JP2020002475A - Fabric and textile product - Google Patents

Abstract

To provide a fabric and a textile product excellent in not only flame retardancy but also stretchability, surface quality and ant-pilling property.SOLUTION: A fabric comprises both of a spun yarn containing a flame retardant fiber having a limiting oxygen index of 25 or more measured according to JIS K7201, and an elastic fiber. The fabric has a pilling of grade 3 or greater measured in accordance with JIS L1076-1992 A method (ICI type, for 10 hours).SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a fabric and a fiber product excellent not only in flame retardancy but also in elasticity, surface quality and anti-pilling property.

  2. Description of the Related Art Flame-retardant fabrics have conventionally been used as work clothes worn by people engaged in work that may be exposed to fire, such as firefighting, electric power, and chemical companies. This flame-retardant fabric mainly uses flame-retardant fibers such as meta-type wholly aromatic polyamide fibers and para-type wholly aromatic polyamide fibers, and it is generally considered difficult to impart elasticity. .

  In order to impart elasticity to the fabric using the flame-retardant fiber, a method using an elastic yarn (for example, see Patent Document 1, Patent Document 2, Patent Document 3) or heat-setting after twisting the flame-retardant fiber is used. A twisting method (for example, see Patent Literature 4, Patent Literature 5, and Patent Literature 6) has been proposed.

  However, fabrics using elastic yarns have problems such as normal use due to low heat resistance, flame retardancy and chemical resistance, particularly low chlorine resistance, and a sharp decrease in stretchability during washing. In addition, in the case of a fabric using a flame-retardant fiber that has been twisted and then heat-set and then untwisted, the weaving, the post-processing step, and the problem that the stretchability is reduced during wearing and sufficient performance and quality as the fabric cannot be obtained. There was a problem that the cost was high.

  On the other hand, these stretchable flame-retardant fabrics have problems of poor surface quality and pilling due to the difference in yarn foot.

JP 2003-193314 A JP 2006-124865 A JP 2007-9378 A JP 2001-248027 A JP 2005-307429 A JP 2008-190103 A

  The present invention has been made in view of the above background, and an object of the present invention is to provide a fabric and a fiber product which are excellent in not only flame retardancy but also elasticity, surface quality and anti-pilling property.

  The present inventors have conducted intensive studies to achieve the above-mentioned object, and as a result, by skillfully devising yarns and the like constituting a fabric, not only flame retardancy, but also excellent elasticity, surface quality and anti-pilling properties were excellent. The present inventors have found that a fabric and a fiber product can be obtained, and have made extensive studies to complete the present invention.

  Thus, according to the present invention, "a spun yarn containing a flame-retardant fiber having a limiting oxygen index measured by JIS K7201 of 25 or more and a stretchable fiber, which is measured by JIS L1076-1992A method ICI type 10 hours Characterized in that the pilling to be performed is a third-class or higher. "

At this time, the flame-retardant fiber is preferably a meta-type wholly aromatic polyamide fiber having a residual solvent amount of 0.1% by weight or less. Preferably, the meta-type wholly aromatic polyamide fiber is dyed. At that time, it is preferable that the meta-type wholly aromatic polyamide fiber is dyed using a swelling agent. The crystallinity of the meta-type wholly aromatic polyamide fiber is preferably in the range of 15 to 25%. The meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber is a main structural unit having a repeating structure in an aromatic polyamide skeleton containing a repeating structural unit represented by the following formula (1). It is preferable that the aromatic polyamide is obtained by copolymerizing different aromatic diamine components or aromatic dicarboxylic acid halide components as the third component so as to be 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide. .
-(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 parallel axis direction.
In this case, the aromatic diamine serving as the third component is preferably represented by Formulas (2) and (3), or the aromatic dicarboxylic acid halide is preferably represented by Formulas (4) and (5).
_{H 2 N-Ar2-NH 2} ··· formula (2)
_{H 2 N-Ar2-Y-} Ar2-NH 2 ··· 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 selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group. Or a functional group, and X represents a halogen atom.

  Further, in the spun yarn, it is preferable that a blending ratio of the meta-type wholly aromatic polyamide fiber is in a range of 2 to 100% by weight. Further, in the spun yarn, it is preferable that a twist coefficient is in a range of 2.5 to 4.5. Further, it is preferable that the elastic fiber is a composite fiber in which two components are bonded in a side-by-side type or an eccentric core-sheath type. At that time, the two components constituting the conjugate fiber may be any combination selected from the group consisting of polytrimethylene terephthalate / polytrimethylene terephthalate, polytrimethylene terephthalate / polyethylene terephthalate, and polyethylene terephthalate / polyethylene terephthalate. preferable. Further, it is preferable that the spun yarn and the elastic fiber are twisted or covered.

In the fabric of the present invention, the weight ratio of the flame-retardant fiber is 40% by weight or more based on the weight of the fabric, and the weight ratio of the stretchable fiber is in the range of 1 to 25% by weight based on the weight of the fabric. Is preferred. Preferably, the fabric is a woven or knitted fabric. In the fabric, the elongation percentage in the warp direction and / or the weft direction is preferably in the range of 3 to 50%. Further, in the fabric, the elongation recovery rate in the warp direction and / or the weft direction is preferably 70% or more. Further, in the fabric, it is preferable that the value of the yarn foot difference represented by the following equation is in the range of 3 to 20%.
Yarn difference = ((spun yarn length <cm> -10 <cm>) / 10 <cm>) x 100
However, the cloth is cut 10 cm in the direction in which the spun yarn is arranged, and the initial load when measuring the spun yarn length is set to the fineness of the spun yarn / 36 <gr>.
In the fabric of the present invention, the wicking test is preferably carried out for 10 seconds or less after the washing is performed 10 times by the JIS L10217-1998 103 method, as measured by the wicking test ISO17617.
Further, according to the present invention, any one selected from the group consisting of protective clothing, firefighting and fire protection clothing, firefighting activity clothing, rescue clothing, workwear, police uniform, SDF clothing, and military uniform is provided by using the cloth described above. Are provided.

  ADVANTAGE OF THE INVENTION According to this invention, in addition to flame retardancy, the fabric and fiber products excellent in elasticity, surface quality, and anti-pilling property are obtained.

  Hereinafter, embodiments of the present invention will be described in detail. The fabric of the present invention comprises a spun yarn containing a flame-retardant fiber having a limiting oxygen index measured by JIS K7201 of 25 or more (hereinafter, sometimes simply referred to as “flame-retardant fiber”) and an elastic fiber. Including.

  Here, as the flame-retardant fiber, meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polyparaphenylenebenzoxazole fiber, polybenzimidazole fiber, polyimide fiber, polyetherimide fiber, polyamideimide fiber , Carbon fiber, polyphenylene sulfide fiber, polyvinyl chloride fiber, flame retardant rayon, modacrylic fiber, flame retardant acrylic fiber, flame retardant polyester fiber, flame retardant vinylon fiber, melamine fiber, fluorine fiber, flame retardant wool, flame retardant cotton, etc. Is exemplified. One or more of these flame-retardant fibers can be used.

  Among them, the following meta-type wholly aromatic polyamide fibers, ie, metaphenylene isophthalamide fibers, are useful from the viewpoint of exhibiting an excellent limiting oxygen index and excellent mechanical properties. As commercially available products, "Conex Neo" (trade name) manufactured by Teijin Limited, "Nomex" (trade name) manufactured by DuPont, and the like are known. Also, para-type wholly aromatic polyamide fibers, that is, paraphenylene terephthalamide fibers (commercially available products such as "Twaron" (trade name) manufactured by Teijin Limited, "Kevlar" (trade name) manufactured by Toray Dupont Co., Ltd.), It is also preferable to mix paraphenylene-3,4′-oxydiphenylene terephthalamide fiber (a commercially available product, “Technola” (trade name) manufactured by Teijin Limited).

  These flame-retardant fibers contain additives such as antioxidants, ultraviolet absorbers, heat stabilizers, flame retardants, titanium oxide, coloring agents, and inert fine particles, as long as the objects of the present invention are not impaired. Is also good.

  In the flame-retardant fiber, the fiber may be a long fiber (multifilament) or a short fiber. In particular, short fibers having a fiber length of 25 to 200 mm (more preferably 30 to 150 mm) are preferred for blending with other fibers. The single fiber fineness is preferably in the range of 1 to 5 dtex.

  The meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber is a fiber made of a polymer in which 85 mol% or more of the repeating units are m-phenylene isophthalamide. Such a meta-type wholly aromatic polyamide may be a copolymer containing the third component in a range of less than 15 mol%.

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

  The meta-type wholly aromatic polyamide may contain an alkylbenzenesulfonic acid onium salt. Examples of the alkylbenzenesulfonic acid onium salt include hexylbenzenesulfonic acid tetrabutylphosphonium salt, hexylbenzenesulfonic acid tributylbenzylphosphonium salt, dodecylbenzenesulfonic acid tetraphenylphosphonium salt, and dodecylbenzenesulfonic acid tributyltetradecylphosphonate. Compounds such as a sodium salt, tetrabutylphosphonium dodecylbenzenesulfonate, and tributylbenzylammonium dodecylbenzenesulfonate are preferably exemplified. Among them, tetrabutylphosphonium dodecylbenzenesulfonate or tributylbenzylammonium dodecylbenzenesulfonate is easily available, has good thermal stability, and has a high solubility in N-methyl-2-pyrrolidone. It is preferably exemplified.

  The content ratio of the above-mentioned alkylbenzenesulfonic acid onium salt is at least 2.5 mol%, preferably 3.0 to 7.0 mol, based on poly-m-phenyleneisophthalamide in order to obtain a sufficient effect of improving dyeability. % Is preferred.

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

The polymer used for the meta-type wholly aromatic polyamide fiber has a repeating structure in an aromatic polyamide skeleton containing a repeating structural unit represented by the following formula (1) for the purpose of improving dyeing resistance and discoloration resistance. It is also possible to copolymerize an aromatic diamine component or an aromatic dicarboxylic acid halide component, which is different from the main structural unit, as the third component in an amount of 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide. It is.
-(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 parallel axis direction.

It is also possible to copolymerize as the third component. Specific examples of the aromatic diamine represented by the formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, Examples include acetylphenylenediamine, aminoanisidine, benzidine, bis (aminophenyl) ether, bis (aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene, and the like. Specific examples of the aromatic dicarboxylic acid dichloride 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.
_{H 2 N-Ar2-NH 2} ··· formula (2)
_{H 2 N-Ar2-Y-} Ar2-NH 2 ··· 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 selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group. Or a functional group, and X represents a halogen atom.

  The crystallinity of the meta-type wholly aromatic polyamide fiber is 5 to 35% in that the dye has a good exhaustion property and is easily adjusted to a target color even with a smaller amount of dye or weak dyeing conditions. Preferably, there is. Further, the content is more preferably from 15 to 25% from the viewpoint that the uneven distribution of the dye on the surface hardly occurs, the discoloration resistance is high, and the dimensional stability required for practical use can be secured.

  In addition, when the residual solvent amount of the meta-type wholly aromatic polyamide fiber is 0.1% by weight or less (preferably 0.001 to 0.1% by weight), the fiber shrinks by dyeing, and the density increases, In addition, since the gap is eliminated by increasing the count, the anti-pilling property is improved, which is preferable.

  The meta-type wholly aromatic polyamide fiber can be produced by the following method, and in particular, the crystallinity and the amount of the residual solvent can be adjusted to the above ranges by the method described later.

  The method of polymerizing the meta-type wholly aromatic polyamide polymer is not particularly limited. For example, the solution weight described in Japanese Patent Publication No. 35-14399, U.S. Pat. No. 3,360,595, and Japanese Patent Publication No. 47-10863 may be used. A legal method or an interfacial polymerization method may be used.

  The spinning solution is not particularly limited, but an amide-based solvent solution containing an aromatic copolyamide polymer obtained by the above solution polymerization or interfacial polymerization may be used, or the polymer may be converted from the polymerization solution. It may be used after isolation and dissolution in an amide solvent.

  Examples of the amide-based solvent used herein include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, and the like. In particular, N, N-dimethylacetamide Is preferred.

  The copolymerized aromatic polyamide polymer solution obtained as described above is further stabilized by containing an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and at a lower temperature, which is preferable. Preferably, the alkali metal salt and alkaline earth metal salt are at most 1% by weight, more preferably at most 0.1% by weight, based on the total weight of the polymer solution.

  In the spinning / coagulation step, the spinning solution (meta-type wholly aromatic polyamide polymer solution) obtained above is spun into a coagulation solution and coagulated.

  The spinning device is not particularly limited, and a conventionally known wet spinning device can be used. The number of spinning holes, arrangement state, hole shape, etc. of the spinneret need not be particularly limited as long as the spinning can be performed stably. For example, the number of spinning holes is 1,000 to 30,000, and the spinning hole diameter is 0.05. A multi-hole spinneret or the like for a soup having a thickness of 0.2 mm may be used.

  Further, the temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) when spinning from the spinneret is suitably in the range of 20 to 90 ° C.

  As a coagulation bath used for obtaining the fiber, an aqueous solution of an amide-based solvent, preferably having an NMP concentration of 45 to 60% by mass, containing substantially no inorganic salt at a bath solution temperature of 10 to 50 ° C is used. Used. If the concentration of the amide-based solvent (preferably NMP) is less than 45% by mass, the skin will have a thick structure, the washing efficiency in the washing step will be reduced, and it will be difficult to reduce the residual solvent amount of the fiber. On the other hand, when the concentration of the amide-based solvent (preferably NMP) exceeds 60% by mass, uniform coagulation cannot be carried out to the inside of the fiber. Becomes difficult. In addition, the immersion time of the fiber in the coagulation bath is suitably in the range of 0.1 to 30 seconds.

  Subsequently, an amide-based solvent, preferably an aqueous solution having an NMP concentration of 45 to 60% by mass, in a plastic stretching bath in which the temperature of the bath solution is in the range of 10 to 50 ° C., at a stretching ratio of 3 to 4 times. Perform stretching. After the stretching, washing is sufficiently performed through an aqueous solution having an NMP concentration of 20 to 40% by mass at 10 to 30 ° C, and subsequently to a warm water bath at 50 to 70 ° C.

  The washed fiber is subjected to a dry heat treatment at a temperature of 270 to 290 ° C. to obtain a meta-type wholly aromatic polyamide fiber satisfying the above-mentioned range of crystallinity and residual solvent amount.

  Most preferably, the spun yarn comprises only the flame-retardant fibers described above, but may also contain non-flame-retardant fibers (fibers having a limiting oxygen index of less than 25 as measured by JIS K7201). At this time, examples of the non-flame-retardant fiber include polyester fiber, nylon fiber, rayon fiber, polynosic fiber, lyocell fiber, acrylic fiber, vinylon fiber, cotton, hemp, and wool. One or more of these non-flame-retardant fibers can be used.

  These non-flame retardant fibers contain additives such as antioxidants, ultraviolet absorbers, heat stabilizers, flame retardants, titanium oxide, coloring agents, and inert fine particles, as long as the objects of the present invention are not impaired. Is also good.

  In the non-flame retardant fiber, the fiber may be a long fiber (multifilament) or a short fiber. In particular, short fibers having a fiber length of 25 to 200 mm (more preferably 30 to 150 mm) are preferred for blending with other fibers. The single fiber fineness is preferably in the range of 1 to 5 dtex.

  In the spun yarn, the total fineness may be appropriately selected in consideration of the surface appearance, heat resistance, thermal protection, stretchability, texture, and the like according to the application. In particular, the fineness of the spun yarn is 58 dtex (English cotton). A range of 100 counts of single yarn) to 580 dtex (10 counts of English cotton count) is preferable.

  In the spun yarn, the twist coefficient K is preferably in the range of 2.5 to 4.5 from the viewpoint of physical properties and flexibility of the fabric. Here, T = K√n, where T is the number of twists per inch (2.54 cm), n is the English cotton count, and K is the twist coefficient. Further, the spun yarn may be a single yarn or a double yarn.

  In the present invention, examples of the stretchable fiber include a conjugate fiber (conjugate fiber), a false-twisted crimped yarn, an elastic yarn (urethane fiber), and a polyester-based elastomer fiber). Among them, composite fibers (conjugate fibers) are preferred.

  The conjugate fiber is a conjugate fiber in which two components are bonded in a side-by-side type or an eccentric core-sheath type. Since the composite yarn contained in the fabric of the present invention includes not only the spun yarn but also such a composite fiber, the composite fiber takes a form of a three-dimensional coil crimp in the heat treatment step of the fabric, and the composite yarn has elasticity. As a result, the fabric is also given elasticity.

  Here, examples of the two components forming the composite fiber include combinations of polyester / polyester, polyester / nylon, and the like. More specifically, combinations of polytrimethylene terephthalate / polytrimethylene terephthalate, polytrimethylene terephthalate / polyethylene terephthalate, polyethylene terephthalate / polyethylene terephthalate, and the like are preferable. At that time, it is preferable to make the intrinsic viscosities different from each other. Further, additives such as an antioxidant, an ultraviolet absorber, a heat stabilizer, a flame retardant, titanium oxide, a colorant, and inert fine particles may be contained.

  In the conjugate fiber, the shape of the fiber is not particularly limited, and may be a long fiber (multifilament) or a short fiber, but a long fiber (multifilament) is preferable for obtaining excellent elasticity.

  The total fineness and single fiber fineness of the conjugate fiber are appropriately selected depending on the application, and are preferably in the range of 20 to 200 dtex in total fineness and 0.5 to 10.0 dtex in single fiber fineness.

  In the present invention, the spun yarn and the stretchable fiber are preferably included in a fabric as a composite yarn of both. At this time, the weight ratio of the stretchable fiber contained in the composite yarn is 2 to 40% by weight (more preferably, the weight ratio of the stretchable fiber to the weight of the composite yarn in order to achieve both flame retardancy and stretchability). (4 to 30% by weight, particularly preferably 4 to 20% by weight).

  In the composite yarn, the composite method is not particularly limited, but is preferably a twisted yarn or a covering yarn. More specifically, using the above-mentioned spun yarn and stretchable fibers such as conjugate fibers, a commercially available up twister, a covering machine, an Italian twisting machine, a double twister, etc., are plied or covered. Is preferred. At that time, the twist prevention set may be implemented according to required quality. As the twist-stopping set of the composite twisted yarn, a vacuum steam set used for setting a normal spun yarn can be used. The temperature at the time of setting the composite twisted yarn is preferably in the range of 50 to 95 ° C (more preferably 50 to 85 ° C). If the twist setting temperature of the composite ply-twisted yarn is too high, the stretchability of the finally obtained fabric may be impaired.

  In the fabric of the present invention, in order to obtain excellent flame retardancy, the weight ratio of the flame-retardant fiber is 40% by weight or more (preferably 60 to 95% by weight, particularly preferably 75 to 95% by weight) with respect to the weight of the fabric. (% By weight) is important. If the weight ratio of the flame-retardant fiber is small, the flame retardancy may be undesirably reduced.

  Further, it is preferable that the weight ratio of the elastic fiber is in the range of 1 to 25% by weight based on the weight of the fabric. If the weight ratio of the stretchable fiber exceeds 25% by weight with respect to the weight of the fabric, it is not preferable because the flame is easily transmitted along the stretchable fiber and easily burns. On the other hand, when the weight ratio of the stretchable fiber is less than 1% by weight, the stretchability of the fabric may decrease, which is not preferable.

  The fabric structure of the fabric is not particularly limited, but is preferably a woven or knitted fabric. In the case of a woven fabric, examples include a flat structure, a twill structure, a satin structure, and ripstop of each structure. In the case of a knit, a machine knit, a crochet knit, a bar needle knit, an Afghan knit, a lace knit, and the like are exemplified. For example, in the case of a woven fabric, the composite yarn may be entirely disposed in the warp direction and / or the weft direction, or the spun yarn and the composite yarn may be arranged, for example, in a ratio of 1: 1, 2: 1, 3: They may be arranged at an arrangement ratio of 1, 1: 2, 1: 3. The method of knitting and weaving is not particularly limited, and a method using a normal knitting machine or a loom may be used.

  Next, by subjecting such a fabric to a heat treatment such as refining, relaxation, dyeing treatment, and setting, the composite fiber in which the two components contained in the fabric are bonded in a side-by-side type or an eccentric core-sheath type is subjected to three-dimensional coil crimping. Takes the form and gives the fabric elasticity.

  The dyeing treatment is preferably performed using a swelling agent. Examples of the swelling agent include methanol, ethanol, propanol, isopropyl alcohol, benzyl alcohol, acetone, acetophenone, NMP, DMSO, DMF, ethylene glycol, and acetonitrile. It is characterized in that it is treated with at least one selected from propylene or ethylene glycol phenyl ether, or a commercially available swelling agent, but it swells in consideration of the dyeing environment (processing capacity, working environment, etc.) and in consideration of environmental load reduction. It is preferable to use an agent.

  Various types of fabrics having functions such as water-absorbing, water-repellent, raising, flame-retardant, ultraviolet shielding or antibacterial agents, deodorants, insect repellents, phosphorescent agents, retroreflective agents, negative ion generators, etc. Processing may be additionally applied.

  Since the fabric thus obtained has the above-mentioned constitution, it is excellent not only in flame retardancy but also in stretchability, surface quality and anti-pilling property.

  Here, the stretchability of the fabric is preferably such that the elongation percentage in the warp direction and / or the weft direction is in the range of 3 to 50%. Further, as the elongation recovery rate of the fabric, the elongation recovery rate in the warp direction and / or the weft direction is preferably 70% or more (more preferably 73 to 99%). Further, as for flame retardancy, it is preferable that the limiting oxygen index of the fabric measured by JIS K7201 is 25 or more (more preferably 25 to 40).

Further, in the fabric, it is preferable that the value of the yarn foot difference represented by the following equation is in the range of 3 to 20%.
Yarn difference = ((spun yarn length <cm> -10 <cm>) / 10 <cm>) x 100
However, the cloth is cut 10 cm in the direction in which the spun yarn is arranged, and the initial load when measuring the spun yarn length is set to the fineness of the spun yarn / 36 <gr>.

  Further, it is preferable that the wicking test is performed for 10 seconds or less after the washing is performed 10 times according to the JIS L10217-1998 103 method in the wicking test ISO17617.

  Next, the fiber product of the present invention is obtained by using the above-mentioned cloth. Since such a fiber product uses the above-mentioned cloth, it is excellent not only in flame retardancy but also in elasticity, surface quality and anti-pilling property. Such textile products include firefighting clothing, fire protection clothing, working clothing, racing suits for motor sports, work clothing, gloves, hats, vests, and various industrial materials (seats, tents, membrane materials, hoods, building materials, housing materials, vehicles) Interior materials). Further, the work clothes include work clothes for a steel mill or a steel factory, work clothes for welding work, work clothes in an explosion-proof area, and the like. The gloves include work gloves used in the aircraft industry, information equipment industry, precision equipment industry, and the like that handle precision parts.

Next, Examples and Comparative Examples of the present invention will be described in detail, but the present invention is not limited by these. In addition, each measurement item in an Example was measured by the following method.
(1) Flame retardancy The limiting oxygen index (LOI) was measured according to JIS K7201: 1999 (combustion test method for polymer materials by the oxygen index method) and used as an index of flame retardancy.
(2) Elasticity The elongation rate and elongation recovery rate were measured according to JIS L1096: 2011 (method B, constant load method).
(3) Flammability According to JIS L1091 A-4 Annex 8, after-flame time, residual dust time, and carbonization length were measured and used as indices of flammability.
(4) Measurement of yarn foot difference The fabric was cut by 10 cm in the direction in which the spun yarn was arranged, and calculated by the following equation. However, the initial load at the time of measuring the spun yarn length was the fineness of the spun yarn / 36 <gr>.
Yarn difference = ((spun yarn length <cm> -10 <cm>) / 10 <cm>) x 100
(5) Pilling measurement Pilling measurement was performed according to JIS L1076 A method (ICI 10 hr).
(6) Wicking measurement Wicking measurement was performed according to ISO17617.
(7) Amount of Residual Solvent About 8.0 g of the raw fiber was collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and weighed (M1). Subsequently, the fiber was subjected to reflux extraction in methanol for 1.5 hours using a Soxhlet extractor to extract an amide-based solvent contained in the fiber. The fiber after the extraction was taken out, vacuum-dried at 150 ° C. for 60 minutes, allowed to cool in a desiccator, and weighed (M2). The amount of the solvent remaining in the fiber (the weight of the amide-based solvent) was calculated by the following equation using the obtained M1 and M2.
Residual solvent amount (%) = [(M1-M2) / M1] × 100
(8) Crystallinity Using an X-ray diffractometer (RINT TTRIII, manufactured by Rigaku Corporation), the raw fibers were arranged in a fiber bundle having a diameter of about 1 mm, mounted on a fiber sample table, and the diffraction profile was measured. The measurement conditions were a Cu-Kα radiation source (50 kV, 300 mA), a scanning angle range of 10 to 35 °, continuous measurement of 0.1 ° width measurement, and scanning at 1 ° / min. Air scattering and incoherent scattering were corrected by linear approximation from the measured diffraction profile to obtain a total scattering profile. Next, the crystal scattering profile was obtained by subtracting the amorphous scattering profile from the total scattering profile. The crystallinity was determined by the following equation from the area intensity of the crystal scattering profile (crystal scattering intensity) and the area intensity of the total scattering profile (total scattering intensity).
Crystallinity (%) = [crystal scattering intensity / total scattering intensity] × 100

[Production of meta-type wholly aromatic aramid fiber]
The meta-type wholly aromatic aramid fiber was produced by the following method.
20.0 parts by mass of a polymetaphenylene isophthalamide powder having an intrinsic viscosity (IV) of 1.9, produced by an interfacial polymerization method according to the method described in JP-B-47-10863, was cooled to -10 ° C. The suspension was suspended in 80.0 parts by mass of cooled N-methyl-2-pyrrolidone (NMP) to form a slurry. Subsequently, the suspension was heated to 60 ° C. and dissolved to obtain a transparent polymer solution. To the polymer solution, 3.0% by mass of 2- [2H-benzotriazol-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol powder (solubility in water: 0% by mass relative to the polymer) was added. .01 mg / L), and the mixture was dissolved under reduced pressure to obtain a spinning solution (spinning dope).

[Spinning / coagulation process]
The above spinning dope was discharged from a spinneret having a hole diameter of 0.07 mm and a number of holes of 500 into a coagulation bath at a bath temperature of 30 ° C and spun. The composition of the coagulation liquid was water / NMP = 45/55 (parts by mass), and the coagulation liquid was spun by discharging into a coagulation bath at a yarn speed of 7 m / min.

[Plastic stretching bath stretching step]
Subsequently, the film was stretched at a stretch ratio of 3.7 times in a plastic stretching bath having a composition of water / NMP = 45/55 at a temperature of 40 ° C.

[Washing process]
After stretching, it was washed with a 20 ° C water / NMP = 70/30 bath (immersion length 1.8 m), followed by a 20 ° C water bath (immersion length 3.6 m), and further washed with a 60 ° C warm water bath (immersion length 5 .4m).

[Dry heat treatment process]
The washed fiber was subjected to dry heat treatment with a hot roller having a surface temperature of 280 ° C. to obtain a meta-type wholly aromatic aramid fiber.

[Physical properties of fibrils]
Physical properties of the obtained meta-type wholly aromatic aramid fiber were a fineness of 1.7 dtex, a residual solvent amount of 0.08% by weight, a crystallinity of 19%, and an LOI of 26. The obtained raw fiber was crimped and cut to obtain a staple fiber (raw cotton) having a length of 51 mm.

[Example 1]
As a spun yarn, in the spinning process, a single fiber having a single fiber fineness of 1.7 dtex, a cut length (fiber length) of 51 mm, an LOI of 26, and a short fiber made of the meta-type wholly aromatic aramid fiber, and a single fiber fineness of 1.7 dtex, Polyparaphenylene terephthalamide (PPTA) fiber ("Twaron" (trade name) manufactured by Teijin Limited) having a cut length (fiber length) of 51 mm and an LOI of 25, a single fiber fineness of 3.3 dtex, and a cut length (fiber length) ) Short fibers made of a conductive fiber (Mitsubishi Chemical's “Coribrit ET10” (trade name)) having a length of 38 mm are blended at a weight ratio of 93: 5: 2 in this order, and the number of twists is 24T / 2.54 cm (twist coefficient = 3). .4), a 40th single yarn was obtained with an English cotton count.

  On the other hand, as a conjugate fiber (stretchable fiber), two kinds of polytrimethylene terephthalates having different intrinsic viscosities are bonded in an eccentric core-sheath type, with a total fineness of 40 dtex / 24 filaments, an elongation of 26%, and a boiling water shrinkage of 55.0. % Multifilament (long fiber) was prepared.

  Next, the two spun yarns are combined and twisted with a double twister at a twist number of 20.9 T / 2.54 cm, and then set with a vacuum steam setting machine at a set temperature of 120 ° C. and a set time of 20 minutes. To obtain a flame-resistant plied yarn A.

  Further, two spun yarns and one conjugate fiber (multifilament) were combined and twisted with a double twister at a twist number of 19.8 T / 2.54 cm, and then with a vacuum steam set machine. Twisting was set under the conditions of a setting temperature of 70 ° C. and a setting time of 20 minutes to obtain a composite yarn B.

  Next, 100% (whole amount) of the flame-retardant ply twisted yarn A is arranged on the warp, and 100% (whole amount) of the composite yarn B is arranged on the weft, and the woven fabric density is 54 warps / 2.54 cm, 63 wefts / The woven fabric was woven with a 2/1 twill at 2.54 cm.

  The woven fabric was baked, scoured and set (temperature: 180 ° C. × time: 30 seconds), and subjected to the following dyeing processing.

[Method of dyeing fabric]
(Staining conditions)
The temperature was raised from room temperature at a rate of 2 ° C./min in the following dyeing bath, and dyeing was performed at 130 ° C. for 60 minutes.
・ Cation dye (Kayacryl Blue GSL-ED) 3% owf
・ Sodium nitrate 25 g / l
・ Acetic acid 1 g / l
・ Swelling agent 40 g / l
・ Bath ratio 1:20
(Reduction cleaning conditions)
The obtained dyed product was washed in the following reducing bath.
・ Reducing bath: hydrosulfite 1g / l, sodium carbonate 1g / l
・ Bath ratio; 1:20
・ Temperature × time: 90 ° C. × 20 minutes Next, after drying at 120 ° C. in a dryer, heat treatment was performed at 160 ° C. for 30 seconds to obtain a dyed cloth.

  In the obtained woven fabric, the woven fabric density was 68 / 2.4 cm, weft 64 / 2.54 cm, the weight ratio of the non-flame-retardant fiber was 11.0% by weight, the limiting oxygen index was 29.0, and the weft elongation was A favorable elasticity of 10.0% was obtained, and the elongation recovery rate was 85%. Table 1 shows the evaluation results.

  Next, when work clothes were obtained using the woven fabric, they were excellent not only in flame retardancy but also in elasticity, surface quality and anti-pilling property.

[Example 2]
As spun yarn, a short fiber composed of the same meta-type wholly aromatic aramid fiber as in Example 1 and polyparaphenylene terephthalamide (PPTA) having a single fiber fineness of 1.7 dtex, a cut length (fiber length) of 51 mm, and an LOI of 25 were used. ) Fiber ("Twaron" (trade name) manufactured by Teijin Limited) and a conductive fiber having a short fiber fineness of 3.3 dtex and a cut length (fiber length) of 38 mm ("Cabrit E10" manufactured by Mitsubishi Chemical Corporation) Name) and a short fiber composed of polyethylene terephthalate fiber (manufactured by Teijin Limited) having a single fiber fineness of 1.7 dtex, a cut length (fiber length) of 51 mm, and an LOI of 21 were produced in a weight ratio of 84: 5: 2 in this order. : 9 in the ratio of 9.87 T / 2.54 cm (twist coefficient = 3.3), and a 40th single yarn was obtained with an English cotton count. The evaluation results are shown in Table 1.

[Example 3]
In Example 1, two types of polytrimethylene terephthalate having different intrinsic viscosities were bonded in an eccentric core-sheath type as a composite fiber, with a total fineness of 84 dtex / 24 filaments, an elongation of 41%, and a boiling water shrinkage of 42.0%. The procedure was the same as in Example 1 except that a multifilament (long fiber) was used. Table 1 shows the evaluation results.

[Example 4]
The knitting was performed in the same manner as in Example 1 using only the same composite yarn B as in Example 1 and using a 20-gauge single-port knitting machine. Table 1 shows the evaluation results.

[Comparative Example 1]
Example 1 is the same as Example 1 except that the composite yarn B was not used and the flame-retardant twisted yarn A was woven with 100% of the warp and weft. Table 2 shows the evaluation results.

[Example 5]
In Example 1, two kinds of polytrimethylene terephthalates having different intrinsic viscosities were bonded as conjugate fibers in an eccentric core-sheath type, with a total fineness of 165 dtex / 24 filaments, an elongation of 41%, and a boiling water shrinkage of 42.0%. The procedure was the same as in Example 1 except that a multifilament (long fiber) was used. Table 2 shows the evaluation results.

[Example 6]
The composite yarn obtained in Example 5 was knitted using a 20-gauge single-knitting machine using 100% of the composite yarn, and the knitting was performed in the same manner as in Example. Table 2 shows the evaluation results.

[Comparative Example 2]
Example 1 was the same as Example 1 except that the amount of the residual solvent in the meta-type wholly aromatic aramid fiber was changed to 2 to 3% by weight. Table 2 shows the evaluation results.

  ADVANTAGE OF THE INVENTION According to this invention, in addition to flame retardancy, the textiles and fiber products excellent in elasticity, surface quality, and anti-pilling property are provided, and the industrial value is very large.

Claims (19)

  A spun yarn containing a flame-retardant fiber having a limiting oxygen index of 25 or more measured according to JIS K7201 and a stretchable fiber, and a pilling measured at JIS L1076-1992 A method ICI type 10 hours with a class of 3 or more. A cloth characterized by the following.   The fabric according to claim 1, wherein the flame-retardant fiber is a meta-type wholly aromatic polyamide fiber having a residual solvent amount of 0.1% by weight or less.   The fabric according to claim 2, wherein the meta-type wholly aromatic polyamide fiber is dyed.   The fabric according to claim 3, wherein the meta-type wholly aromatic polyamide fiber is dyed using a swelling agent.   The fabric according to any one of claims 1 to 4, wherein the crystallinity of the meta-type wholly aromatic polyamide fiber is in a range of 15 to 25%. The meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber has a different aromatic structure from the main structural unit of the repeating structure in the aromatic polyamide skeleton containing the repeating structural unit represented by the following formula (1). An aromatic polyamide obtained by copolymerizing an aromatic diamine component or an aromatic dicarboxylic acid halide component as a third component in an amount of 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide. 5. The flame-retardant fabric according to any one of 5.
-(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 parallel axis direction. The fabric according to claim 6, wherein the aromatic diamine serving as the third component is represented by Formulas (2) and (3), or the aromatic dicarboxylic acid halide is represented by Formulas (4) and (5).
_{H 2 N-Ar2-NH 2} ··· formula (2)
_{H 2 N-Ar2-Y-} Ar2-NH 2 ··· 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 selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group. Or a functional group, and X represents a halogen atom.   The fabric according to any one of claims 1 to 7, wherein in the spun yarn, a blending ratio of the meta-type wholly aromatic polyamide fiber is in a range of 2 to 100% by weight.   The fabric according to any one of claims 1 to 8, wherein the spun yarn has a twist coefficient in a range of 2.5 to 4.5.   The fabric according to any one of claims 1 to 9, wherein the elastic fiber is a composite fiber in which two components are bonded in a side-by-side type or an eccentric core-sheath type.   11. The composite according to claim 10, wherein the two components constituting the composite fiber are any combination selected from the group consisting of polytrimethylene terephthalate / polytrimethylene terephthalate, polytrimethylene terephthalate / polyethylene terephthalate, and polyethylene terephthalate / polyethylene terephthalate. The described fabric.   The fabric according to any one of claims 1 to 11, wherein the spun yarn and the elastic fiber are twisted or covered.   The weight ratio of the flame-retardant fiber is 40% by weight or more based on the weight of the fabric, and the weight ratio of the stretchable fiber is in the range of 1 to 25% by weight based on the weight of the fabric. The fabric according to any one of the above.   The fabric according to any one of claims 1 to 13, wherein the fabric is a woven or knitted fabric.   The fabric according to any one of claims 1 to 14, wherein the fabric has an elongation ratio in a warp direction and / or a weft direction in a range of 3 to 50%.   The fabric according to any one of claims 1 to 15, wherein the fabric has an elongation recovery rate in a warp direction and / or a weft direction of 70% or more. The fabric according to any one of claims 1 to 16, wherein a value of a yarn foot difference represented by the following formula is in a range of 3 to 20%.
Yarn difference = ((spun yarn length <cm> -10 <cm>) / 10 <cm>) x 100
However, the cloth is cut 10 cm in the direction in which the spun yarn is arranged, and the initial load when measuring the spun yarn length is set to the fineness of the spun yarn / 36 <gr>.   The fabric according to any one of claims 1 to 17, wherein the fabric has a wicking test of ISO17617 of 10 seconds or less after being washed 10 times according to JIS L10217-1998 103 method.   The cloth according to any one of claims 1 to 18, wherein the cloth is selected from the group consisting of protective clothing, fire and fire protection clothing, fire fighting clothing, rescue clothing, workwear, police uniform, SDF clothing, and military clothing. Any textile products.