The present invention, flame retardancy, excellent in appearance quality as well antistatic relates preferably fabrics and their preparation and fiber products also have protection performance against electrical arc.
BACKGROUND
[0002]
　Conventionally, firefighters, astronauts, race driver, in clothes such as operator power companies and chemical companies to wear, on the assumption that the contact with the fire or hot, using a wholly aromatic polyamide fibers (aramid fibers) flame-retardant fabric is being used.
[0003]
　In these clothes, to be required also antistatic performance as well flame-retardant, conductive fibers such as a conductive aliphatic polyamide fibers (conductive nylon fibers) may be mixed in the fabric has been proposed ( Patent Document 1). By mixing conductive fibers into the fabric, is reduced static electricity generated by friction of the fabric can be prevented dust deposition, adverse effects due to discharge, and the ignition operation in hazardous environments. Moreover, applying a dyeing flame retardant fabric with wholly aromatic polyamide fibers are proposed (e.g., Patent Documents 2 and 3).
[0004]
　However, conductive aliphatic polyamide fibers, because they are not colored by cationic dyes used in the case of dyeing a flame retardant fabric with wholly aromatic polyamide fibers, is lowered the appearance quality of the flame retardant fabric there were.
[0005]
　On the other hand, and people working near electrical equipment, emergency personnel corresponding to accident near electrical equipment are potentially may be exposed to electrical arcs or flash fires, fabric also has a protection performance against electrical arc there is a demand.
CITATION
Patent Document
[0006]
Patent Document 1: WO 2016/035638 pamphlet
Patent Document 2: WO 2015/159749 pamphlet
Patent Document 3: JP 2003-209776 JP
Summary of the Invention
Problems that the Invention is to Solve
[0007]
　The present invention has been made in consideration of the above situation, and its object is flame-retardant, excellent in appearance quality as well antistatic, preferably a fabric, and a manufacturing method thereof also has a protection performance against electrical arc and to provide a textile product.
Means for Solving the Problems
[0008]
　The present inventors have result of intensive investigations to achieve the above object, which can be colored with the same dye, a flame retardant by using a wholly aromatic polyamide fiber and conductive fibers, the appearance quality as well Antistatic It found that even better fabric obtained, and have completed the present invention by overlapping further intensive studies.
[0009]
　Thus, a fabric containing "meta-type wholly aromatic polyamide fiber and conductive fibers, according to the present invention, wherein the meta-type wholly aromatic polyamide fiber and conductive fiber formed by both colored fabric . "it is provided.
[0010]
　At that time, it is preferable that the meta-type wholly aromatic polyamide fiber and the conductive fibers comprise the same dye. At that time, it is preferable that the dye is a cationic dye. Further, it is preferable that the meta-type wholly aromatic polyamide fiber and the conductive fiber is colored in the same color. Further, it is preferable that the conductive fiber is a conductive acrylic fiber. Further, it is preferable that the conductive acrylic fiber is a core-sheath composite yarn. At that time, the conductive acrylic fiber, a core portion containing conductive fine particles is preferably core-sheath composite fibers composed of non a sheath portion containing conductive particles. Further, the conductive fibers in the fabric is preferably contained fabric weight versus 1-30% by weight. Further, it is preferable that the meta-type wholly aromatic polyamide fiber and the conductive fibers contained in the fabric as a blended yarn. Moreover, further to the fabric, para-type wholly aromatic polyamide fibers, polyphenylene sulfide fibers, polyimide fibers, polybenzimidazole fibers, polybenzoxazole fibers, polyamideimide fibers, polyetherimide fibers, pyrolytic Mex ®, and carbon fibers , it includes one or more selected from the group consisting of is preferred. Further, it is preferred that the fabric has a weave. Further, the spun yarn containing the meta-type wholly aromatic polyamide fiber and antistatic fiber is preferably formed arranged in all warp and weft. Also, the basis weight of the fabric ~ 9.0Oz 3.0 / yd 2 is preferably in the range of.
[0011]
　In fabrics of the present invention, frictional charge amount measured by JIS L1094-2014 C method 7.0MyuC / m 2 is preferably less. Further, it is preferable that JIS L1091-1992 A-4 method after flame time in the flammability measured as defined in (12 sec flame contact) is less than 1.0 seconds.
[0012]
　Further, according to the present invention, with reference to the fabric, protective clothing, work clothing, protective clothing, camouflage, happi, and any textile product selected from the group consisting of the apron is provided.
[0013]
　Further, according to the present invention, subjected to dyeing the fabric containing meta-type wholly aromatic polyamide fiber and conductive fibers, the production method of the fabric is provided.
Effect of the invention
[0014]
　According to the present invention, flame retardancy, excellent in appearance quality as well antistatic, preferably fabrics and their preparation and fiber products also have protection performance against electrical arcing is obtained.
DESCRIPTION OF THE INVENTION
[0015]
　It will be described in detail embodiments of the present invention. First, the meta-type wholly aromatic polyamide fiber used in the present invention (meta-type aramid fiber), a fiber 85 mol% or more of the repeating units consisting of a polymer is a m- phenylene isophthalamide. Such meta-type wholly aromatic polyamide, may safely be a copolymer containing a third component in the range of less than 15 mol%.
[0016]
　Such meta-type wholly aromatic polyamide may be prepared by a known interfacial polymerization method conventionally. The polymerization degree of the polymer, and the inherent viscosity measured in N- methyl-2-pyrrolidone solution at a concentration of 0.5g / 100ml (I.V.) is those in the range of 1.3 ~ 1.9 dl / g preferably used.
[0017]
　The above meta-type wholly aromatic polyamide may contain alkylbenzene sulfonic acid onium salt. The alkylbenzene sulfonic acid onium salts, hexyl benzene sulfonic acid tetrabutyl phosphonium salt, hexyl benzene sulfonic acid tributyl benzyl phosphonium salt, dodecylbenzenesulfonic acid tetraphenyl phosphonium salt, dodecylbenzenesulfonic acid tributyl tetradecyl phosphonium salts, dodecylbenzenesulfonic acid tetrabutylphosphonium phosphonium salts, compounds such as dodecylbenzenesulfonic acid tributyl benzyl ammonium salt is preferably exemplified. Among them dodecylbenzenesulfonate tetrabutyl phosphonium salt or dodecylbenzenesulfonic acid tributyl benzyl ammonium salt, is readily available, thermal stability upon satisfactory, especially since high solubility N- methyl-2-pyrrolidone It is preferably exemplified.
[0018]
　Content of the alkylbenzene sulfonic acid onium salts, in order to obtain sufficient dyeability improving effect, 2.5 mol% or more of the poly -m- phenylene isophthalamide (more preferably 3.0-7.0 it is preferable mole%).
[0019]
　As a method of mixing the poly -m- phenylene isophthalamide and alkylbenzenesulfonic acid onium salt, a method of dissolving and mixing the poly -m- phenylene isophthalamide in the solvent, dissolve, it alkylbenzene sulfonic acid onium salt in the solvent such as is used. The thus obtained dope is formed into fibers by a conventionally known method.
[0020]
　Polymer used in the meta-type wholly aromatic polyamide fibers, the like to improve the dyeing property and tarnish discoloration, the aromatic polyamide backbone comprising repeating structural unit represented by the formula (1) below, a repeating structure the main different aromatic diamine component and constitutional units or the aromatic dicarboxylic acid halide component, also as be copolymerized a 1 ~ 10 mol% relative to the total amount of repeating units of the aromatic polyamide as a third component, the it is.
[0021]
　　- (NH-Ar1-NH- CO-Ar1-CO) - ··· Equation (1)
where, Ar @ 1 is a divalent aromatic group having a bonding group other than the meta-coordinated or parallel axial direction.
[0022]
　It is also possible to copolymerize a third component as described below. Equation (2), (3) Specific examples of the aromatic diamine as shown in, for example, p- phenylenediamine, chloro-phenylenediamine, methylphenylenediamine, acetyl phenylenediamine, amino Ani chlorhexidine, benzidine, bis (aminophenyl) ether, bis (aminophenyl) sulfone, diamino benzanilide, diamino azobenzene and the like. Equation (4), specific examples of the aromatic dicarboxylic acid dichloride as shown in (5) is, for example, chlorides of terephthalic acid, 1,4-naphthalene dicarboxylic acid chloride, 2,6-naphthalene dicarboxylic acid chloride, 4,4 '- biphenyl dicarboxylic acid chloride, 5-chloro isophthalic acid chloride, 5-methoxy-isophthalic acid chloride, and the like bis (chlorocarbonyl) ether.
[0023]
　　H 2 N-Ar @ 2-NH　2 · · · formula (2)
H 2 N-Ar @ 2-Y-Ar @ 2-NH　2 · · · formula 　　(3) XOC-Ar @ 3-COX · · · formula 　　(4) XOC-Ar3- Y-Ar3-COX ··· equation (5) 　where, Ar @ 2 is a divalent aromatic group different from the Ar @ 1, Ar @ 3 is a divalent aromatic group different from the Ar @ 1, Y is an oxygen atom, a sulfur atom, an alkylene at least one atom or functional group selected from the group consisting of radicals, X represents a halogen atom.

[0024]
　Further, crystallinity of meta-type wholly aromatic polyamide fibers may exhaustion of dye, in terms of easily adjusted to aim color weak fewer dye or dyeing conditions, at 5-35% there it is preferable. Furthermore, it is more preferable point higher surface uneven distribution occurs hardly tarnish discoloration of dyes and practically necessary dimensional stability in that it can secure 15-25%.
[0025]
　Further, the residual solvent amount of meta-type wholly aromatic polyamide fibers, in that it does not impair the excellent flame retardant performance of the meta-type wholly aromatic polyamide fibers, 0.1 wt% or less (more preferably from 0.001 to zero. is preferably 1 mass%).
[0026]
　The meta-type wholly aromatic polyamide fiber can be produced by the following method. Especially by a method described later, the crystallinity and the remaining solvent amount can be in the above range.
[0027]
　No particular limitation is imposed on the polymerization method of meta-type wholly aromatic polyamide polymer. For example, JP-B-35-14399, JP-U.S. Patent No. 3360595 discloses, may be used a solution polymerization or an interfacial polymerization method as described in, JP-B-47-10863.
[0028]
　No particular limitation is imposed on the spinning solution. The solution polymerization or interfacial polymerization obtained, etc., may be used amide-based solvent solution containing an aromatic copolyamide polymer, the polymer from the polymerization solution was isolated, those which was dissolved in an amide solvent it may be used.
[0029]
　As the amide solvents to be used herein, N, N- dimethylformamide, N, N- dimethylacetamide, N- methyl-2-pyrrolidone, and the like can be exemplified dimethyl sulfoxide. In particular N, N-dimethylacetamide are preferred.
[0030]
　Obtained above copolymerization aromatic polyamide polymer solution is further stabilized by containing an alkali metal salt or alkaline earth metal salts, higher concentrations, preferably allows the use of a low temperature. 1 mass% or less alkali metal salts and alkaline earth metal salts based on the total weight of the polymer solution (more preferably 0.1 mass% or less) is.
[0031]
　In the spinning and solidification step to solidify by spinning the spinning solution obtained in the above (the meta-type wholly aromatic polyamide polymer solution) into a coagulating liquid.
[0032]
　There are no particular restrictions on the spinning apparatus can be used conventionally known wet spinning apparatus. Further, as long as it can stably wet spinning, spinning hole number of spinneret arrangement state, the hole shape is not particularly limited. For example, the number of holes of 1000 to 30000, the spinning hole diameter may be used a multi-hole spinneret and the like for staple of 0.05 ~ 0.2 mm.
[0033]
　The temperature of the spinning liquid when spinning from a spinneret (meta-type wholly aromatic polyamide polymer solution) is preferably in the range of 20 ~ 90 ° C..
[0034]
　The coagulation bath used to obtain the fibers, is substantially free of inorganic salts, amide solvents, preferably an aqueous solution concentration of 45-60% by weight of NMP, at a temperature range of 10 ~ 50 ° C. bath solution it is preferably used. The concentration is less than 45 wt% of an amide solvent (preferably NMP) becomes a skin thick structure, washing efficiency is lowered in the washing step, it may be difficult to reduce the residual solvent amount of fiber . On the other hand, if the concentration of the amide solvent (preferably NMP) is more than 60 wt% can not perform a uniform solidification up to the inner fiber, Therefore again, to reduce the residual solvent amount of fiber it may be difficult. Incidentally, the immersion time of the fiber into the coagulation bath is preferably in the range of 0.1 to 30 seconds.
[0035]
　Subsequently, amide solvents, preferably an aqueous solution concentration of 45-60% by weight of NMP, C. in plasticization drawing bath having a temperature of the bath in the range of 10 ~ 50 ℃, 3 ~ 4 times at a draw ratio subjected to the stretching. After stretching, an aqueous solution the concentration of NMP in 10 ~ 30 ° C. of 20 to 40 wt%, followed by thoroughly washing through warm water bath at 50 ~ 70 ° C. performed. Fibers after washing, subjected to a dry heat treatment at a temperature of 270 ~ 290 ° C..
[0036]
　By the production method, it is possible to obtain a meta-type wholly aromatic polyamide fiber satisfying the above ranges of crystallinity and residual solvent amount.
[0037]
　In the meta-type wholly aromatic polyamide fiber, in the form of fibers, it may be the long fiber (multifilament) or a short fiber. In particular, (more preferably 30 ~ 150 mm) Fiber length 25 ~ 200 mm in order to blend with other fibers preferably staple fibers. Further, the range of 1 ~ 5 dtex is preferred as the single fiber fineness.
[0038]
　In fabrics of the invention, the mass ratio of the meta-type wholly aromatic polyamide fiber is preferably a fabric weight versus 70 to 99 wt% (more preferably 75 to 95% by weight) in the range of. When the mass ratio of the meta-type wholly aromatic polyamide fiber is less than the above range, there is a possibility that the flame retardancy of the fabric is reduced. If conversely the mass ratio of the meta-type wholly aromatic polyamide fiber is greater than the range, the mass ratio of the conductive fibers is reduced, there is a possibility that antistatic property is deteriorated.
[0039]
　On the other hand, as the conductive fiber, conductive acrylic fiber is preferred. When fabric contains meta-type wholly aromatic polyamide fiber and conductive acrylic fibers, by staining with cationic dyes, in the dark none meta-type wholly aromatic polyamide fiber and conductive acrylic fibers, and the fabric It is uniformly dyed as a whole. At that time, it is preferable that the meta-type wholly aromatic polyamide fiber and the conductive fiber is colored in the same color. Here, as the hue difference of the meta-type wholly aromatic polyamide fiber and conductive fibers, it is preferred ΔE is 3 or less.
[0040]
　Examples of the conductive acrylic fibers, fibers kneaded conductive carbon acrylic fiber, a core portion containing conductive particles, such as from configured sheath-core composite fiber sheath containing no conductive fine particles are preferred . In particular, it consists acrylic sheath does not contain conductive particles, and the like sheath-core conjugate fiber core is made of a conductive carbon-containing polymer (or an eccentric core-sheath composite yarn) is preferred. By including such a conductive acrylic fiber fabric, it is possible to reduce the static electricity generated by friction of the fabric, resulting in reducing adhesion of dust, harmful effects due to the discharge, problems such as ignition of explosion-proof environment can.
[0041]
　As the conductive acrylic fibers, for example, it is preferred according to JP 2009-221632. That is, a core portion containing conductive particles, is composed of the sheath containing no conductive fine particles, core-sheath ratio is 15 / 85-50 / 50, the conductive particles content in the core 20 to 60 is the mass%, monofilament resistivity of 10 1 ~ 10 6 is a core-sheath type conductive acrylic fiber of Omega · cm.
[0042]
　In the conductive fibers in the form of fibers, it may be the long fiber (multifilament) or a short fiber. In particular, (more preferably 30 ~ 150 mm) Fiber length 25 ~ 200 mm in order to blend with other fibers preferably staple fibers. Further, the range of 1 ~ 5 dtex is preferred as the single fiber fineness.
[0043]
　In fabrics of the invention, the mass ratio of the conductive fibers is preferably in the range of the cloth mass versus 1-30 weight% (more preferably 1 to 20 mass%). When the weight ratio of the conductive fibers is less than the above range, there is a possibility that the antistatic properties of the fabric is lowered. Conversely, if the mass ratio of the conductive fibers is greater than the range, the mass ratio of the meta-type wholly aromatic polyamide fiber is decreased, there is a risk of lowering the flame retardancy.
[0044]
　Fabric of the present invention, the may be configured only by the meta-type wholly aromatic polyamide fiber and conductive fibers, but further, para-type wholly aromatic polyamide fibers, polyphenylene sulfide fibers, polyimide fibers, polybenzimidazole fibers, polybenzoxazole fibers, polyamideimide fibers, polyetherimide fibers, pyrolytic Mex ®, and one or more may be included that are selected from the group consisting of carbon fibers.
[0045]
　For example, fabric para-type wholly aromatic polyamide fiber when the contain fabric strength (tensile strength, etc.) is improved preferably. At that time, the mass ratio of para-type wholly aromatic polyamide fibers, preferably in the range of the cloth mass versus 1-10% by weight.
[0046]
　In fabrics of the invention may contain further polyester fibers. It may be contained in polyester fiber to fabric. At that time, the mass ratio of the polyester fibers is preferably in the range of the cloth mass versus 1-10% by weight.
[0047]
　Here, in order to obtain flame retardancy, excellent fabric in appearance quality as well antistatic, these fibers are blended, it is preferably included in the fabric as a blended yarn. At that time, the fiber length of each fiber is preferably a 25 ~ 200 mm (more preferably 30 ~ 150 mm). Incidentally, the fiber length of each fiber may be different or may be identical.
[0048]
　In the present invention, in order to obtain a high-quality appearance, the meta-type wholly aromatic polyamide fiber and conductive fibers is essential that are both colored. In particular, it is preferable that the meta-type wholly aromatic polyamide fiber and conductive fibers is colored in the same color (Delta] E is 3 or less).
[0049]
　Here, it is preferable that the meta-type wholly aromatic polyamide fiber and the conductive fibers comprise the same dye. It is particularly preferred that the dye is a cationic dye.
[0050]
　The cationic dye is soluble in water refers to water-soluble dye having a group showing basicity, in which acrylic fibers, are widely used for dyeing such as natural fibers or cationic dyeable polyester fiber. As the cationic dyes, for example diacrylic methane, triacrylate methane, quinone imine (azine, oxazine, thiazine), xanthene, methine (polymethine, azamethine), heterocyclic azo (Chiazoruazo, triazole azo, benzothiazole azo), and the like anthraquinone. In recent years, the cationic dye was distributed by sequestering basic groups are also known, can be used with both. Among them, azo-based is preferred. For example, C. as azo I. Basic Blue54, C. I. Basic Blue3, C. I. Basic Red29, C. I. Can be preferably exemplified, etc. Basic Yellow67.
[0051]
　In the present invention, a method of manufacturing the fabric is not particularly limited, it is possible to use in any known method. For example, to obtain a spun yarn and cotton mixing at least meta-type wholly aromatic polyamide fiber and conductive fibers.
[0052]
　At that time, the spun yarn fineness (count) is cotton count (Ecc) 20 ~ 80 fastest is preferred in view of such anti-thread breakage and strength. Preferably at least 60 present as the number of single fibers. Or less (more preferably 0.001 ~ 3.0 dtex) are preferred 3.0 dtex as raw cotton single fiber fineness. As (more preferably 3.8 to 4.0) from 3.6 to 4.2 is twist coefficient of the spun yarn (lower twist coefficient) preferably in the range of. More該撚coefficient is large, while the pilling resistance of the fabric and fluff convergence is improved, the spun yarn becomes rigid, tear strength is or reduction of fabric elongation is lowered, there is a risk that the fabric is cured . Incidentally, the twist coefficient is expressed by the following equation.
Twist coefficient = twist number (times /2.54cm)/ spinning cotton count (Ecc) of thread 1/2
　spinning method of spinning yarn ring spinning, MTS, MJS, the usual spinning methods, such as innovation spinning and ring spinning, such as MVS it is. Lay direction may be either in the Z direction or S direction.
[0053]
　Then, such after the spun yarn set stop twist as needed (vacuum steam set), two or more spun yarns as necessary (preferably present 2-4, particularly preferably 2) Pull aligned with spinning and to Goyo. The twisting machine used in case twist, up twister, covering machines, Italy type twisting machine, twisting machine is exemplified such as a double twister.
[0054]
　At this time, twisting direction of Goyo (upper twist) is additionally twisted direction. For example, twisting direction of the spun yarn For Z twist, perform twisting in the Z direction in the same direction. Further, the twist number is preferably 2000 turns / m or more, more preferably 2100 to 3000 turns / m, particularly preferably from 2300 to 2800 times / m. If 該撚 number is less than 2000 times / m, twist stopping set, after untwisting, there is a possibility that the form of the spun yarn is not a coiled.
[0055]
　Then, subjected to (a similar high vacuum steam set to those used in setting stop twisting conventional aramid ply yarns.) According twisted yarn to twist stopping set. In the case of need to grant a strong twist stopping set, or increase the number of twist stopping set, may change the stop set temperature and set time twist. For example, the set temperature is 115 ~ 125 ° C., a set time is 20-40 minutes, the number may be 1 to 3 times. Higher setting temperature is high, also well preferred longer set of the set time. Or increasing the number of set stop twist, or longer processing time, by raising the temperature, it is possible to enhance the setting ability. (Work safety management, quality control, etc.) production management it is desirable to increase the processing time and production processing costs to consider. In addition, the higher the degree of vacuum quality is improved preferable.
[0056]
　Then, (the twist direction of Goyo reverse lay direction) twist stopping the set of twisted yarn untwisting, and thermally set as required. At that time, number of twists of untwisting the twist number of the alloy twist is preferably in the range of 70-90%. By performing the untwisting in twist number in this range it had stretch spun yarn which exhibits coiled is obtained. In the spun yarn exhibiting such coiled, it is preferably in the range of twist number in obtaining an excellent stretchability is 200 to 860 times / m.
[0057]
　Also, raw cotton used for spun yarn, dyed (dyed) raw cotton, may be a spun-dyed cotton, using functionalized processing raw cotton those subjected to (sweat, fast drying, antifouling, flame retardant, ultraviolet absorber, etc.) it may be.
[0058]
　In fabrics of the invention, the fabric of the tissue is not particularly limited, woven, knitted, may be any nonwoven fabric, flame retardant, flame resistant, fabrics are preferred in terms of fabric strength. At that time, as the weave, plain tissue, twill tissue, satin tissue, such as double-layered fabric is preferable.
[0059]
　The density of the fabric, electrically superior protection performance in obtaining a relative arc, warp density 50 present /2.54cm more and weft density of 50 present /2.54cm or more (more preferably a warp density of 60 present /2.54cm or more and weft density 60 present /2.54cm or more and particularly preferably a warp density of 60-80 present /2.54cm and weft density 60 to 80 present /2.54cm higher).
[0060]
　Further, when the spun yarn comprising meta-type aromatic polyamide fiber and antistatic fiber is arranged on all textile warp and weft, improved protection performance for electric arc preferred.
[0061]
　Fabric of the present invention can be woven knitting by a conventional method using the spun yarn. At that time, such as by using a rapier loom at a single yarn or ply yarns, twill, it is preferred to weaving the tissue, such as a plain weave. It may be a knitted fabric or non-woven fabric.
[0062]
　It is preferable to perform post-processing subsequent to the knitting organization. Specific after processing step, scouring, drying, relaxing, singeing, the processes such as dyeing and functionalization process can be exemplified.
[0063]
　Here, as the dyeing, it is preferably subjected to dyeing in the dyeing bath containing a cationic dye as described above. At that time, preferably after staining with 115 ~ 135 ° C., subjected to reduction treatment, but it is possible to employ a method or the like for drying it is not limited to this.
[0064]
　In the dyeing, it is preferable to use a carrier agent, it is preferably subjected to a dyeing treatment in the same bath of a cationic dye and a carrier agent. Further, by treating the fabric with a special surfactant before the cationic dyeing, stain reduction can be performed with open width dyeing.
[0065]
　The carrier agent, for example, DL-beta-ethyl-phenethyl alcohol, 2-ethoxy benzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p- isopropyl alcohol, 2-methyl phenethyl alcohol, 3-methyl-phenethyl alcohol, 4-methyl-phenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamic alcohol, is at least one selected from among p- anisyl alcohol and benzhydrol It is preferred. The specific product, benzyl alcohol, Dow Chemical Co. DOWANOL PPH, is BOZZETTO made CINDYE DNK preferred. In terms of further improving the dyeing property, benzyl alcohol, among others, it is preferable to use 2,5-dimethyl benzyl alcohol or 2-nitrobenzyl alcohol.
[0066]
　The amount of carrier agent, 1 to 10 parts by weight with respect to the meta-type wholly aromatic polyamide fiber 100 parts by weight (more preferably 1 to 5 parts by weight) is preferred.
[0067]
　The scouring and relaxation treatment may be a open-width process, may be a liquid flow scouring-relaxation process. Specifically, a method of processing in open-width non tension machine in a continuous scouring and continuous drying. For example, Sofusa scouring machine or Inui絨, shrink surfer, short loop, the method using a firefly dryer. Sometimes, it is also possible to omit the scouring and relaxation process.
[0068]
　Further, in order to improve other properties, it may be subjected to a shaved and / or singeing. Furthermore, sweat agents, water repellents, regenerating agent, UV shielding, antistatic agents, antibacterial agents, deodorants, insect repellents, Bokazai ,, luminescent agent, various other to impart functions such as retroreflective agents processing may be an additional application. Woven or knitted fabric used may be a dyed product, may be a dyed product, may be a dyed product.
[0069]
　As the sweat agent, polyethylene glycol diacrylate or polyethylene glycol diacrylate derivatives or polyethylene terephthalate - polyethylene glycol copolymer or a water-soluble polyurethane is preferred.
[0070]
　As a method for imparting a sweat agent to the fabric, a method of padding, a method of treating the dyeing liquid and the bath during dyeing are exemplified.
[0071]
　Thus, in the obtained fabric, it is preferable that the thickness of the fabric than 0.30 mm (more preferably 0.35 ~ 0.50 mm) is. If the thickness of the fabric is less than 0.30 mm, protection performance against electrical arcing may be reduced. Conversely, if the thickness of the fabric is greater than 0.50 mm, there is a possibility that light weight and wearing comfort is reduced.
[0072]
　Also, the basis weight of the fabric ~ 9.0Oz 3.0 / yd 2 (more preferably ~ 9.0Oz 5.0 / yd 2 are preferably) in the range of. When the basis weight of the fabric is less than the above range, protection performance against electrical arcing may be reduced. Conversely, when the basis weight of the fabric is greater than the above range, there is a possibility that light weight and wearing comfort is reduced.
[0073]
　Since the fabric of the present invention has a configuration described above, excellent in flame retardancy, appearance quality as well antistatic, further also has the protection performance against electrical arc.
[0074]
　In fabrics of the present invention, when the conductive fine particles core and conductive fine conductive acrylic fibers composed of a sheath portion not containing containing is included, electrically conductive fine particles contained in the core portion absorb the irradiation energy of the arc flash, to suppress the energy transmitted through the fabric, excellent protection performance of the human body. Sheath because it is an acrylic polymer containing no conductive fine particles, it is possible to dye the same cationic dye and the meta-type wholly aromatic polyamide fibers.
[0075]
　Examples of the antistatic, frictional charge amount measured by JIS L1094-2014 C method 7.0MyuC / m 2 or less (more preferably ~ 4.0MyuC 0.1 / m 2 is preferably a) . As the flame retardant, it is preferable JIS L1091-1992 A-4 method after flame time in the flammability measured as defined in (12 sec flame contact) is less than 1.0 seconds. Further, the arc resistance test ASTM F1959-1999, ATPV value 8.0Cal / cm 2 or more (preferably ~ 12.0Cal 8.0 / cm 2 is preferably a). Further, it is preferable that a limit oxygen index (LOI) is 26 or more.
[0076]
　Further, according to the present invention, with reference to the fabric, protective clothing, work clothing, protective clothing, camouflage, happi, and any textile product selected from the group consisting of the apron is provided.
[0077]
　Since such fiber products are using the fabric excellent in flame retardancy, appearance quality as well antistatic, further also has the protection performance against electrical arc.
Example
[0078]
　Hereinafter, detailed explanation of the present invention by way of example, the present invention is not limited thereto by any means. Incidentally, physical properties in Examples were measured by the following methods.
(1) Flame retardancy of the fabric
　of the remaining flame time was measured in flammability measurements defined in JIS L1091-1992 A-4 method (12 seconds contact dermatitis).
(2) the residual solvent content
　fibrils were about 8.0g collected, allowed to cool in a desiccator after drying for 120 minutes at 105 ° C., and weighed fibers mass (M1). Subsequently, this fiber, 1.5 hours in methanol, subjected to reflux extraction using a Soxhlet extractor and extracted for amide solvent contained in the fiber. Remove the fibers having been subjected to the extraction, and allowed to cool in a desiccator after vacuum dried for 60 minutes at 0.99 ° C., and weighed fibers mass (M2). Amount solvent remaining in the fiber (amide solvent mass), using the M1 and M2 obtained, was calculated by the following equation.
Residual solvent amount (%) = [(M1-M2) / M1] × 100
(3) Crystallinity
　X-ray diffractometer using (manufactured by Rigaku Corporation RINT TTR III), were measured diffraction profile aligned pull the fibrils into fiber bundles of about 1mm diameter was attached to the fiber sample mount. Measurement conditions, Cu-K [alpha ray source (50 kV, 300 mA), a scanning angle range 10 ~ 35 °, continuous measurement 0.1 ° width measurement was performed at 1 ° / minute scan. Air scattered from actually measured diffraction profile, a non-coherent scattering and corrected by the linear approximation to obtain a total scattering profile. Then, to give crystals scattering profile by subtracting the amorphous scattering profile from the total scattering profile. Crystallinity, the area intensity of the crystalline scattering profiles (crystalline scattering intensity) and integrated intensity of the total scattering profile (total scattering intensity) was calculated by the following equation.
Crystallinity (%) = [crystal scattering intensity / total scattering intensity] × 100
(4) dyeability
　perform colorimetry in Macbeth spectrophotometer (Color-Eye3100), it was determined Delta] E.
(5) Antistatic
　were measured frictional charge amount by JIS L1094-2014 C method. 7.0MyuC / M 2 the following was passed.
(6) having a basis weight
　was measured by JIS L1096.
(7) ATPV value
　was measured ATPV value by the arc resistance test ASTM F1959-1999. 8.0Cal / Cm 2 pass more than the (level 2 clear).
Production of meta-type wholly aromatic polyamide fiber]
　Meta-type wholly aromatic polyamide fiber was prepared in the following manner.
[0079]
　Was produced by interfacial polymerization method in accordance with the method of JP-B-47-10863 JP, an intrinsic viscosity (I.V.) is poly-m-phenylene isophthalamide powder 20.0 parts by weight of 1.9, the -10 ° C. cooled N- methyl-2-pyrrolidone (NMP) was suspended in 80.0 parts by weight, it was slurried. Subsequently, and dissolved by heating the suspension to 60 ° C., to give a clear polymer solution. To the polymer solution, the polymer compared 3.0 mass% of 2-[2H-benzotriazol-2-yl] -4-6- bis (1-methyl-1-phenylethyl) phenol powder (solubility in water: 0 .01mg / L) were mixed and dissolved to obtain a spinning solution (spin dope) to reduced pressure defoaming.
[Spinning and coagulation step]
　The above spinning dope, pore size 0.07 mm, the spinneret holes of 500, was spun by ejecting into a coagulation bath at a bath temperature of 30 ° C.. The composition of the coagulation liquid is a water / NMP = 45/55 (parts by weight) was spun by discharging at a yarn speed 7m / min into a coagulation bath.
[Plasticization drawing bath drawing step]
　Subsequently, at plasticizer stretching bath of the composition of a temperature 40 ° C. water / NMP = 45/55, was stretched 3.7-fold stretching ratio.
Washing Step]
　After stretching, 20 ° C. water / NMP = 70/30 bath (immersion length 1.8 m), followed by washing with 20 ° C. water bath (immersion length 3.6 m), further 60 ° C. warm water bath It was thoroughly washed through (immersion length 5.4 m).
[Dry heat treatment step]
　The fiber after washing was subjected to dry heat treatment at a surface temperature 280 ° C. of the heat roller, to obtain a meta-type wholly aromatic polyamide fibers.
[Physical Properties of the original fiber]
　The properties of the obtained meta-type wholly aromatic polyamide fibers (meta-aramid fibers) a fineness 1.7 dtex, the residual solvent amount 0.08 mass%, crystallinity was 19%. Using the obtained raw fibers, crimping, performs cut to obtain short fibers (raw cotton) length 51 mm.
[0080]
　　[Example 1]
　The meta-type wholly aromatic polyamide fiber, single fiber fineness 1.7 dtex, fiber length 50mm para-type wholly aromatic polyamide fibers (Teijin Aramid Co., trade name "Twaron"), single fiber fineness 3. 3 dtex, fiber length 38mm conductive acrylic fibers (Mitsubishi Chemical Co., Ltd., trade name "COREBRID", sheath: acrylic / core: an eccentric core-sheath type conductive acrylic fiber of conductive carbon-containing polymer) with, meta-type wholly aromatic polyamide fiber: 93 wt%, the para-type wholly aromatic polyamide fiber: 5% by mass, the conductive acrylic fiber: as a 2 wt%, making the spun yarn of the fastest 1/68, Soitogo to obtain a twisted yarn.
[0081]
　Then, by arranging all of the warp and weft of Article yarn, a warp density of 57 present per 2.54 cm, it was woven flat tissue fabric weft density 50 present per 2.54 cm.
[0082]
　The resulting undyed fabric (greige), using jet dyeing machine (Hisaka Works Ltd. hot circular dyeing machine), cationic dye (manufactured by Nippon Kayaku Co., Ltd., Kayacryl Red GL-ED, 15% owf ) and the carrier agent (Dow Chemical Co., Dowanol PPH, in a dyebath containing 40 g / L), and stained for 60 minutes at a temperature increase to 130 ° C. from room temperature.
[0083]
　The resulting dyed fabric appearance quality was good without color unevenness in dark. Also, the meta-type wholly aromatic polyamide fiber and conductive fibers are colored in the same color, both hue difference ΔE was 3 or less. Further, the amount of triboelectric charge is 3.3MyuC / m 2 was as good as. In addition, the remaining flame time was superior to 0 seconds and the flame retardant.
[0084]
　　[Example 2]
　In Example 1, the meta-type wholly aromatic polyamide fiber: 80 wt%, the para-type wholly aromatic polyamide fiber: 5% by mass, the conductive acrylic fibers: so that 15 wt%, 1/68 except that made the spun yarn count, to obtain a dyed fabric in the same manner as in example 1.
[0085]
　The resulting dyed fabric appearance quality was good without color unevenness in dark. Also, the meta-type wholly aromatic polyamide fiber and conductive fibers are colored in the same color, both hue difference ΔE was 3 or less. Further, the amount of triboelectric charge is 1.4MyuC / m 2 was as good as. In addition, the remaining flame time was superior to 0 seconds and the flame retardant.
[0086]
　　[Comparative Example 1]
　As the conductive fibers, single fiber fineness 4.5Dtex, conductive aliphatic polyamide fiber having a fiber length 51 mm (sheath: Nylon 6 / core: an eccentric core-sheath type conductive nylon fiber white metal compound) except for using got a dyed fabric in the same manner as in example 1.
[0087]
　The resulting dyed fabric, the amount of triboelectric charge is 2.4MyuC / m 2 but was as good as, appearance quality conductive aliphatic polyamide fibers was observed uneven color not colored. In addition, the remaining flame time was superior to 0 seconds and the flame retardant.
[0088]
　　Example 3
　Poly isophthalamide fibers (Teijin Ltd. Teijinconex (TM) neo (trade name), single fiber fineness 1.7 dtex, fiber length 51 mm), conductive acrylic fiber (Mitsubishi Chemical Co., Ltd. Core Brides (trade name), para-type wholly aromatic polyamide fibers (Teijin aramid KK Twaron (registered trademark) TW1072, single fiber fineness 1.7 dtex, fiber length 51 mm) is in this order 85/10/5 (mass%) spun yarn uniformly cotton mixing with cotton mixing ratio of (twist Z direction, the number of 800 to 950 times / m, cotton count 40/1 twist) and doubling and twisting at double twister (S direction 900 times / m) and then subjected to steam set 120 ° C. × 30 minutes as a twist stopping sets, to obtain a 2 Hongo Itoitojo.
[0089]
　Also, was obtained by the same three Hongo Itoitojo plus conductive thread to those doubling the yarn (Teijin (Ltd.) B-TCF U300HX, total fineness 31dtex / 5 filaments).
[0090]
　Then, the two Hongo Itoito conditions and 3 Hongo using the Itoito conditions, about 2 wt arranged 3 Hongo Itoito Article with a pitch of each width 2.02Cm (3 Hongo Itoito conditions of the warp % equivalent) was warping the warp Shi tailoring creel. Sizing the resulting warping beam was performed shedding, the warp preparation by performing pull through. Further, as the weft, using the 2 Hongo Itoito conditions.
[0091]
　Then, warp density of 69 per 2.54 cm, were woven 2/2 twill tissue fabric with weft density 62 present per 2.54 cm.
[0092]
　Obtained against a conventional method by Kaihan Yui the raw machine, desizing scouring in open-width non tension scouring machine (Sofusa), cylinder drying, singeing and stained, performs a finishing set (180 ℃ × 45 ~ 90 seconds) , weight per unit area 5.4Oz / Yd 2 to give the finishing Han.
[0093]
　Then, conduct dyeing the fabric under the following conditions, colored poly isophthalamide fibers and conductive acrylic fibers contained in the fabric.
(Dyeing conditions)
　cationic dye produced by Nippon Kayaku Co., Ltd., trade name: Kayacryl Red GL-ED 6.0% owf, swelling agent 40 g / L, acetate 3 cc / L, dispersing agent 1 cc / L, sodium nitrate 25 g / L
bath ratio; 1:20
temperature × time; 130 ° C. × 60 minutes
　ATPV value 8.7Cal / cm 2 are, were acceptable (level 2 clear).
[0094]
　　[Example 4]
　In Example 3, para-type wholly aromatic polyamide fibers (Teijin Aramid KK Twaron (registered trademark) TW1072, single fiber fineness 1.7 dtex, fiber length 51 mm) instead of, co polyparaphenylene - 3,4 'oxydiphenylene terephthalamide (PPODPA) fibers (Teijin Ltd. Technora (TM)) was used to was in the same manner as in example 3. ATPV value 8.9Cal / cm 2 are, it was acceptable (Level 2 clear).
[0095]
　　[Example 5]
　In the actual example 3, the poly meta-phenylene isophthalamide fibers in place of (Teijin Ltd. Teijinconex (TM) neo (trade name), single fiber fineness 1.7 dtex, fiber length 51 mm), Porimeta except for using phenylene isophthalamide fibers (Teijin Ltd. Teijinconex (TM) FRNB3 single fiber fineness 1.7 dtex, fiber length 51 mm) were treated as in example 3. ATPV value 8.9Cal / cm 2 are, it was acceptable (Level 2 clear).
[0096]
　　[Example 6]
　In Example 3, after the weaving design density Density 62 present per 2.54 cm, weaving 1/1 plain weave fabric with weft density 52 present per 2.54 cm, except for this in the same manner as in Example 3 a basis weight 4.5Oz / yd 2 to give a finishing reaction of, was evaluated in the same manner. ATPV value 6.7Cal / Cm 2 is, was rejected.
[0097]
　　[Comparative Example 2]
　In Example 3, except that the fiber material and cotton mixing amount of 0 wt% conductive acrylic fiber was treated similarly evaluated. ATPV value 7.8Cal / Cm 2 is, was rejected.
Industrial Applicability
[0098]
　According to the present invention, excellent flame retardancy, appearance quality as well antistatic preferably provided fabrics and their preparation and fiber products also have protection performance against electrical arc, its industrial value it is extremely large.

WE claims

[Requested item 1]
　A fabric comprising a meta-type wholly aromatic polyamide fiber and conductive fibers, wherein the meta-type wholly aromatic polyamide fiber and conductive fiber formed by both colored fabric.
[Requested item 2]
　The meta-type wholly aromatic polyamide fiber and the conductive fibers comprise the same dye, fabric according to claim 1.
[Requested item 3]
　It said dye is a cationic dye, fabric according to claim 2.
[Requested item 4]
　The meta-type wholly aromatic polyamide fiber and the conductive fiber is colored in the same color, fabric according to any one of claims 1-3.
[Requested item 5]
　The conductive fiber is conductive acrylic fiber, fabric according to any one of claims 1 to 4.
[Requested item 6]
　The conductive acrylic fiber, a core portion containing conductive fine particles, a core-sheath type composite fiber composed of non a sheath portion containing conductive particles, fabric as claimed in claim 5.
[Requested item 7]
　The conductive fibers in the fabric, includes fabric weight versus 1-30 wt%, the fabric according to any one of claims 1 to 6.
[Requested item 8]
　The meta-type wholly aromatic polyamide fiber and the conductive fibers contained in the fabric as a blended yarn, fabric according to any one of claims 1 to 7.
[Requested item 9]
　Furthermore the fabric, para-type wholly aromatic polyamide fibers, polyphenylene sulfide fibers, polyimide fibers, polybenzimidazole fibers, polybenzoxazole fibers, polyamideimide fibers, polyetherimide fibers, pyrolytic Mex ®, and carbon fibers, from consisting includes one or more selected from the group, fabric according to any one of claims 1-8.
[Requested item 10]
　Fabric having a weave, fabric according to any one of claims 1-9.
[Requested item 11]
　The spun yarn comprising meta-type wholly aromatic polyamide fiber and antistatic fiber is arranged in all warp and weft fabric of claim 10.
[Requested item 12]
　Basis weight of the fabric ~ 9.0Oz 3.0 / yd 2 is in the range of, fabric according to any one of claims 1 to 11.
[Requested item 13]
　Frictional charge amount measured by JIS L1094-2014 C method 7.0MyuC / m 2 or less, the fabric according to any one of claims 1 to 12.
[Requested item 14]
　JIS L1091-1992 A-4 method after flame time in the flammability measured as defined in (12 sec flame contact) is less than 1.0 seconds, the fabric according to any one of claims 1 to 13.
[Requested item 15]
　Using the fabric according to any of claims 1 to 14, protective clothing, work clothing, protective clothing, camouflage, happi, and any textile product selected from the group consisting of apron.
[Requested item 16]
　Meta-type subjected to dyeing the fabric comprising wholly aromatic polyamide fibers and conductive fibers, the manufacturing method of a fabric according to claim 1.