Technical field
[0001]
The present invention, the uneven structure is developed upon exposure by a flame or heat, to the fabric and multilayer structures fabrics and textiles and a thermal barrier and flame-retardant.
BACKGROUND
[0002]
Various conventional fabric have been proposed as fabric for use in protective clothing, such as a firefighter uniform. For example, Patent Document 1, the outermost layer has a flame retardancy-heat shielding function, the intermediate layer has a moisture-permeable waterproof, it has been proposed a multilayer structure fabric innermost layer with a thermal barrier function. In Patent Document 2, a fabric having a double weave is proposed.
[0003]
　However, it not is said still satisfactory in point of achieving both thermal barrier and flame-retardant.
CITATION
Patent Document
[0004]
Patent Document 1: JP 2010-255129 Patent Publication
Patent Document 2: WO 2007/018082 pamphlet
Summary of the Invention
Problems that the Invention is to Solve
[0005]
　The present invention has been made in consideration of the above situation, and its object is uneven structure is developed upon exposure by a flame or heat, fabrics and multilayer fabrics and textiles and a thermal barrier and flame-retardant It is to provide a.
Means for Solving the Problems
[0006]
　The present inventors have result of intensive investigations to achieve the above object, by thermal shrinkage constituting the fabric by skillfully using two yarns different from each other, concavo-convex structure when exposed by a flame or heat but expressing, it found that a fabric having a thermal barrier and flame retardance obtained, and have completed the present invention by overlapping further intensive studies.
[0007]
　Thus, according to the present invention, "a yarn B heat shrinkage is large thread A and the heat shrinkage rate is small in the warp direction or weft direction, the fabric characterized by comprising arranged alternately." Is provided that.
[0008]
　At that time, it is preferable JIS L1091-1992 A-4 method after flame time in the combustion measured as defined in (12 seconds heating method) is less than 2.0 seconds. Further, the warp-direction or thermal shrinkage in the weft direction is greater yarn A and heat shrinkage and a small thread B, is preferably formed by alternately arranged at intervals of 2 ~ 100 mm. Further, the thermal shrinkage is large yarn A and / or thermal shrinkage is small yarn B, and preferably a spun yarn or filament. The difference HAB dry heat shrinkage of the yarn heat shrinkage is large thread A and the heat shrinkage rate is small B is preferably 10% or more.
Dry heat shrinkage (%) = ((length before test (mm) - Length after test (mm)) / (length before test (mm)) × 100
thermal shrinkage difference HAB (%) = (dry heat shrinkage of the fiber a (%)) - (dry heat shrinkage of the yarn B (%))
　in addition, the yarn heat shrinkage is large yarn a and / or thermal shrinkage is small B is meta- preferably contains aramide fibers and / or para-aramid fibers. in addition, the thermal shrinkage ratio is large thread a comprises a meta-aramid fiber of 50 wt% or more, and para-aramid thermal shrinkage is small yarn B preferably contains fibers 50% by weight or more. in addition, 300 ° C., the thickness difference D (formula) when subjected to a dry heat treatment of 5 minutes is preferably 1.3mm or more.
the thickness difference D = (process fabric thickness d2) after - (pre-treatment of the fabric thickness d1)
　The temperature 300 ° C., by applying a dry heat treatment of 5 minutes, it is preferable to express an uneven structure that is continuous in a stripe shape in the warp direction or weft direction. Further, it is preferable that the moisture permeable waterproof membrane is laminated on one surface of the fabric. At that time, it said moisture-permeable waterproof film is preferably made of fluorine-based film or a polyurethane film or a polyethylene film or a polyester film.
[0009]
　Further, according to the present invention, arranged above the fabric to the middle layer, the multilayer structure fabric formed by laminating the outermost layer and the innermost layer to the intermediate layer. At that time, it is preferable heat shielding (ISO17492) is equal to or more than 3 seconds TPP TIME.
[0010]
　Further, any according to the present invention, obtained by using the above fabric or multilayer structure fabric, which protective clothing, fire protective clothing, firefighting suits, rescue clothing, work wear, police uniforms, it is selected from the group consisting of SDF clothing Kano fiber product is provided.
Effect of the invention
[0011]
　According to the present invention, the uneven structure is developed upon exposure by a flame or heat, fabrics and multilayer fabrics and textiles and a thermal barrier and flame retardancy can be obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012]
In fabric of FIG 1 the present invention, how the uneven structure is not expressed is a diagram schematically illustrating.
In fabric of [2] The present invention is a diagram schematically showing a state in which uneven structure is expressed.
DESCRIPTION OF THE INVENTION
[0013]
　It will be described in detail embodiments of the present invention. First, in the warp direction or weft direction of the fabric of the present invention, the thermal shrinkage ratio is large thread A that (hereinafter, sometimes referred to as "thread A".) And yarn thermal shrinkage rate is small B (hereinafter, "yarn B ' it is also there.) and are arranged alternately. At that time, the thermal shrinkage ratio is large thread A and the heat shrinkage and a small thread B, it is preferable that arranged alternately between the plurality of alternating or one alternating, or a plurality of the one.
[0014]
　That is, in the warp direction or weft direction of the fabric, heat shrinkage is large thread A and the heat shrinkage is as small yarn B, switched alternately at regular intervals. The switching interval is 2 ~ 100 mm (more preferably 4 ~ 60 mm, more preferably 6 ~ 50 mm) is preferred. That is, it is preferable that the heat shrinkage is large thread A and the heat shrinkage is as small yarn B are arranged alternately for each said interval. If such a switching interval is less than or if 2mm exceeds 100 mm, there is a possibility that the uneven structure when the fabric is exposed by flame or heat is not expressed.
[0015]
　The "heat-shrinkage ratio" in the present invention, when subjected to dry heat treatment at 450 ° C. 5 min, a shrinkage of yarn length before and after heat treatment. The difference HAB dry heat shrinkage of the heat shrinkage is large thread A and thread thermal shrinkage rate is small B is 10% or more (preferably 15% or more, more preferably 17 to 40%) is preferably . When the difference HAB such dry heat shrinkage is smaller than 10%, there is a possibility that the uneven structure when the fabric is exposed by flame or heat is not expressed.
Dry heat shrinkage (%) = ((length before test (mm) - Length after test (mm)) / (length before test (mm)) × 100
thermal shrinkage difference HAB (%) = (dry heat shrinkage of the fiber a (%)) - (dry heat shrinkage of the yarn B (%))
　as the yarn heat shrinkage is large thread a and the heat shrinkage rate is small B, the point of the flame retardant in preferably both containing aramid fibers (wholly aromatic polyamide fiber), both aramid fiber and is more preferably made of (wholly aromatic polyamide fiber) only. in particular, the thermal shrinkage ratio is large thread a is meta-aramid fiber 50 to 98% by weight, preferably contains a para-aramid fibers 2 to 50% by weight. the thermal shrinkage rate is low yarn B is a para-aramid fiber 50 to 100 wt% (more preferably para-aramid 80-100% by weight of fibers), 0-50 fold meta-aramid fiber Preferably includes%.
[0016]
　Meta-aramid fibers are generally high heat resistance temperature, and has a characteristic that the thermal shrinkage ratio is large. On the other hand, the para-aramid fibers are generally high heat resistance temperature, and has the property that small thermal shrinkage rate, and strength is large. If meta-aramid fibers constituting the fiber A is larger than 98% by weight, high heat fire upon exposure intensity when pulling the thread B is low, will cut, there is a possibility that uneven structure is not formed. Further, if less than 50 wt% has a low shrinkage rate, there is a possibility that no unevenness structure. If para-aramid fibers constituting the yarn B is less than 50% by weight, when pulled to the yarn A when high heat flame exposure, the strength is insufficient, uneven structure would cut it might not expressed.
[0017]
　Here, meta-aramid fibers are fibers less than 85 mole% of the repeating units consisting of a polymer is a m- phenylene isophthalamide. Such meta-aramid (wholly aromatic polyamide) are may safely be third containing component copolymer in the range of less than 15 mol%.
[0018]
　Such meta-aramid (wholly aromatic polyamide) can be produced by a known interfacial polymerization method conventionally, the polymerization degree of the polymer, the concentration of 0.5 g / 100 ml N-methyl-2- an intrinsic viscosity measured at pyrrolidone solution (I.V.) is in the range of 1.3 ~ 1.9 dl / g is preferably used.
[0019]
　In the meta-aramid (wholly aromatic polyamide) it may be contained 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.
[0020]
　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 (preferably 3.0-7.0 moles %) and it is preferable.
[0021]
　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 etc. is one that may be used used. The thus obtained dope is formed into fibers by a conventionally known method.
[0022]
　Polymer used in the meta-aramid fiber, in such order to improve the dyeing property and tarnish discoloration, the aromatic polyamide backbone comprising repeating structural unit represented by the formula (1) below, the main structure of the repeating structure different aromatic diamine component units or an aromatic dicarboxylic acid halide component, it is also possible way be copolymerized a 1 ~ 10 mol% relative to the total amount of repeating units of the aromatic polyamide as a third component.
[0023]
　　- (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.
[0024]
　It is also possible to copolymerize as a third component, the equation (2), specific examples of the aromatic diamine as shown in (3), 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.
[0025]
　　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.

[0026]
　Further, crystallinity of meta-aramid fibers may exhaustion of dye, in terms of easily adjusted to aim color weak fewer dye or dyeing conditions, it is 5 to 35% 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%.
[0027]
　Further, the residual solvent amount of meta-aramid fibers have excellent points does not impair the flame retardancy and surface localization occurs hardly tarnish discoloration of the dye of the meta-aramid fiber also high points, at 0.1 wt% or less there it is preferable.
[0028]
　The meta-aramid fibers can be produced by the following method, by a method particularly described below, the degree of crystallinity and residual solvent amount can be in the above range.
[0029]
　Solution as the polymerization method of meta-aramid (wholly aromatic polyamide) polymer is not particularly limited, for example, Japanese Patent Publication 35-14399 Patent Publication U.S. Pat. No. 3,360,595, JP-that as described in, JP-B-47-10863 polymerization method, may be used interfacial polymerization method.
[0030]
　The spinning solution is not particularly necessary to limit, 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 isolated, this may be used after dissolved in an amide solvent.
[0031]
　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 It is preferred.
[0032]
　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. Preferably from 1% by weight or less based on the total weight of the alkali metal salts and alkaline earth metal salt polymer solution (more preferably 0.1 wt% or less).
[0033]
　In the spinning and solidification step to solidify by spinning the spinning solution obtained in the above (the meta-aramid polymer solution) into a coagulating liquid.
[0034]
　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 and the like need not be particularly limited, for example, the number of holes of 1000 to 30000, the spinning hole diameter 0.05 of ~ 0.2 mm staple fibers may be used (short fibers) multi-hole spinneret and the like for.
[0035]
　The temperature of the spinning liquid when spinning from a spinneret (meta-aramid polymer solution) is suitably in the range of 20 ~ 90 ° C..
[0036]
　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 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 suitably in the range of 0.1 to 30 seconds.
[0037]
　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.
[0038]
　Fiber after washing can be subjected to a dry heat treatment at a temperature of 270 ~ 290 ° C., to obtain a meta-aramid fiber that satisfies the above range of crystallinity and residual solvent amount.
[0039]
　In the meta-aramid fiber, in the form of fibers, it may be the long fiber (multifilament) or a short fiber. In particular, short fibers of fiber length 25 ~ 200 mm is preferred for blends with other fibers. Further, the range of 1 ~ 5 dtex is preferred as the single fiber fineness.
[0040]
　Examples of commercially available meta-aramid fibers, CONEX (trade name), CONEX (trade name) Neo, etc. Nomex (trade name) and the like.
[0041]
　As the para-aramid fiber, a fiber made of polyamide having an aromatic ring in the main chain, poly -p- phenylene terephthalamide (PPTA) may be the copolymer type copoly-para-phenylene-3,4 ' it may be oxydiphenylene terephthalamide (PPODPA). Examples of commercially available para-aramid fibers, Technora (trademark), etc. Kevlar (trade name) and Twaron (TM) are exemplified.
[0042]
　Further, para-aramid fibers, the meta-aramid fibers in the mixed fibers that may be used, polybenzimidazole fibers, polyimide fibers, polyamideimide fibers, polyetherimide fibers, polyarylate fibers, polyparaphenylene benzobisoxazole fibers, novoloid fibers the flame-retardant acrylic fibers, polychlal fibers, flame-retardant polyester fibers, flame 燃綿 fibers, flame-retardant rayon fibers, flame-retardant vinylon fibers, flame-retardant wool fibers.
[0043]
　The yarn heat shrinkage is large thread A and the heat shrinkage rate is small B is may be the spun yarn (staple fiber) may be filament (long fiber). At that time, as the spinning method, it is preferable to use air jet spinning, ring spinning.
[0044]
　In fabrics of the present invention, the basis weight 300 g / m 2 or less (more preferably 50 ~ 300 g / m 2 is preferably a). A basis weight of 300 g / m 2 relief structure may not be expressed in a large self-weight than.
[0045]
　In fabrics of the invention, the fabric tissue is not limited, may be a fabric may be knitted such through knitted or circular knitted fabric (weft knitted fabric). Among them, the fabric is preferable. Preferably it has a plain weave in the fabric. Basis weight is increased in twill, there is a possibility that the expression of the concavo-convex structure is inhibited by its own weight. Yarn warp direction yarns and the weft direction may be together may be a single yarn Soito. In particular, one of the yarns of the warp direction yarns and weft direction and two-ply yarn, the other is a single yarn, preferably it is possible to maintain the strength while reducing the basis weight.
[0046]
　Also, if the fabric of the present invention is a woven fabric, of the warp and weft constituting the woven fabric only to either (preferably weft only), the thermal shrinkage ratio is large thread A and the heat shrinkage is as small yarn B and are arranged alternately at regular intervals, preferably expressed large uneven structure than if the warp and weft both thermal shrinkage larger yarn a and heat shrinkage is small and the yarn B is disposed.
[0047]
　Method for producing a fabric is not particularly limited, the thermal shrinkage different from two or more other (preferably 2-4 or, especially preferably two) can be knitted jobs by a conventional method using a yarn. At that time, as a preferred loom shuttle loom, rapier loom, an air jet loom and the like. The knitting machine and the like tricot knitting machine and circular knitting machine.
[0048]
　Thus, in the obtained fabric, it is preferable JIS L1091-1992 A-4 method after flame time in the combustion measured as defined in (12 seconds heating method) is less than 2.0 seconds.
[0049]
　In fabrics of the present invention, the thermal shrinkage ratio is large thread A and the heat shrinkage and a small thread B in the warp direction or weft direction, because it is arranged alternately (switched at constant intervals), exposed by a flame or heat is expressed heat shielding properties are improved convex structure when the. At that time, the heat shrinkage ratio is large thread A and the heat shrinkage is small yarn B containing both aramid fibers, preferably also improved flame retardancy. In particular, when the heat shrinkage is large thread A and the heat shrinkage is smaller thread B both consisting only of aramid fibers, provides excellent flame retardancy preferred.
[0050]
　At this time, by performing 300 ° C., dry heat treatment of 5 minutes, it is preferable to express an uneven structure that is continuous in a stripe shape in the warp direction or weft direction. At that time, the thickness difference D is more than 1.3mm represented by the following formula (preferably 1.5 ~ 5.0 mm, more preferably 2.0 ~ 5.0 mm) is preferably. The thickness referred to in the present invention exhibit a sum of the air layer bulging after the dough thickness and dry heat treatment. When measuring the thickness, use a circular load diameter 35 mm, 7 g / cm 2 and that adds pressure.
Fabric Thickness difference D = (thickness after dry heat treatment d2) - (dry heat treatment prior to the thickness d1)
　Further, ISO17492 a defined are 80 kW / m to fabric 2 thickness difference D (below after flame and heat exposure before / expression) or 0.1 mm (more preferably 1.3 mm ~ 5.0 mm, it is preferable particularly preferably 2.0 ~ 5.0 mm). The thickness referred to in the present invention exhibit a sum of the inflated air layer after exposure and fabric thickness. When measuring the thickness, use a circular load diameter 35 mm, 7 g / cm 2 and that adds pressure.
Fabric Thickness difference D = (thickness after flame and heat exposure) - (the flame and heat exposure prior to thickness)
　When the fabric of the present invention is moisture permeable waterproof membrane on one side of the fabric are laminated, not only Breathable waterproof effect is added to the fabric, when exposed by a flame or heat, a larger relief structure expression It preferred to. At that time, it said moisture-permeable waterproof film is preferably made of fluorine-based film or a polyurethane film or a polyethylene film or a polyester film. Preferably laminated to the fabric one side as a method of bonding the fabric.
[0051]
　Next, the multilayer structure fabric of the present invention, arranged above the fabric to the middle layer, the multilayer structure the outermost layer was laminated on one surface of the intermediate layer, formed by laminating the innermost layer to the other surface of the intermediate layer it is a fabric.
[0052]
　Here, the outermost layer is preferably made of a fabric made of meta-aramid fiber and para-aramid fibers. The types of fabrics, but woven or knitted fabric or nonwoven fabric is used, practically the fabric is preferable from the viewpoint of strength. Also, the meta-aramid fiber and para-aramid fibers, filaments, combined filament yarn, can be used in the form of yarn or the like, preferably those used blend to form the spun yarn. The mixing ratio of the para-aramid fibers, based on the total fiber weight constituting the outermost layer is preferably 1 to 70 wt%. The mixing ratio of the para-aramid fibers is less than 1 wt%, the fabric when exposed to flame fracture, i.e. there is a pitting fear. If it exceeds 70 wt%, there is a possibility that the para-aramid fiber abrasion resistance decreases fibrillated.
[0053]
　Also, the thermal barrier coating is comprised of meta-aramid fiber 99-50 wt% and a para-aramid fiber 1-50 wt% of the spun yarn or meta-aramid fibers, a spun yarn or filament composed of only the para-aramid fiber it is preferable that the fabric. Fabric woven or knitted, or nonwoven fabric can be used. As the fabric tissue, in order to prevent the sticky feel when worn, to reduce the area of ​​the fabric directly touches the skin, tissues expressing irregularities during weaving at or dyeing is preferred.
[0054]
　Further, in such a multi-layer structure fabric, it is preferable that moisture permeable waterproof membrane on one side of the fabric disposed in the intermediate layer are laminated. At that time, it said moisture-permeable waterproof film is preferably made of fluorine-based film or a polyurethane film or a polyethylene film or a polyester film. Preferably laminated to the fabric one side as a method of bonding the fabric.
[0055]
　Such multi-layer structure fabric, since the fabric intermediate layer is disposed, by a flame and heat exposure, the fabric (intermediate layer) of the portion exposed to increased expression and heat shielding convex structure. At that time, the thermal shrinkage ratio is large thread A and the heat shrinkage is small yarn B is also improved flame retardancy comprising aramid fibers.
[0056]
　At that time, defined as 80 kW / m to ISO17492 2 by flame and heat exposure, the fabric (intermediate layer) express an uneven structure, the warp direction direction or weft direction (preferably the relief structure via sites exposed it is preferable that the continuous stripes either one of the weft direction only) and.
[0057]
　Further, in such a multi-layer structure fabric is preferably heat shielding (ISO17492) is equal to or more than 3 seconds TPP TIME.
[0058]
　Next, textile products of the present invention, the using of a fabric or a multilayer structure fabric, protective clothing, fire protective clothing, firefighting suits, rescue suits, are selected work wear, police uniforms, from the group consisting of SDF clothing is any of the fiber products. Since such fiber products are using the fabric or multilayer structure fabric, concave-convex structure is expressed when exposed by a flame or heat, having a thermal barrier and flame-retardant.
Example
[0059]
　It explained in detail below Examples and Comparative Examples of the present invention, but the present invention is not limited thereto.
(1) Dry heat shrinkage
　yarns 10mm extracted from the fabric in an electric furnace of 450 ° C. Put 5 minutes, was calculated dry heat shrinkage by the following equation.
Dry heat shrinkage (%) = ((length before test (mm) - Length after test (mm)) / (length before test (mm)) × 100
Measurement of bulge (2)
　15cm × 15cm of samples cut to a size, placed 5 minutes in an electric furnace at temperature 300 ° C., was measured bulge degree of expressed irregular structure (fabric thickness difference D). when measuring thickness, a circle having a diameter of 35mm using the load of the shape, 7 g / cm 2 of pressure was added.
fabric thickness difference D = (thickness after dry heat treatment d2) - (dry heat treatment prior to the thickness
d1) (3) after-flame time
　JIS L1091-1992 a -4 methods the remaining flame time at the combustion measured as defined in (12 seconds heating method) were measured.
(4) heat shielding
　by laminating outermost and intermediate layer, thermal barrier layer, the outermost layer side, 80 kW / m 2 (ISO17492 specified) were exposed. At this time, carrying the sensor to the fabric. after exposure T It was measured P TIME (seconds).
[0060]
　In this case, the outermost layer, polymetaphenylene isophthalamide fibers (manufactured by Teijin Ltd., trade name: Conex) and Koparafeniren-3,4 'oxydiphenylene terephthalamide fibers (Teijin Company Ltd., trade name: Technora) preparative spun yarn weight ratio composed of a heat-fibers weight ratio to 90:10 (count: 40/2) fabric woven in twill 2/1 with (basis weight: 240 g / m 2 ) was used . Barrier polymetaphenylene isophthalamide fibers (manufactured by Teijin Ltd., trade name: Conex) in hot layer and Koparafeniren-3,4 'oxydiphenylene terephthalamide fibers (Teijin Company Ltd., trade name: Technora) and weight ratio of 95: spun yarn comprising a heat-fibers weight ratio to form 5 (count: 40/2) to weaving as waffles tissue, the basis weight 150 g / m 2 was used for.
[0061]
　　[Example 1]
　meta-aramid fibers (MA), para-aramid fibers (PA) yarn was blended with the staple fibers weight ratio of MA / PA = 95/5 (both fiber length of 51 mm) made of 40 count / yarn ply yarns the warp direction, and the weft direction of yarns a, the spun yarn 40 fastest consisting only PA / ply yarn was the weft direction yarn B, the yarn of the yarn a and the weft direction of the weft direction 20mm cycle swapped and B, basis weight 70 g / m by a rapier loom 2 was woven fabric (plain weave). Thereafter, refining conventional method, heat set after staining the meta-aramid fibers, to obtain a fabric.
[0062]
　The MA / PA yarn dry heat shrinkage ratio of 30% (thermal shrinkage ratio is large thread A), PA spun yarn (yarn B thermal shrinkage rate is small) is 0%, HAB was 30%.
[0063]
　The obtained was subjected to 300 ° C. 5 minutes dry heat treatment with respect to the fabric, irregular structure is expressed in the weft direction, the thickness difference became 2.0 mm. In addition, the remaining flame time was 1.0 seconds.
[0064]
　Then, the fabric as an intermediate layer, thermal barrier when used as a laminated structure thermal protection reliability was 3.4 seconds. Then, when to obtain a fireproof clothing made of such a laminated structure, it was excellent in thermal barrier and flame-retardant.
[0065]
　　Example 2
　meta-aramid fiber (MA), para-aramid fibers (PA) yarn was blended with the staple fibers weight ratio of MA / PA = 95/5 (both fiber length of 51 mm) made of 40 count / ply yarn warp, and the weft a, the spun yarn 40 fastest / ply yarn consisting only PA and weft B, interchanging the weft a and wefts B at 10mm period, in rapier loom 70 g / m 2 of fabric ( plain weave) was weaving. Thereafter, refining conventional method, heat set after staining the meta-aramid fibers, to obtain a fabric.
[0066]
　The dry heat shrinkage ratio of MA / PA spun yarn 30%, PA spun yarn with 0%, HAB was 30%.
[0067]
　The obtained was subjected to 300 ° C. 5 minutes dry heat treatment with respect to the fabric, irregular structure is expressed in the weft direction, the thickness difference became 2.0 mm. In addition, the remaining flame time was 1.0 seconds.
[0068]
　Then, the fabric as an intermediate layer, thermal barrier when used as a laminated structure thermal protection reliability was 3.5 seconds.
[0069]
　　[Example 3]
　meta-aramid fibers (MA), para-aramid fibers (PA) yarn was blended with the staple fibers weight ratio of MA / PA = 95/5 (both fiber length of 51 mm) made of 40 count / yarn ply yarns the warp direction, and the weft direction of yarns a, the spun yarn 40 fastest consisting only PA / ply yarn was the weft direction yarn B, the yarn of the yarn a and the weft direction of the weft direction 20mm cycle swapped and B, basis weight 70 g / m by a rapier loom 2 was woven fabric (plain weave). Thereafter, refining conventional method, heat set after staining the meta-aramid fibers, to obtain a fabric.
[0070]
　The MA / PA yarn dry heat shrinkage ratio of 30% (thermal shrinkage ratio is large thread A), PA spun yarn (yarn B thermal shrinkage rate is small) is 0%, HAB was 30%.
[0071]
　The resulting fabric one side polytetrafluoroethylene moisture-permeable waterproof film (Japan Gore-Tex, manufactured by basis weight 35 g / m 2 ) was laminated.
[0072]
　Temperature 300 ° C. To the resulting fabric was subjected to a dry heat treatment of 5 minutes, the uneven structure is expressed in the weft direction, the thickness difference became 2.4 mm. In addition, the remaining flame time was 1.0 seconds.
[0073]
　Then, the fabric as an intermediate layer, thermal barrier when used as a laminated structure thermal protection reliability was 3.4 seconds. Then, when to obtain a fireproof clothing made of such a laminated structure, it was excellent in thermal barrier and flame-retardant.
[0074]
　　[Example 4]
　meta-aramid fiber (MA), para-aramid fibers (PA) yarn was blended with the staple fibers weight ratio of MA / PA = 95/5 (both fiber length of 51 mm) made of 40 count / ply yarn warp, and the weft a, the spun yarn 40 fastest / ply yarn consisting only PA and weft B, interchanging the weft a and wefts B at 10mm period, in rapier loom 70 g / m 2 of fabric ( plain weave) was weaving. Thereafter, refining conventional method, heat set after staining the meta-aramid fibers, to obtain a fabric.
[0075]
　The dry heat shrinkage ratio of MA / PA spun yarn 30%, PA spun yarn with 0%, HAB was 30%.
[0076]
　The resulting fabric one side polytetrafluoroethylene moisture-permeable waterproof film (Japan Gore-Tex, manufactured by basis weight 35 g / m 2 ) was laminated.
[0077]
　Temperature 300 ° C. To the resulting fabric was subjected to a dry heat treatment of 5 minutes, the uneven structure is expressed in the weft direction, the thickness difference became 2.5 mm. In addition, the remaining flame time was 1.0 seconds.
[0078]
　Then, the fabric as an intermediate layer, thermal barrier when used as a laminated structure thermal protection reliability was 3.5 seconds.
[0079]
　　[Example 5]
　In Example 1, the meta-aramid fiber (MA), each staple fiber (both fiber length 51 mm) of the para-aramid fibers (PA) in a weight ratio of MA / PA = 95/5 consisting of blend were spun yarn 40 fastest / ply yarn warp a, and the weft yarn a, the spun yarn 40 fastest consisting only PA / ply yarn warp B, and weft B, interchanging the weft a and wefts B at 20mm cycle and 20mm period interchanging the warp a warps B, the weight per unit area 70 g / m 2 by weaving of the fabric (plain weave), other was obtained similarly to the fabric as in example 1.
[0080]
　Temperature 300 ° C. relative to the cloth was subjected to a dry heat treatment of 5 minutes, the uneven structure is expressed in the warp and weft directions, the thickness difference was smaller than the fabric obtained in Example 1. In addition, the remaining flame time was 1.0 seconds. Then, the fabric as an intermediate layer, thermal barrier when used as a laminated structure thermal protection reliability was 3.3 seconds.
[0081]
　　[Comparative Example
　1] using the MA / PA = 95/5 yarn 40 fastest / ply yarn was blended at a weight ratio of the warp and weft, mass per unit area of 70 g / m 2 was woven fabric (plain weave). Thereafter, refining conventional method, heat set after staining the meta-aramid fibers, to obtain a fabric.
[0082]
　The dry heat shrinkage of the MA / PA yarn was 30%. The temperature 300 ° C. relative to the fabric was subjected to dry heat treatment of 5 minutes, the uneven structure is not expressed.
[0083]
　The resulting fabric as an intermediate layer, thermal barrier when used as a laminated structure thermal protection property was insufficient in 2.0 seconds.
[0084]
　　[Comparative Example
　2] using the MA / PA = 95/5 yarn 40 fastest / ply yarn was blended at a weight ratio of the warp and weft, mass per unit area of 70 g / m 2 was woven fabric (plain weave). Thereafter, refining conventional method, heat set after staining the meta-aramid fibers, to obtain a fabric. Dry heat shrinkage ratio of the MA / PA yarn was 30%.
[0085]
　On one side of the obtained cloth made of polytetrafluoroethylene moisture-permeable waterproof film (Japan Gore-Tex Co., basis weight 35 g / m 2 ) was laminated. Temperature 300 ° C. relative to the fabric was subjected to dry heat treatment of 5 minutes, the uneven structure is not expressed.
[0086]
　The resulting fabric as an intermediate layer, thermal barrier when used as a laminated structure thermal protection property was insufficient in 2.0 seconds.
Industrial Applicability
[0087]
　According to the present invention, the uneven structure is developed upon exposure by a flame or heat, fabrics and multilayer fabrics and textiles and a thermal barrier and flame retardancy is provided and industrial value is extremely large is there.
DESCRIPTION OF SYMBOLS
[0088]
1-1 and 1-2 heat shrinkage is small yarn B is disposed a position
locations 2-1 thermal shrinkage is large yarn A disposed

The scope of the claims
[Requested item 1]
Fabric warp direction or heat shrinkage in the weft direction is greater yarn A and heat shrinkage and a small yarn B is characterized by comprising alternately arranged.
[Requested item 2]
　JIS L1091-1992 A-4 method after flame time in the combustion measured as defined in (12 seconds heating method) is less than 2.0 seconds, the fabric of claim 1.
[Requested item 3]
　Warp direction or thermal shrinkage in the weft direction is greater yarn A and heat shrinkage and small yarn B, composed of alternately disposed at intervals of 2 ~ 100 mm, the fabric according to claim 1 or claim 2.
[Requested item 4]
　Thermal shrinkage of the is larger yarn A and / or thermal shrinkage rate is small yarn B, and spun yarn or filament, fabric according to any one of claims 1-3.
[Requested item 5]
　Difference HAB dry heat shrinkage of less yarn B heat shrinkage is large thread A and the heat shrinkage of the is 10% or more, the fabric according to any crab of claims 1-4.
Dry heat shrinkage (%) = ((length before test (mm) - Length after test (mm)) / (length before test (mm)) × 100
thermal shrinkage difference HAB (%) = (dry heat shrinkage of the yarn a (%)) - (dry heat shrinkage of the yarn B (%))
[Requested item 6]
　Fabric according to the yarn heat shrinkage is large yarn A and / or thermal shrinkage is small B comprises meta-aramid fibers and / or para-aramid fibers, any one of claims 1 to 5.
[Requested item 7]
　Heat shrinkage ratio is large thread A of the comprises a meta-aramid fiber of 50 wt% or more and comprises yarns thermal shrinkage is small B is a para-aramid fiber of 50 wt% or more, in any one of claims 1 to 6 fabric according.
[Requested item 8]
　300 ° C., the thickness difference D when subjected to dry heat treatment for 5 minutes (the following scheme) is is 1.3mm or more, the fabric according to any one of claims 1 to 7.
The thickness difference D = (fabric thickness after processing d2) - (pre-treatment of the dough thickness d1)
[Requested item 9]
　Temperature 300 ° C., by applying a dry heat treatment of 5 minutes, to express an uneven structure that is continuous in the warp direction or weft direction in stripes, fabric according to any one of claims 1-8.
[Requested item 10]
　Moisture permeable waterproof membrane on one side of the fabric are laminated, fabric according to any one of claims 1-9.
[Requested item 11]
　Wherein the moisture-permeable waterproof film, made of fluorine-based film or a polyurethane film or a polyethylene film or a polyester film, fabric of claim 10.
[Requested item 12]
　The fabric according to any one of claims 1 to 11 arranged in an intermediate layer, a multilayer structure fabric formed by laminating the outermost layer and the innermost layer to the intermediate layer.
[Requested item 13]
　Heat shielding (ISO17492) is equal to or more than 3 seconds TPP TIME, multilayer fabric according to claim 12.
[Requested item 14]
　Fabric according to any one of claims 1 to 11 comprising using a multi-layer structure fabric according or claim 12 or claim 13, protective clothing, fire protective clothing, firefighting suits, rescue clothing, work wear, police uniform any textile product is selected from the group consisting of SDF clothing.