096: 2010 Measured by the method specified by the A method.
(2) Combustibility The
　measurement was performed by the method specified by ISO 15025: 2000 A method and JIS L1091: 1999 A-1 method.
(3) Washing shrinkage rate
　The shrinkage rate after washing 5 times by the method specified in ISO 5077 was measured. The sutra and weft were measured with n number 5 and the average of both was taken.
(4) Dry heat shrinkage rate
　The heat shrinkage rate after heat treatment at 180 ° C. for 5 minutes specified in ISO 17493 was measured. The sutra and weft were measured with n number 5 and the average of both was taken.
(5) Water absorption
　The water absorption performance of the target fabric was measured by the method specified in JIS L1907: 2010.
(6)
　Rigidity and softness The rigidity and softness of the target fabric was measured by the method specified in JIS L1096: 2010 A method (cantilever).
(7)
　Antistatic property According to JIS L1094: 2014 (antistatic property). The amount of charged charge was measured. A pass of 7.0 μC or less is considered.
(8) Amount of residual solvent
　Approximately 8.0 g of the raw fiber was collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and the fiber weight (M1) was weighed. Subsequently, the fibers were reflux-extracted in methanol for 1.5 hours using a Soxhlet extractor to extract the amide-based solvent contained in the fibers. The extracted fibers were 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 (weight of amide-based solvent) was calculated by the following formula using the obtained M1 and M2.
Residual solvent amount (%) = [(M1-M2) / M1] × 100
(9) Crystallinity Using an
　X-ray diffraction measuring device (RINT TTRIII manufactured by Rigaku Co., Ltd.), the raw fibers are drawn into a fiber bundle having a diameter of about 1 mm. The diffraction profile was measured by mounting them on a fiber sample table. The measurement conditions were a Cu—Kα radiation source (50 kV, 300 mA), a scanning angle range of 10 to 35 °, continuous measurement of 0.1 ° width measurement, and 1 ° / min scanning. From the measured diffraction profile, air scattering and non-coherent scattering were corrected by linear approximation to obtain a total scattering profile. Next, the amorphous scattering profile was subtracted from the total scattering profile to obtain a crystal scattering profile. The 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
[Production of
　Meta-Type Total Aromatic Polyamide Fiber ] The meta-type total aromatic polyamide fiber was produced by the following method.
[0065]
　20.0 parts by weight of polymetaphenylene isophthalamide powder having an intrinsic viscosity (IV) of 1.9, produced by an interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863, was brought to −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. 2- [2H-benzotriazole-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol powder (solubility in water: 0) in the polymer solution in an amount of 3.0% by weight based on the polymer. 0.01 mg / L) was mixed and dissolved, and the solution was decompressed under reduced pressure to prepare a spinning solution (spinning dope).
[Spinning / Coagulation Step]
　The spinning dope was discharged from a spinneret 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. for spinning. The composition of the coagulating liquid was water / NMP = 45/55 (parts by weight), and the coagulating liquid was spun by being discharged at a yarn speed of 7 m / min in a coagulation bath.
[Plastic Stretching Bath Stretching Step]
　Subsequently, stretching was carried out 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 step]
　After stretching, washing is performed in a bath of 20 ° C. water / NMP = 70/30 (immersion length 1.8 m), then in a water bath of 20 ° C. (immersion length 3.6 m), and further in a warm water bath of 60 ° C. It was thoroughly washed by passing it through (immersion length 5.4 m).
[Dry heat treatment step] The
　washed fibers were subjected to dry heat treatment with a hot roller having a surface temperature of 280 ° C. to obtain meta-type total aromatic polyamide fibers.
[Physical characteristics of raw fibers]
　The physical characteristics of the obtained meta-type total aromatic polyamide fiber were 1.7 dtex of fineness, 0.08% by weight of residual solvent, and 19% of crystallinity. The obtained raw fiber was crimped and cut to obtain a staple fiber (raw cotton) having a length of 51 mm.
[0066]
　The following fiber raw cotton was used.
-Modacryl fiber; Kaneka Co., Ltd .: "ProtexM (registered trademark)" -Conductive
fiber (nylon-based conductive fiber) used in Examples 1 to 3: Solcia Co., Ltd. "NO SHOCK (registered trademark)" (conductive carbon) Nylon conductive fiber kneaded with fine particles
) -Conductive fiber used in Example 4 (acrylic conductive fiber): Fineness 3.3 dtex, fiber length 38 mm (core-sheath type with conductive carbon fine particles kneaded into the core) Acrylic conductive fiber)
[Post-processing]
　Post-processing was performed by hair burning, scouring, and final set.
[0067]
　　[Example 1]
　Staple fibers of meta-type total aromatic polyamide fiber (MA) (length 51 mm), modacrylic fiber (MD) (length 51 mm), and nylon conductive fiber (AS) (length 51 mm) are used. 40 counts / twin yarns of spun yarn blended at a ratio of MA / MD / AS = 18/80/2, weaving with a weaving density of 100 warp / 25.4 mm and 55 wefts / 25.4 mm, with a grain of 200 g / m. Two twill fabrics were obtained. Using this, it was processed by the above method. The antistatic property was 7.0 μC or less, which was a pass. The results are shown in Table 1.
[0068]
　　[Example 2]
　Staple fibers of meta-type total aromatic polyamide fiber (MA) (length 51 mm), modacrylic fiber (MD) (length 51 mm), and nylon conductive fiber (AS) (length 51 mm) are used. 40 counts / twin yarns of spun yarn blended at a ratio of MA / MD / AS = 28/70/2, weaving with a weaving density of 100 yarns / 25.4 mm and wefts of 55 yarns / 25.4 mm, with a grain of 200 g / m. Two twill fabrics were obtained. Using this, it was processed by the above method. The antistatic property was 7.0 μC or less, which was a pass. The results are shown in Table 1.
[0069]
　　[Example 3]
　Staple fibers of meta-type total aromatic polyamide fiber (MA) (length 51 mm), modacrylic fiber (MD) (length 51 mm), and nylon conductive fiber (AS) (length 51 mm) are used. 40 counts / twin yarns of spun yarn blended at a ratio of MA / MD / AS = 38/60/2, weaving with a weaving density of 100 yarns / 25.4 mm and wefts of 55 yarns / 25.4 mm, with a grain of 200 g / m. Two twill fabrics were obtained. Using this, it was processed by the above method. The antistatic property was 7.0 μC or less, which was a pass. The results are shown in Table 1.
[0070]
　　[Example 4] The same
　procedure as in Example 1 was carried out except that the conductive fibers were changed to acrylic conductive fibers (AAS) and the fabric was dyed with a cationic dye. The antistatic property was 7.0 μC or less, which was a pass. Further, the meta-type total aromatic polyamide fiber, the modacrylic fiber, and the acrylic fiber were all dyed in a dark color and uniformly as a whole fabric. The results are shown in Table 1.
[0071]
　　[Comparative Example 1]
　MA / MD / RY / PA = 25 composed of meta-type total aromatic polyamide fiber (MA), modacrylic fiber (MD), flame-retardant rayon (RY), and para-type total aromatic polyamide fiber (PA). A 40-count / twin yarn spun yarn blended at a ratio of / 30/40/5 is woven with a weaving density of 100 yarns / 25.4 mm and a weft of 55 yarns / 25.4 mm, and a twill fabric with a grain of 200 g / m 2 is woven. Obtained. Using this, it was processed by the above method. The antistatic property was unacceptable. The results are shown in Table 1.
[0072]
　　[Comparative Example 2]
　MA / MD / RY / PA = 35 composed of meta-type total aromatic polyamide fiber (MA), modacrylic fiber (MD), flame-retardant rayon (RY), and para-type total aromatic polyamide fiber (PA). A 40-count / twin yarn spun yarn blended at a ratio of / 30/15/20 is woven with a weaving density of 100 yarns / 25.4 mm and a weft of 55 yarns / 25.4 mm, and a twill fabric with a grain of 200 g / m 2 is woven. Obtained. Using this, it was processed by the above method. The antistatic property was unacceptable. The results are shown in Table 1.
[0073]
[table 1]

Industrial applicability
[0074]
　According to the present invention, there are provided fabrics and textile products having extremely excellent flame retardancy, excellent washing shrinkage resistance, texture and antistatic properties, and which can be dyed uniformly as a whole fabric, and its industrial use. The value is enormous.
The scope of the claims
[Claim 1]
　A fabric characterized by containing a spun yarn containing a meta-type total aromatic polyamide fiber, a modacrylic fiber, and a conductive fiber.
[Claim 2]
　The fabric according to claim 1, wherein the spun yarn contains 5% by weight or more of the meta-type total aromatic polyamide fiber with respect to the weight of the spun yarn.
[Claim 3]
　The fabric according to claim 1 or 2, wherein the spun yarn contains modacrylic fibers in an amount of 30% by weight or more based on the weight of the spun yarn.
[Claim 4]
　The fabric according to any one of claims 1 to 3, wherein the spun yarn contains conductive fibers in an amount of 1% by weight or more based on the weight of the spun yarn.
[Claim 5]
　The fabric according to any one of claims 1 to 4, wherein the spun yarn is composed of only meta-type total aromatic polyamide fibers, modacrylic fibers, and conductive fibers.
[Claim 6]
　The fabric according to any one of claims 1 to 5, wherein the amount of residual solvent in the meta-type total aromatic polyamide fiber is 0.1% by weight or less.
[Claim 7]
　The fabric according to any one of claims 1 to 6, wherein the degree of crystallinity of the meta-type total aromatic polyamide fiber is in the range of 15 to 25%.
[Claim 8]
　In the meta-type total aromatic polyamide fiber, the meta-type total aromatic polyamide forming the meta-type total aromatic polyamide fiber is repeated in the aromatic polyamide skeleton containing the repeating structural unit represented by the following formula (1). Aroma obtained by copolymerizing an aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main structural unit of the structure as a third component so as to be 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide. The cloth according to any one of claims 1 to 7, which is a group polyamide.
　-(NH-Ar1-NH-CO-Ar1-CO)-... Formula (1)
Here, Ar1 is a divalent aromatic group having a binding group other than the meta-coordination or the parallel axis direction.
[Claim 9]
　The fabric according to claim 8, wherein the aromatic diamine as the third component is the formulas (2) and (3), or the aromatic dicarboxylic acid halide is the formulas (4) and (5).
　　H 2 N-Ar @ 2-NH　2 · · · formula
　　(2) H2 N-Ar @ 2-Y-Ar @ 2-NH　2 · · · formula
　　(3) XOC-Ar @ 3-COX · · · formula
　　(4) XOC-Ar @ 3-Y- Ar @ 3-COX · · · formula (5)
wherein, Ar @ 2 is a divalent aromatic group different from the Ar1, Ar @ 3 is a divalent fang different from Ar1
Kozokumoto, Y is an oxygen atom, a sulfur atom, an alkylene group It is at least one atom or functional group selected from the group consisting of, and X represents a halogen atom.
[Claim 10]
　The fabric according to any one of claims 1 to 9, wherein the meta-type total aromatic polyamide fiber further contains an organic dye or an organic pigment or an inorganic pigment.
[Claim 11]
　The fabric according to any one of claims 1 to 10, wherein the conductive fiber is an acrylic fiber.
[Claim 12]
　The fabric according to any one of claims 1 to 11, wherein the modacrylic fiber and the conductive fiber are dyed with the same dye.
[Claim 13]
　The fabric according to any one of claims 1 to 12, wherein the fabric contains an ultraviolet absorber and / or a reflector.
[Claim 14]
　The fabric according to any one of claims 1 to 13, wherein the basis weight of the fabric is in the range of 130 to 300 g / m 2 .
[Claim 15]
　ISO 15025: 2000 The fabric according to any one of claims 1 to 14, which has a residual flame time of 2 seconds or less as measured by a method specified by the A method.
[Claim 16]
The fabric according to any one of claims 1 to 15, which 　has a carbonized area of ​​30 cm 2 or less as measured by a method specified by JIS L1091: 1999 A-1 method .
[Claim 17]
　The fabric according to any one of claims 1 to 16, wherein the shrinkage rate after washing 5 times by the method specified in ISO 5077 is 5% or less.
[Claim 18]
　The fabric according to any one of claims 1 to 17, wherein the heat shrinkage rate when heat-treated at 180 ° C. for 5 minutes specified in ISO 17493 is 10% or less.
[Claim 19]
　The fabric according to any one of claims 1 to 18, wherein the water absorption time is 30 seconds or less as measured by the method specified in JIS L1907: 2010 (dropping method).
[Claim 20]
　The fabric according to any one of claims 1 to 19, wherein the hardness and softness are measured by a method specified in JIS L1096: 2010 A method (cantilever) and are 7.0 cm or less.
[Claim 21]
　The fabric according to any one of claims 1 to 20, wherein the antistatic property is measured by the method specified in JIS L1094: 2014 (antistatic property) and is 7.0 μC or less.
[Claim 22]
　Using the fabric according to any one of claims 1 to 21, select from the group consisting of protective clothing, fire-fighting fire-retardant clothing, fire-fighting personnel activity clothing, rescue clothing, workwear, police uniforms, self-defense force clothing, and military clothing. Any textile product that will be.