JP6570703B2 - COLORED ORGANIC FIBER AND FABRIC, AND METHOD FOR PRODUCING APPAREL AND FABRIC - Google Patents

Description

  The present invention relates to a colored organic fiber that is dark and excellent in flame retardancy, and a fabric, a garment, and a method for manufacturing the fabric using the organic fiber.

  Conventionally, as a method of coloring a flame-retardant fabric containing organic fibers such as meta-type aromatic polyamide fibers, a method of adding a pigment to organic fibers or a method of dyeing a fabric using a carrier agent is known.

  However, it has been difficult to obtain a product having excellent darkness by the method of incorporating a pigment into an organic fiber. On the other hand, the method of dyeing using a carrier agent is not sufficient in terms of flame retardancy.

  In order to solve such a problem, for example, Patent Documents 1 to 3 propose using core-sheath structured yarn. However, when the core-sheath structure yarn is used, there is a problem that it takes a lot of time and cost, and a problem that the flame retardant property is not sufficient because it is necessary to use a normal synthetic fiber inferior in flame retardancy for the sheath yarn. there were. Further, for example, Patent Document 4 proposes to wash a fabric after dyeing it using a carrier agent, but it has not been sufficient in terms of flame retardancy.

JP 2009-249758 A JP 2009-209488 A JP 2003-147651 A JP 2012-207348 A

  The present invention has been made in view of the above-described background, and an object thereof is a colored organic fiber that is dark and excellent in flame retardancy, a fabric and a garment using the organic fiber, and a fabric. It is in providing the manufacturing method of.

  As a result of intensive studies to achieve the above-mentioned problems, the inventor of the present invention has a dark color and flame retardancy by reducing the amount of the carrier agent remaining in the organic fiber in the organic fiber dyed with the carrier agent. The inventors have found that an excellent organic fiber can be obtained, and have further studied earnestly to complete the present invention.

  Thus, according to the present invention, there is provided “colored organic fiber, characterized in that the content of the carrier agent is 1.8% by mass or less with respect to the mass of the fiber”.

  In that case, it is preferable that the content rate of the said carrier agent exists in the range of 0.1-1.8 mass% with respect to fiber mass. The carrier agent may be DL-β-ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methyl. Phenethyl alcohol, 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamic alcohol, p-anisyl alcohol, benzhydrol, benzyl alcohol, propylene glycol phenyl ether, ethylene It is preferably at least one selected from the group consisting of glycol phenyl ether and N-methylformanilide. The organic fiber may be a meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide (PI). ) Fiber, polysulfonamide (PSA), polyether ether ketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber It is preferably any one selected from the group consisting of

  The organic fiber is preferably a meta-type wholly aromatic polyamide fiber having a crystallinity of 15 to 25%. Moreover, it is preferable that the said organic fiber is a meta-type wholly aromatic polyamide fiber whose residual solvent amount is 1.0 mass% or less. Moreover, it is preferable that the said organic fiber is a meta type wholly aromatic polyamide fiber whose residual solvent amount is 0.1 mass% or less. In that case, it is preferable that the residual solvent is any one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide.

  The organic fiber is a meta-type wholly aromatic polyamide fiber, and the meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber includes a repeating structural unit represented by the following formula (1). In the aromatic polyamide skeleton, an aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main structural unit of the repeating structure is 1 to 10 mol% based on the total amount of the repeating structural unit of the aromatic polyamide as the third component. An aromatic polyamide copolymerized as described above is preferable.

-(NH-Ar1-NH-CO-Ar1-CO) -... Formula (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.

  In that case, it is preferable that the aromatic diamine 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—Ar ₂ —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 it is a functional group and X represents a halogen atom.

Moreover, according to this invention, the fabric containing the said colored organic fiber is provided. At that time, the fabric is polyester fiber, cellulose fiber, polyamide fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, acetate fiber, and polycarbonate fiber. It is preferable to include any one or more selected from the group consisting of: Moreover, it is preferable that any fiber which comprises a fabric contains a flame retardant. Moreover, it is preferable that any fiber which comprises a fabric contains a ultraviolet absorber or a ultraviolet reflector. Moreover, it is preferable that the fabric weight is 300 g / m ² or less. Moreover, it is preferable that LOI is 26 or more. Moreover, it is preferable that the afterflame time is 1 second or less in a vertical combustion test (JIS L1091A-4 method 3s flame contact). Moreover, it is preferable that the lightness index L value is 80 or less.

  Moreover, according to this invention, the clothing which uses the said fabric is provided.

  In addition, according to the present invention, there is provided a method for producing a fabric containing the above-described colored organic fiber, wherein the fabric is dyed with a carrier agent, and then the fabric is heated at a temperature of 90 to 140 ° C. By washing with water for 10 to 30 minutes, there is provided a method for producing a fabric in which the content of the carrier agent contained in the organic fiber is 1.8% by mass or less relative to the mass of the fiber.

  ADVANTAGE OF THE INVENTION According to this invention, the organic fiber which was the colored organic fiber and was dark and excellent in the flame retardance, the fabric and clothing using this organic fiber, and the manufacturing method of a fabric are obtained.

  Hereinafter, embodiments of the present invention will be described in detail. First, the present invention is directed to colored organic fibers. In such an organic fiber, the content of the carrier agent is 1.8% by mass or less with respect to the mass of the fiber.

  Here, the carrier agent is a dyeing assistant and is also referred to as a swelling agent. The kind of carrier agent is not particularly limited. Specifically, L-β-ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol , 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamon alcohol, p-anisyl alcohol, benzhydrol, benzyl alcohol, propylene glycol phenyl ether, ethylene glycol phenyl Examples include ether and N-methylformanilide.

  In the colored organic fiber of the present invention, the type of the organic fiber is not particularly limited. However, in order to obtain excellent flame retardancy, meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) ) Fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide (PI) fiber, polysulfonamide (PSA), polyetheretherketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber and the like are preferable.

  Of these, meta-type wholly aromatic polyamide fibers are preferable. The meta-type wholly aromatic polyamide fiber is a fiber made 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%.

  Such a meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method. The degree of polymerization of the polymer is such that the intrinsic viscosity (IV) measured with an N-methyl-2-pyrrolidone solution having a concentration of 0.5 g / 100 ml is in the range of 1.3 to 1.9 dl / g. Preferably used.

  The meta-type wholly aromatic polyamide may contain an onium salt of alkylbenzene sulfonic acid. Examples of the onium salt of alkylbenzene sulfonate include tetrabutyl phosphonium salt of hexyl benzene sulfonate, tributyl benzyl phosphonium salt of hexyl benzene sulfonate, tetraphenyl phosphonium salt of dodecyl benzene sulfonate, tributyl tetradecyl phosphonate of dodecyl benzene sulfonate. Preferred examples include compounds such as a nium salt, tetrabutylphosphonium salt of dodecylbenzenesulfonate, and tributylbenzylammonium salt of dodecylbenzenesulfonate. Among them, dodecylbenzenesulfonic acid tetrabutylphosphonium salt or dodecylbenzenesulfonic acid tributylbenzylammonium salt is particularly easy to obtain and has good thermal stability and high solubility in N-methyl-2-pyrrolidone. Preferably exemplified.

  The content ratio of the onium salt of alkylbenzene sulfonate is 2.5 mol% or more, preferably 3.0 to 7.0 mol with respect to poly-m-phenyleneisophthalamide in order to obtain a sufficient dyeing effect. Those in the range of% are preferred.

  In addition, as a method of mixing poly-m-phenylene isophthalamide and alkylbenzenesulfonic acid onium salt, a method of mixing and dissolving poly-m-phenyleneisophthalamide in a solvent and dissolving alkylbenzenesulfonic acid onium salt in the solvent. Any of these 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 (2) for the purpose of improving dyeability and resistance to discoloration. It is also possible to copolymerize an aromatic diamine component or aromatic dicarboxylic acid halide component different from the main structural unit of 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide as the third component. It is.

-(NH-Ar1-NH-CO-Ar1-CO) -... Formula (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.

  Moreover, 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 Examples include '-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis (chlorocarbonylphenyl) ether, and the like.

H ₂ N—Ar ₂ —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 it is a functional group and X represents a halogen atom.

  Further, the crystallinity of the meta-type wholly aromatic polyamide fiber is 5 to 35% in that the dye exhaustion is good and it is easy to adjust to the target color even with less dye or weak dyeing conditions. Preferably there is. Furthermore, it is more preferably 15 to 25% in that the surface uneven distribution of the dye hardly occurs, the discoloration resistance is high, and the dimensional stability necessary for practical use can be secured.

  Further, the residual solvent amount of the meta-type wholly aromatic polyamide fiber is 1. The point that the excellent flame retardancy performance of the meta-type wholly aromatic polyamide fiber is not impaired and the surface uneven distribution of the dye hardly occurs and the discoloration resistance is high. It is preferably 0% by mass or less (more preferably 0.1% by mass or less, and still more preferably 0.01 to 0.09% by mass).

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

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

  The spinning solution is not particularly limited. An amide solvent solution containing an aromatic copolyamide polymer obtained by the solution polymerization or interfacial polymerization may be used, or the polymer is isolated from the polymerization solution and dissolved in an amide solvent. It may be used.

  Here, examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like, and in particular, N, N-dimethylacetamide. Is preferred.

  The obtained copolymerized aromatic polyamide polymer solution is further stabilized by containing an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and lower temperature, which is preferable. Preferably, the alkali metal salt and alkaline earth metal salt are 1% by weight or less, more preferably 0.1% by weight or less, 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 coagulating solution and coagulated.

  The spinning device is not particularly limited, and a conventionally known wet spinning device can be used. Further, the number of spinning holes, the arrangement state, the hole shape and the like of the spinneret are not particularly limited. For example, a multi-hole spinneret for sufu having 1,000 to 30,000 holes and a spinning hole diameter of 0.05 to 0.2 mm may be used.

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

  As a coagulation bath used for obtaining the fiber, an aqueous solution substantially containing no inorganic salt and having an amide solvent (preferably NMP) concentration of 45 to 60% by mass is used. It is preferable to use in. If the concentration of the amide solvent (preferably NMP) is less than 45% by mass, the skin has a thick structure, and the cleaning efficiency in the cleaning process may be reduced, making it difficult to reduce the amount of residual solvent in the fiber. . On the other hand, when the concentration of the amide solvent (preferably NMP) exceeds 60% by mass, uniform coagulation cannot be performed up to the inside of the fiber. May become difficult. In addition, as for the immersion time of the fiber in a coagulation bath, the range of 0.1-30 seconds is preferable.

  Subsequently, an amide solvent, preferably an aqueous solution having a concentration of NMP of 45 to 60% by mass, and a stretch ratio of 3 to 4 times in a plastic stretching bath in which the temperature of the bath liquid is in the range of 10 to 50 ° C. It is preferable to perform stretching. After stretching, it is preferable to perform sufficient washing through an aqueous solution having an NMP concentration of 10 to 30 ° C. of 20 to 40% by mass and subsequently a hot water bath of 50 to 70 ° C.

  The washed fibers can be subjected to a dry heat treatment at a temperature of 270 to 290 ° C. to obtain meta-type wholly aromatic aramid fibers that satisfy the above-mentioned ranges of crystallinity and residual solvent amount.

  In the colored organic fiber of the present invention, 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 are preferable in blending with other fibers. The single fiber fineness of the organic fiber is preferably in the range of 1 to 5 dtex.

  In the colored organic fiber of the present invention, the coloring method is preferably a dyeing method using a carrier agent. In particular, a method of dyeing with a cationic dye is preferred for obtaining excellent darkness. The conditions for the dyeing process are not particularly limited.

  In such a colored organic fiber, the content of the carrier agent is 1.8% by mass or less with respect to the mass of the fiber (preferably 0.1 to 1.8% by mass, more preferably 0.1 to 1.0% by mass, and further preferably Is 0.3 to 0.9 mass%). If the content is greater than 1.8% by mass, flame retardancy may be impaired. On the other hand, if the content is less than 0.1% by weight, excellent darkness may not be obtained, and the hot water washing process described later may be complicated.

  As a method of reducing the content of the carrier agent, for example, after dyeing and washing the dyed fabric as necessary, hot water at a temperature of 90 to 140 ° C. (more preferably 110 to 140 ° C.) is used for 10 to 30. A method of washing with hot water for a minute is exemplified.

  Next, the fabric of the present invention is a fabric containing the colored organic fiber. Such a fabric may be composed of only the above-mentioned colored organic fibers, and further, polyester fiber, cellulose fiber, polyamide fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, poly Other fibers such as vinyl chloride fiber, polyvinylidene chloride fiber, acetate fiber, and polycarbonate fiber may be included.

  At that time, it is preferable that the meta-type wholly aromatic polyamide fiber contained in the fabric is 50% by mass or more based on the mass of the fabric because excellent flame retardancy is obtained. The flame retardant fiber, synthetic fiber, regenerated fiber, and natural fiber can be arbitrarily mixed according to the application and use needs. As a more specific example, the meta-type wholly aromatic polyamide fiber is 50 to 98% by mass, the polyester fiber is 2 to 50% by mass, and the cellulosic mass fiber is 0 to 50% and has both dyeability and comfort. It can also be done. The ratio may be adjusted according to the performance to be emphasized.

  Moreover, it is also preferable to include a flame retardant or an ultraviolet absorber or an ultraviolet reflector in any of the fibers constituting the fabric. In that case, in the said ultraviolet absorber, it is preferable that the solubility to water is 0.04 mg / L or less. If the solubility in water is greater than 0.04 mg / L, the ultraviolet absorber may be eluted when dyeing with a carrier agent, which may reduce the light resistance after dyeing.

  The method for producing the fabric is not particularly limited. For example, after obtaining a spun yarn using the organic fiber (or the organic fiber and other fibers), weaving or knitting with a single yarn or twin yarn, dyed with a carrier agent, It is good to wash with hot water by the method.

At that time, the fabric structure is preferably a woven fabric such as plain weave, twill weave, satin, double weave,
A knitted fabric or a non-woven fabric may be used. The method for producing the fabric is not particularly limited. For example, known knitting and knitting machines such as rapier looms and gripper looms can be used.

  Since the obtained fabric uses the organic fiber, it is excellent in dark color and flame retardancy. At that time, the darkness is preferably 80 or less (more preferably 52.5 or less, still more preferably 10 to 52.3) in terms of lightness index L value. Further, as flame retardancy, LOI is preferably 26 or more (more preferably 26 to 40). Moreover, it is preferable that the afterflame time is 25 seconds or less (more preferably 1 second or less) in the vertical combustion test (JIS L1091 A-4 method 3 seconds flame contact).

Further, in the fabric, it is preferred basis weight is 300 g / ^{m 2} or less (preferably 50~250g / ^{m 2).} If the weight per unit area is larger than 300 g / m ² , the lightness of the fabric may be impaired.

Next, the garment of the present invention is a garment using the above-mentioned fabric. Such clothing includes protective clothing,
Fire clothes, fire clothes, rescue clothes, activity clothes, office clothes, motorsport racing suits, work clothes, gloves, hats, vests, etc. are included. In addition, the work clothes include work clothes worn when working in steelworks or steel factories, work clothes for welding work, work clothes in an explosion-proof area, and the like. The gloves include working gloves used in the aircraft industry, the information equipment industry, the precision equipment industry, etc. that handle precision parts.

  Moreover, you may use the said fabric for textiles, such as a curtain, a car seat, and a bag.

Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited by these. Moreover, each physical property in an Example is measured with the following method.
(1) Flame retardancy of fabric (vertical combustion test)
Residual flame time (seconds) was evaluated based on JIS L1091 A-4 method (3 second flame contact).
(2) Amount of residual solvent About 8.0 g of fiber was collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and the fiber mass (M1) was weighed. Subsequently, the fiber was subjected to reflux extraction using a Soxhlet extractor in methanol for 1.5 hours to extract an amide solvent contained in the fiber. The fiber after extraction was taken out, vacuum-dried at 150 ° C. for 60 minutes, allowed to cool in a desiccator, and the fiber mass (M2) was weighed. The amount of solvent remaining in the fiber (amide solvent mass) was calculated by the following formula using the obtained M1 and M2.
Residual solvent amount (%) = [(M1-M2) / M1] × 100
(3) Crystallinity Using an X-ray diffractometer (RINT TTRIII, manufactured by Rigaku Corporation), the fibrils were aligned on a fiber bundle having a diameter of about 1 mm and mounted on a fiber sample table to measure a diffraction profile. The measurement conditions were Cu-Kα radiation source (50 kV, 300 mA), scanning angle range 10 to 35 °, continuous measurement 0.1 ° width measurement, and 1 ° / min scanning. From the measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain a total scattering profile. Next, a crystal scattering profile was obtained by subtracting the amorphous scattering profile from the total scattering profile. The degree of 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
(4) Amount of residual carrier agent Measurement method: A GC / MS sample comprising a fiber sample was packed in a sample tube and measured by ATD. After confirming the carrier agent by qualitative analysis, quantitative analysis was performed under the following conditions.
Calibration curve Dawanol PPH 10.180mg / ml (n-hexane) 0.50 ・ 0.75 ・ 1.00μl
Column: DB-5ms 0.25mm × 28m
Carrier: He
Inject: ATD 350 ℃ × 20min (sample heating) 300 ℃ × 10min (purge)
ColdTrap: 10 ℃
Interface valve transfer: 250 ° C Mass Range 94 108 152
Detecter: GCMS-QP2010
Ion source: 200 ℃
Voltage: 1.35KV (-0.48KV)
Oven: 110 ℃ × 2min 110 ~ 190 ℃ (10 ℃ / min)
Gas flow rate primary = 10: 90 secondary = 1: 4 2.0%
(5) Dark color (L value)
The color was measured with a Macbeth spectrophotometer Color-Eye 3100.
(6) Fabric weight A fabric weight (g / m ² ) was measured according to JIS L1096.

[Example 1]
Meta-type wholly aromatic aramid fibers were produced by the following method.

20.0 parts by mass of polymetaphenylene isophthalamide powder having an intrinsic viscosity (IV) of 1.9 produced by an interfacial polymerization method in accordance with the method described in Japanese Patent Publication No. 47-10863 is placed at −10 ° C. It 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) .01 mg / L) was mixed and dissolved, and depressurized to obtain a spinning solution (spinning dope).
[Spinning and coagulation process]
The spinning dope was spun from a spinning nozzle having a hole diameter of 0.07 mm and a hole number of 500 into a coagulation bath having a bath temperature of 30 ° C. The composition of the coagulation liquid is water / NMP = 45/55 (parts by mass). Spinning was performed by discharging into a coagulation bath at a yarn speed of 7 m / min.
[Plastic stretching bath stretching process]
Subsequently, the film was stretched at a stretching ratio of 3.7 times in a plastic stretching bath having a composition of water / NMP = 45/55 at a temperature of 40 ° C.
[Washing process]
After stretching, the film 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 then a 60 ° C. hot water bath (immersion length 5). 4m) and thoroughly washed.
[Dry heat treatment process]
The washed fiber was subjected to a dry heat treatment with a heat roller having a surface temperature of 280 ° C. to obtain a meta-type wholly aromatic aramid fiber.
[Cut process]
The meta-type wholly aromatic aramid fiber was used for crimping and cutting to obtain a staple fiber (raw cotton) having a length of 51 mm.
[Physical properties of raw cotton]
The physical properties of the obtained meta-type wholly aromatic aramid fiber were as follows: the single fiber fineness was 1.7 dtex, the residual solvent amount was 0.08% by mass, and the crystallinity was 19%.

  On the other hand, as other fiber raw materials, para-type aramid fibers: Teijin Aramid "Twaron (registered trademark)" and conductive yarn (nylon): Solcia "NO SHOCK (registered trademark)" (conducting conductive carbon fine particles Nylon conductive yarn) was prepared.

Next, each staple fiber of meta type fully aromatic aramid fiber (MA) (length 51 mm), para type fully aromatic polyamide (PA) (length 50 mm), nylon conductive yarn (AS) (length 51 mm), MA / PA / AS = 93/5/2 blended spun yarn 40 count / twist yarn, weaved at warp density of 65 / 25.4mm, weft 55 / 25.4mm, with a basis weight of 170g / m ^Two plain texture fabrics were obtained.

The fabric was then treated with the following dyeing recipe and hot water washing recipe.
(Dyeing prescription)
First, it dye | stained with the following prescription.
Cationic dye: Nippon Kayaku Co., Ltd., trade name: Kayacryl Red GL-ED 6.0% owf
Carrier agent: Propylene glycol phenyl ether (Dow Chemical Pdanol PPH) 40 g / L
“40 g / L” means “40 grams per liter of water”.
・ Acetic acid 0.3cc / L
・ Dispersant 0.5cc / L
・ Sodium nitrate 25g / L
・ Bath ratio; 1:20
-Temperature * time; 135 degreeC * 60 minutes Then, the obtained colored fabric was wash | cleaned in the following reduction bath.
・ Bath ratio; 1:20
・ Temperature x time: 90 ° C. × 20 minutes ・ Reduction bath; Hydrosulfite 1 g / L, Soda ash 1 g / L
(Hot water cleaning prescription)
Subsequently, the fabric was washed with hot water at a temperature of 130 ° C. for 20 minutes. Subsequently, the fabric was subjected to a dry heat setting at a temperature of 180 ° C. for 2 minutes.

  Table 1 shows the evaluation results of the obtained fabric.

[Example 2]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes once in the hot water cleaning prescription was changed to 130 ° C. × 20 minutes twice. The evaluation results are shown in Table 1.

[Example 3]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes once in the hot water washing prescription was changed to 120 ° C. × 20 minutes twice. The evaluation results are shown in Table 1.

[Example 4]
The same operation as in Example 1 was performed except that Dawanol PPH 40 g / L in the above dyeing prescription was changed to benzyl alcohol 60 g / L. The evaluation results are shown in Table 1.

[Example 5]
Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. × 20 minutes of the hot water washing prescription is changed to 120 ° C. × 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.

[Example 6]
Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. × 20 minutes of the hot water washing prescription is changed to 120 ° C. × 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.

[Example 7]
Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. × 20 minutes of the hot water washing prescription is changed to 120 ° C. × 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.

[Comparative Example 1]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes of the hot water washing prescription was changed to 90 ° C. × 20 minutes once. The evaluation results are shown in Table 1.

[Example 8]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes of the hot water washing prescription was changed from 90 ° C. × 20 minutes to 5 times. The evaluation results are shown in Table 1.

[Example 9]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes of the hot water washing prescription was changed from 90 ° C. × 20 minutes to 10 times. The results are shown in Table 1.

[Example 10]
The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 30 g / L. The evaluation results are shown in Table 1.

[Example 11]
The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 20 g / L. The evaluation results are shown in Table 1.

[Example 12]
The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 10 g / L. The evaluation results are shown in Table 1.

  ADVANTAGE OF THE INVENTION According to this invention, the organic fiber which was the colored organic fiber and was dark and excellent in the flame retardance, the fabric and clothing using this organic fiber, and the manufacturing method of a fabric are provided, The industrial value is the It is extremely large.

Claims (10)

A fabric comprising colored organic fibers,
The content of the carrier agent in the organic fiber is in the range of 0.1 to 1.5 % by mass relative to the fiber mass, and the carrier agent is DL-β-ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3- Chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol, 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3- Selected from the group consisting of iodobenzyl alcohol, cinnamic alcohol, p-anisyl alcohol, benzhydrol, benzyl alcohol, propylene glycol phenyl ether, ethylene glycol phenyl ether, and N-methylformanilide And the Ruizure one or more, wherein the organic fibers, the amount of residual solvent Ri 0.1 mass% or less of the meta-type wholly aromatic polyamide fiber der a crystallinity of 15 to 25% der Rukoto and,
A fabric having an afterflame time of 1 second or less and a lightness index L value of 80 or less in a vertical combustion test (JIS L1091 A-4 method, 3s flame contact) . The fabric according to claim 1 , wherein the residual solvent is any one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. The meta-type wholly aromatic polyamide that forms the meta-type wholly aromatic polyamide fiber is different from the main constituent unit of the repeating structure in the aromatic polyamide skeleton containing the repeating structural unit represented by the following formula (1). The aromatic polyamide obtained by copolymerizing an aromatic diamine component or an aromatic dicarboxylic acid halide component so as to be 1 to 10 mol% based on the total amount of the repeating structural units of the aromatic polyamide as a third component. The fabric described.
-(NH-Ar1-NH-CO-Ar1-CO) -... Formula (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction. The fabric according to claim 3 , wherein the aromatic diamine 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—Ar ₂ —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 it is a functional group and X represents a halogen atom. The fabric according to claim 1 , wherein the fabric includes a spun yarn composed of the organic fiber, para-type wholly aromatic polyamide fiber, and nylon conductive yarn. The fabric according to claim 1 , wherein any of the fibers constituting the fabric contains a flame retardant. The fabric according to claim 1 , wherein any one of the fibers constituting the fabric contains an ultraviolet absorber or an ultraviolet reflector. The fabric according to claim 1 , wherein the fabric has a basis weight of 300 g / m ² or less. The fabric according to claim 1 , wherein the LOI is 26 or more. The clothing which uses the fabric of Claim 1 .