Fabric and textile product capable of detecting thermal history

Abstract

To provide a fabric and textile product capable of detecting thermal history through color change when exposed to high temperatures such as flames.SOLUTION: A fabric and textile product capable of detecting thermal history comprises a yarn 1 containing dope-dyed flame-retardant fibers, and a yarn 2 containing meta-type wholly aromatic polyamide fibers dyed with a dye.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to fabrics and textile products capable of detecting a heat history, which can detect whether an operator is in a dangerous state by changing color when the fabric is exposed to a high temperature such as a flame.

Background Art

[0002] In a high-temperature environment such as a fire-fighting operation, when an operator is concentrating on the work, he may not notice that he is in a dangerous state. Further, although it is known that the fabric deteriorates thermally when the fabric is exposed to a high temperature, a fabric made of inherently flame-retardant fiber has little color change when exposed to a high temperature, so that the user may not notice the thermal deterioration of the fabric. On the other hand, fabrics capable of detecting a heat history have been proposed in Patent Documents 1 and 2, but they have not yet been satisfactory.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention has been made in view of the above background, and an object thereof is to provide a fabric and a textile product capable of detecting a heat history by changing color when the fabric is exposed to a high temperature such as a flame.

Means for Solving the Problems

[0005] As a result of intensive studies by the present inventor to achieve the above problems, the present invention has been completed. Thus, the following invention is provided.

[0006] 1. A fabric capable of detecting a heat history, comprising: a yarn 1 containing an inherently flame-retardant fiber; and a yarn 2 containing a meta-type wholly aromatic polyamide fiber colored with a dye. The fabric capable of detecting a heat history is characterized by this composition. 2. The fabric capable of detecting a heat history according to 1 above, wherein the fabric has a woven texture, and based on the yarn 1, the yarn 2 is intermittently arranged as warp and / or weft yarns. 3. The fabric capable of detecting a heat history according to 2 above, wherein the yarn 2 is aligned with the yarn 1. 4. The fabric capable of detecting a heat history according to 2 or 3 above, wherein the yarn 2 is arranged at 1 piece / 4 inches or more as warp and / or weft yarns. 5. The fabric capable of detecting a heat history according to any one of 1 to 4 above, wherein in the yarn 2, the light fastness based on JIS L0843 - 2006 is grade 3 or higher. 6. The fabric capable of detecting a heat history according to any one of 1 to 5 above, wherein the fineness of the yarn 2 is the same as or smaller than that of the yarn 1. 7. The fabric capable of detecting a heat history according to any one of 1 to 6 above, wherein the yarn 2 is exposed on the outer air side as much as or more than the back side (skin side) of the fabric. 8. The fabric capable of detecting a heat history according to any one of 1 to 7 above, wherein the mixing ratio of the inherently flame-retardant fiber in the yarn 1 is equal to the mixing ratio of the meta-type wholly aromatic polyamide fiber colored with a dye in the yarn 2. 9. Any fiber product selected from the group consisting of work clothes, active wear, duty uniforms, flame-retardant protective clothing, arc protective clothing, gloves, protective aprons, and protective members, made using the fabric according to any one of 1 to 8 above.

Advantages of the Invention

[0007] According to the present invention, a fabric and a fiber product capable of detecting a heat history can be obtained, in which when the fabric is exposed to a high temperature such as a flame, it changes color, enabling an operator to detect a dangerous state.

Embodiments for Carrying Out the Invention

[0008] Hereinafter, embodiments of the present invention will be described in detail. First, the yarn 1 contains inherently flame-retardant fibers. Such inherently flame-retardant fibers are flame-retardant fibers having a LOI of 25 or more according to the JIS L 1091 (1999) E-2 method, and those obtained by adding a pigment to the spinning dope are preferred. Further, additives such as an ultraviolet absorber, an antioxidant, a heat stabilizer, a flame retardant, a matting agent, and inert fine particles may be contained.

[0009] Such inherently flame-retardant fibers preferably have a melting point of 300 °C or higher, and examples include wholly aromatic polyamide fibers (meta-type wholly aromatic polyamide fibers and / or para-type wholly aromatic polyamide fibers), polybenzimidazole fibers, polyimide fibers, polyamideimide fibers, oxidized polyacrylonitrile fibers, etc. In particular, inherently flame-retardant meta-type wholly aromatic polyamide fibers and inherently flame-retardant para-type wholly aromatic polyamide fibers are preferred. The yarn 1 may be composed only of these fibers, or further contains one or more of polyamideimide fibers, polyetherimide fibers, polyarylate fibers, polyparaphenylene benzobisoxazole fibers, novoloid fibers, flame-retardant acrylic fibers, polyvinylidene chloride fibers, flame-retardant polyester fibers, flame-retardant cotton fibers, flame-retardant rayon fibers, flame-retardant vinylon fibers, flame-retardant wool fibers, etc.

[0010] Here, the meta-type wholly aromatic polyamide fiber is a fiber composed of a polymer in which 85 mol% or more of the repeating unit is m-phenylene isophthalamide. Such a meta-type wholly aromatic polyamide may be a copolymer containing a third component within a range of less than 15 mol%.

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

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

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

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

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

[0016] As the third component, an aromatic diamine represented by the formula (2) or (3), or an aromatic dicarboxylic acid halide represented by the formula (4) or (5) is preferable. Specific examples of the aromatic diamines represented by the formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylene diamine, methylphenylenediamine, acetylphenylenediamine, aminoanisidine, benzidine, bis(aminophenyl) ether, bis(aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene and the like. Specific examples of the aromatic dicarboxylic acid dichlorides represented by the formulas (4) and (5) include, for example, terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4'-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis(chlorocarbonylphenyl) ether and the like.

[0017] H2N-Ar2-NH2··· Formula (2) H2N-Ar2-Y-Ar2-NH2··· Formula (3) XOC-Ar3-COX ··· Formula (4) XOC-Ar3-Y-Ar3-COX ··· Formula (5) Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom or functional group selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group, and X represents a halogen atom.

[0018] Examples of the pigment used in the present invention include organic pigments such as azo-based, phthalocyanine-based, perinone-based, perylene-based, anthraquinone-based, etc., or inorganic pigments such as carbon black, ultramarine, red iron oxide, titanium oxide, iron oxide, etc., but are not limited thereto.

[0019] Examples of the method for mixing a meta-type wholly aromatic polyamide and a pigment include a method of preparing an amide solvent slurry in which the pigment is uniformly dispersed in an amide solvent and adding the amide solvent slurry to a solution in which the meta-type wholly aromatic polyamide is dissolved in the amide solvent, or a method of directly adding the pigment powder to a solution in which the meta-type wholly aromatic polyamide is dissolved in the amide solvent, etc., but it is not particularly limited. The spinning solution (as-spun meta-type wholly aromatic polyamide polymer solution) thus obtained is formed into fibers through, for example, the following steps.

[0020] The amount of the pigment compounded is preferably 10.0% by weight or less (more preferably 0.1 to 5.0% by weight) based on the meta-type wholly aromatic polyamide. When added in an amount more than 10.0% by weight, the physical properties of the resulting fibers may deteriorate.

[0021] Also, the residual solvent amount of the meta-type wholly aromatic polyamide fiber is preferably 0.1% by weight or less (preferably 0.001 to 0.1% by weight) in terms of not impairing the excellent flame retardant performance of the meta-type wholly aromatic polyamide fiber.

[0022] Also, the crystallinity of the meta-type wholly aromatic polyamide fiber is preferably 5 to 35% in terms of good exhaustion of the dye and easy adjustment to the target color even with less dye or milder dyeing conditions. Further, it is more preferably 15 to 25% in terms of being less likely to cause surface uneven distribution of the dye, having high resistance to color change and fading, and ensuring the dimensional stability required in practical use.

[0023] Also, the residual solvent amount of the meta-type wholly aromatic polyamide fiber is preferably 0.1% by weight or less (preferably 0.001 to 0.1% by weight) in terms of not impairing the excellent flame retardant performance of the meta-type aromatic polyamide fiber.

[0024] In addition, para-type wholly aromatic polyamide fibers are represented by Technora (registered trademark), Kevlar (registered trademark), and Twaron (registered trademark), and are fibers composed of polyamides having aromatic rings in the main chain, which may be poly-p-phenyleneterephthalamide (PPTA) or a copolymer type copolyparaphenylene-3,4'-oxydiphenylene terephthalamide (PPODPA). Particularly preferred are as-received para-type wholly aromatic polyamide fibers.

[0025] In the present invention, the yarn 2 contains meta-type wholly aromatic polyamide fibers colored with a dye. Such meta-type wholly aromatic polyamide fibers are preferably the same as those described above except that they do not contain a pigment. In addition, examples of the dyeing method for the meta-type aromatic polyamide fibers include yarn dyeing and spun yarn dyeing.

[0026] In addition, in the yarn 2, it is preferable that the light fastness based on JIS L0843-2006 is grade 3 or higher. When the fastness of the spun yarn is less than grade 3, deterioration due to light is significant, so it may be difficult to distinguish the color change when exposed to high temperatures.

[0027] In addition, it is preferable that the mixing ratio of the as-received flame-retardant fibers in the yarn 1 is equal to the mixing ratio of the meta-type wholly aromatic polyamide fibers colored with a dye in the yarn 2. By using the same mixing ratio, the physical properties of the fabric can be made uniform.

[0028] It is preferable that the fineness of the yarn 2 is the same as or smaller than that of the yarn 1. By using a finer yarn as the yarn 2 than the yarn 1, it is possible to notify a dangerous state or the heat history of the fabric without affecting the physical properties of the fabric made of the as-received flame-retardant fibers.

[0029] In the fabric of the present invention, the above-mentioned inherently flame-retardant fiber, which is a flame-retardant fiber containing no pigment, may further contain fibers such as polyetheretherketone (PEEK) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber, polyester fiber, acrylic fiber, acrylic-based fiber, aliphatic polyamide fiber, conductive fiber, cellulose fiber, wool, and silk.

[0030] The present invention includes a yarn 1 containing the above-mentioned inherently flame-retardant fiber and a yarn 2 containing meta-type wholly aromatic polyamide fiber colored with a dye. At that time, it is preferable that the fabric has a woven structure, and based on yarn 1, yarn 2 is intermittently arranged in the warp and / or weft. The woven structure is not particularly limited, but plain weave, 2 / 1 twill weave, 2 / 2 twill weave, etc. are suitable. Also, in the warp and / or weft, the ratio of yarn 1 to yarn 2 is preferably 10 to 30 pieces: 1 piece in this order. In particular, when yarn 2 is arranged in the warp and / or weft at 1 piece / 4 inches or more (more preferably 1 to 30 pieces / 4 inches), it is preferable because it is easy for the operator to recognize the discoloration of the fabric when the fabric is heat-exposed.

[0031] In particular, it is preferable that yarn 2 is aligned with yarn 1. Thereby, yarn 2 can be extracted, and the thermal degradation of the fabric can be known without affecting the physical properties of the complete-structured fabric containing yarn 1. Also, by measuring the mechanical properties of the extracted yarn 2, the degradation of the fabric can be predicted without performing a destructive inspection of the fabric.

[0032] Also, it is preferable that yarn 2 is exposed on the outer air side as much as or more than the back surface (skin side) of the fabric. Thereby, the color change of the spun yarn containing meta-type wholly aromatic polyamide fiber colored with a dye when exposed to high temperature can be easily visually recognized.

[0033] Next, the protective product of the present invention is any protective product selected from the group consisting of work clothes, activity clothes, duty uniforms, flame-retardant protective clothing, arc protective clothing, gloves, protective aprons, and protective members made of the above-mentioned fabric. Since such a protective product uses the above-mentioned fabric, when the fabric is exposed to high temperatures such as flames and changes color, the heat history of the fabric can be known. Needless to say, the above-mentioned fabric may also be used for various fiber products such as clothes.

Example

[0034] Next, the examples and comparative examples of the present invention will be described in detail, but the present invention is not limited thereto. Each measurement item in the examples was measured by the following method. (1) Light fastness It was measured based on JIS L0843-2006. (2) Color change of the fabric after heat exposure Based on ISO6942:2002, the color change after exposure to a heat flux of 40 kW / m 2 for 10 seconds was visually confirmed.

[0035] [Example 1] Original-dyeing meta-type wholly aromatic polyamide fiber (manufactured by Teijin Limited, trade name "Teijinconex", single fiber fineness 1.7 dtex, fiber length 51 mm) containing 0.95% by weight of a mixed pigment (Navy Blue) of Pigment Blue60 / Pigment Black7 as a pigment in the fiber, and original-dyeing para-type wholly aromatic polyamide fiber (manufactured by Teijin Limited, trade name "Technora", single fiber fineness 1.7 dtex, fiber length 51 mm) containing 5% by weight of carbon black as a pigment in the fiber were used. A 20 / 1 spun yarn was made so that the original-dyeing meta-type wholly aromatic polyamide fiber was 90% by weight and the original-dyeing para-type wholly aromatic polyamide fiber was 10% by weight, and a double-yarn twisted yarn (yarn 1) was obtained.

[0036] On the one hand, using a readily dyeable meta-type wholly aromatic polyamide fiber dyed by a conventional method (manufactured by Teijin Limited, trade name "Teijinconex neo", single fiber fineness 1.7 dtex, fiber length 51 mm) and a para-type wholly aromatic polyamide fiber dyed by a conventional method (manufactured by Teijin, trade name "Twaron", single fiber fineness 1.7 dtex, fiber length 5 mm), a spun yarn of 20 / 1 was made so that the readily dyeable meta-type wholly aromatic polyamide fiber was 90% by weight and the para-type wholly aromatic polyamide fiber was 10% by weight, and a double yarn twisted yarn (yarn 2) was obtained. The light fastness of the obtained yarn 2 was grade 3.

[0037] Next, using yarn 1 (double yarn) and yarn 2 (double yarn) as warp and weft, with a weaving density of 50 ends / 2.54 cm in the warp direction and 46 picks / 2.54 cm in the weft direction, in the warp direction, yarn 1 (double yarn) and yarn 2 (double yarn) were arranged at a ratio of 24:1, and in the weft direction, yarn 1 (double yarn) and yarn 2 (double yarn) were arranged at a ratio of 23:1 to weave a plain weave fabric. At that time, in both the warp and weft directions, yarn 2 was arranged aligned with yarn 1. The obtained unprocessed fabric (gray fabric) was subjected to a conventional scouring process and heat set at 190 °C to obtain a fabric. The color of yarn 2 changed in the obtained fabric due to heat exposure.

[0038] [Comparative Example 1] In Example 1, a fabric was obtained in the same manner as in Example 1 except that only yarn 1 was used for weaving. No color change was confirmed in the obtained fabric after heat exposure.

Claims

1. A fabric capable of detecting a thermal history, comprising: a yarn 1 containing an inherently flame-retardant fiber; and a yarn 2 containing a meta-type wholly aromatic polyamide fiber colored with a dye. The fabric capable of detecting a thermal history is characterized by this composition.

2. The fabric capable of detecting a thermal history according to Claim 1, wherein the fabric has a woven structure, and based on the yarn 1, the yarn 2 is intermittently arranged in the warp and / or weft.

3. The fabric capable of detecting a thermal history according to Claim 2, wherein the yarn 2 is aligned with the yarn 1.

4. The fabric capable of detecting a thermal history according to Claim 2, wherein the yarn 2 is arranged at 1 piece / 4 inches or more in the warp and / or weft.

5. The fabric capable of detecting a thermal history according to Claim 1, wherein in the yarn 2, the light fastness based on JIS L0843-2006 is grade 3 or higher.

6. The fabric capable of detecting a thermal history according to Claim 1, wherein the fineness of the yarn 2 is the same as or smaller than that of the yarn 1.

7. The fabric capable of detecting a thermal history according to Claim 1, wherein the yarn 2 is exposed on the outside air side as much as or more than the back surface (skin side) of the fabric.

8. The fabric capable of detecting a thermal history according to Claim 1, wherein the mixing ratio of the inherently flame-retardant fiber in the yarn 1 is equal to the mixing ratio of the meta-type wholly aromatic polyamide fiber colored with a dye in the yarn 2.

9. Any fiber product selected from the group consisting of work clothes, active clothes, duty clothes, flame-retardant protective clothes, arc protective clothes, gloves, protective aprons, and protective members, made using the fabric according to any one of Claims 1 to 8.