TW201606150A - Colored organic fiber, fabric and clothing and method for manufacturing fabric - Google Patents

Abstract

The present invention addresses the problem of providing a colored organic fiber that has a deep color and excellent flame retardancy, a fabric and clothing using the organic fiber, and a method for manufacturing a fabric. To solve this problem, provided is a colored organic fiber wherein the content of a carrier agent is controlled to 1.8 mass% or lower relative to the fiber mass. If required, a fabric or clothing can be obtained using the colored organic fiber.

Description

Colored organic fiber and cloth, and method for manufacturing clothing and cloth

The present invention relates to an organic fiber which is colored and which is excellent in flame retardancy and which is excellent in flame retardancy, and a method of producing a fabric, a clothing, and a cloth using the organic fiber.

In the past, as a method of coloring a flame retardant fabric containing an organic fiber such as a meta-type aromatic polyamide fiber, a method of containing a pigment in an organic fiber or a method of dyeing a cloth using a carrier is known.

However, a method of containing a pigment in an organic fiber is difficult to obtain an excellent color tone. On the other hand, the method of dyeing with a carrier cannot be said to be sufficient in terms of flame retardancy.

In order to solve this problem, for example, Patent Document 1 to 3 propose the use of a core-sheath construction wire. However, when the core sheath is used to construct the yarn, there is a problem that time and cost are expensive, or a general synthetic fiber having poor flame retardancy must be used in the sheath yarn, and there is a problem that the flame retardancy is insufficient. Further, for example, in Patent Document 4, it has been proposed to wash the cloth with a carrier and then wash it, but it is still insufficient in terms of flame retardancy.

[Previous Technical Literature] [Patent Document]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-249758

Patent Document 2: Japanese Laid-Open Patent Publication No. 2009-209488

Patent Document 3: Japanese Patent Laid-Open Publication No. 2003-147651

Patent Document 4: Japanese Laid-Open Patent Publication No. 2012-207348

The present invention has been made in view of the above circumstances, and an object thereof is to provide an organic fiber having a colored organic fiber and having excellent color and flame retardancy, a fabric and a clothing using the organic fiber, and a method for producing the cloth.

As a result of the active review of the above-mentioned problems, the present inventors have found that organic fibers dyed with a carrier can be obtained by reducing the amount of the binder remaining in the organic fibers to obtain an organic fiber having a strong color and excellent flame retardancy. The invention has finally been completed.

According to the present invention, there is provided a "colored organic fiber which is a colored organic fiber characterized in that the content of the carrier is set to be 1.8% by mass or less of the fiber mass".

In this case, the content of the carrier is preferably in the range of 0.1 to 1.8% by mass of the fiber mass. Further, the carrier is preferably selected from any one or more of the group consisting of DL-β-ethylphenethyl alcohol, 2- Ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenylethyl alcohol , 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamyl alcohol, p-anisitol, diphenylmethanol (benzhydrol) , benzyl alcohol, propylene glycol phenyl ether, ethylene glycol phenyl ether, and N-methylformanilide. Further, the organic fiber is preferably selected from the group consisting of: a type of wholly aromatic polyamide fiber, a p-type wholly aromatic polyamide fiber, a polybenzoxazole (PBO) fiber, and a poly Benzimidazole (PBI) fiber, polybenzothiazole (PBTZ) fiber, polyimine (PI) fiber, polydecylamine (PSA), polyetheretherketone (PEEK) fiber, polyether quinone imine (PEI) Fiber, polyacrylate (PAr) fiber, melamine fiber, phenol fiber, fluorine fiber, polyphenylene sulfide (PPS) fiber.

Further, the organic fiber is preferably a wholly aromatic polyamine fiber having a degree of crystallization of 15 to 25%. Further, the organic fiber is preferably a wholly aromatic polyamine fiber having a residual solvent amount of 1.0% by mass or less. Further, the organic fiber is preferably a wholly aromatic polyamide fiber having a residual solvent amount of 0.1% by mass or less. In this case, the residual solvent is preferably selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl azoxide. a group of people.

Further, the organic fiber is a meta-type wholly aromatic polyamide fiber, and the type of the wholly aromatic polyamine which forms the inter-type wholly aromatic polyamide fiber is preferably represented by the following formula (1). The aromatic polyamine skeleton in the repeating structural unit is different from the main constituent unit of the repeated structure Aromatic polycondensation in which the total amount of the aromatic diamine component or the aromatic dicarboxylic acid halide component is 1 to 10 mol% with respect to the total amount of the repeating structural unit of the aromatic polyamine as the third component Guanamine.

-(NH-Ar1-NH-CO-Ar1-CO)-...(1)

Among them, Ar1 is a divalent aromatic group having a meta-coordination or a bonding group other than the parallel axis direction.

In this case, the aromatic diamine which is preferably the third component is represented by the formulae (2) and (3), or the aromatic dicarboxylic acid halide is represented by the formulae (4) and (5).

H ₂ N-Ar2-NH ₂ (2)

H ₂ N-Ar2-Y-Ar2-NH ₂ (3)

XOC-Ar3-COX...(4)

XOC-Ar3-Y-Ar3-COX...(5)

Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, and Y is at least one atom selected from a group consisting of an oxygen atom, a sulfur atom and an alkylene group. Base, X represents a halogen atom.

Further, according to the present invention, there is provided a fabric comprising the aforementioned colored organic fiber. At this time, the cloth preferably comprises polyester fiber, cellulose fiber, polyamide fiber, polyolefin fiber, acrylic fiber, ray fiber, cotton fiber, animal hair fiber, polyurethane fiber, polyvinyl chloride. One or more selected from the group consisting of fibers, polyvinylidene chloride fibers, acetate fibers, and polycarbonate fibers. Further, any of the fibers constituting the cloth preferably contains a flame retardant. Further, any of the fibers constituting the cloth preferably contains an ultraviolet absorber or an ultraviolet reflector. Further, the basis weight of the cloth is preferably 300 g/m ² or less. Further, the LOI is preferably 26 or more. Further, the residual fire time measured by the vertical burning test (JIS L1091A-4 method 3s inflammation) is preferably 1 second or shorter. Further, the luminance index L value is preferably 80 or less.

Further, according to the present invention, there is provided a clothing material which is obtained by using the above-mentioned cloth.

Further, according to the present invention, there is provided a method for producing a fabric comprising the above-described method for producing a colored organic fiber, which comprises dyeing a fabric comprising an organic fiber with a carrier, and then subjecting the fabric to a temperature of 90 to 140 ° C. The water is washed in hot water for 10 to 30 minutes, and the content of the carrier contained in the organic fiber is 1.8% by mass or less.

According to the present invention, there is provided an organic fiber which is colored with an organic fiber and which is excellent in flame retardancy and which is excellent in flame retardancy, a cloth and a clothing which use the organic fiber, and a method for producing the cloth.

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

Herein, the aforementioned carrier is a dyeing auxiliary, also known as swelling Agent. The kind of the carrier is not particularly limited. Specific examples are L-β-ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, and -isopropylbenzyl alcohol, 2-methylphenethyl alcohol, 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol , cinnamyl alcohol, p-anisitol, diphenylmethanol, benzyl alcohol, propylene glycol phenyl ether, ethylene glycol phenyl ether, N-methylformanilide.

In the colored organic fiber of the present invention, the type of the organic fiber is not particularly limited, and based on obtaining excellent flame retardancy, it is preferably a meta-type wholly aromatic polyamide fiber or a p-type wholly aromatic polyamide fiber. Polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzothiazole (PBTZ) fiber, polyimine (PI) fiber, polyamine (PSA), polyetheretherketone ( PEEK) fiber, polyetherimide (PEI) fiber, polyacrylate (PAr) fiber, melamine fiber, phenol fiber, fluorine fiber, polyphenylene sulfide (PPS) fiber, and the like.

Among them, a meta-type wholly aromatic polyamide fiber is preferred. The meta-type wholly aromatic polyamide fiber is a fiber made of a polymer having 85% or more of a repeating unit of m-phenylene phthalamide. The meta-type wholly aromatic polyamine may also be a copolymer containing the third component in a range of less than 15 mol%.

The meta-type wholly aromatic polyamine can be produced by an interfacial polymerization method conventionally known. The degree of polymerization of the polymer is preferably in the range of from 1.3 to 1.9 dl/g as measured by a solution of N-methyl-2-pyrrolidone in a concentration of 0.5 g/100 ml.

The above-mentioned meta-type aromatic polyamine may also contain alkylbenzene Sulfonium sulfonate. The sulfonium alkylbenzenesulfonate is preferably exemplified by tetrabutylphosphonium alkylbenzenesulfonate, tributylbenzylsulfonium hexylbenzenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate, twelve A compound such as a tributyltetradecylsulfonium alkylbenzenesulfonate, a tetrabutylphosphonium dodecylbenzenesulfonate, a tributylbenzylammonium dodecylbenzenesulfonate or the like. Among them, tetrabutylphosphonium dodecylbenzenesulfonate or tributylbenzylammonium dodecylbenzenesulfonate is easy to obtain and has good thermal stability, and is good for N-methyl-2-pyrrolidone. The solubility is also high, so it is the best illustration.

The content ratio of the above-mentioned alkylbenzenesulfonate sulfonium salt is preferably 2.5 mol% or more, preferably 3.0 to 7.0 mol, for the poly-m-phenylene phthalic acid to obtain a sufficient dyeing improvement effect. The range of ear %.

In addition, the method of mixing poly-m-phenyl-phenyl phthalic acid with sulfonium alkylbenzene sulfonate can also be used to mix and dissolve poly-m-phenyl-phenyl phthalic acid in a solvent. Any of them may be used in a method in which a sulfonium alkylbenzenesulfonate salt is dissolved in a solvent. The dope thus obtained is formed into fibers by a conventional method.

The polymer used for the inter-type wholly aromatic polyamide fiber may be contained in an aromatic polyamine skeleton containing a repeating structural unit represented by the following formula (2) for the purpose of improving dyeability or fading resistance. The total amount of the aromatic diamine component or the aromatic dicarboxylic acid halide component different from the main constituent unit of the repeated structure is 1 to 10 mol% with respect to the repeated structural unit of the aromatic polyamine as the third component. The method is agglomerated.

-(NH-Ar1-NH-CO-Ar1-CO)-...(1)

Among them, Ar1 is a divalent aromatic group having a meta-coordination or a bonding group other than the parallel axis direction.

Further, specific examples of the aromatic diamine represented by the formulas (2) and (3) which are copolymerized as the third component are, for example, p-phenylenediamine, phenylphenylenediamine, and methylexene. Phenyldiamine, acetamidophenylene diamine, aminyl anisidine, benzidine, bis(aminophenyl)ether, bis(aminophenyl)anthracene, diaminophenylbenzophenone, diamine Azobenzene and the like. Specific examples of the aromatic dicarboxylic acid dichloride represented by the formulas (4) and (5) are, for example, p-xylylene chloride, 1,4-naphthalene dicarboxylic acid chloride, and 2,6-naphthalenedicarboxylate. Chlorine, 4,4'-biphenyldicarboxyfluorene chloride, 5-chlorom-xylylene chloride, 5-methoxyisophthalic acid chloride, bis(chlorocarbonylphenyl)ether, and the like.

H ₂ N-Ar2-NH ₂ (2)

H ₂ N-Ar2-Y-Ar2-NH ₂ (3)

XOC-Ar3-COX...(4)

XOC-Ar3-Y-Ar3-COX...(5)

Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, and Y is at least one atom selected from a group consisting of an oxygen atom, a sulfur atom, and an alkylene group. Base, X represents a halogen atom.

In addition, the degree of crystallization of the meta-type wholly aromatic polyamide fiber is good based on the dye exhaustion, and it is preferably 5~ in terms of easy to adjust to the target color with less dye or dyeing conditions. 35%. In addition, it is difficult to cause the dye to be biased to the surface and the fading resistance is also high. It is also 15 to 25% better in terms of dimensional stability that can be used to ensure practical use.

In addition, the residual solvent amount of the meta-type wholly aromatic polyamide fiber is based on the fact that the excellent flame resistance of the meta-type wholly aromatic polyamide fiber is not impaired, and the dye is less likely to be biased toward the surface and the fading resistance is also high. In particular, it is preferably 1.0% by mass or less (more preferably 0.1% by mass or less, still more preferably 0.01% to 0.09% by mass).

The above-mentioned meta-type wholly aromatic polyamide fiber can be produced by the following method, and in particular, the degree of crystallization or the amount of residual solvent can be made into the above range 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. Sho 35-14399, No. 3360595, and Japanese Patent Publication No. Sho 47-10863 can be used.

The spinning solution is not particularly limited. The amide-based solvent solution containing the aromatic copolymerized phthalamide polymer obtained by the above solution polymerization or interfacial polymerization or the like may be used, or the polymer may be isolated from the polymerized solution to dissolve it in the amide-based solvent. .

Here, the aforementioned guanamine-based solvent can be exemplified by N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl adenine, and the like. More preferably, it is N,N-dimethylacetamide.

The obtained copolymerized aromatic polyamide polymer solution is preferably further stabilized by an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and at a lower temperature. Preferred alkali metal salts and alkaline earth metals The total weight of the salt relative to the polymer solution is 1% by weight or less, preferably 0.1% by weight or less.

In the spinning and solidifying step, the spinning solution (inter-type wholly aromatic polyamine polymer solution) obtained above is spun into a coagulating liquid to be solidified.

The spinning device is not particularly limited, and a conventional wet spinning device can be used. Further, the number of spinning holes, the arrangement state, the shape of the holes, and the like of the spinning nozzle are not particularly limited. For example, a porous spinning die for a staple fiber having a number of holes of 1,000 to 30,000 and a spinning aperture of 0.05 to 0.2 mm can be used.

Further, the temperature of the spinning solution (inter-type wholly aromatic polyamine polymer solution) when spun from the spinning nozzle is preferably in the range of 20 to 90 °C.

The coagulation bath used for obtaining the fiber preferably contains substantially no inorganic salt, and preferably has a concentration of 45 to 60% by mass of the guanamine solvent (preferably NMP) in the range of the bath temperature of 10 to 50 °C. Aqueous solution. When the concentration of the guanamine-based solvent (preferably NMP) is less than 45% by mass, the structure of the skin layer is thick, and the cleaning efficiency in the washing step is lowered, and it is difficult to reduce the amount of residual solvent of the fiber. On the other hand, when the concentration of the guanamine-based solvent (preferably NMP) exceeds 60% by mass, uniform solidification cannot be performed until it reaches the inside of the fiber. Therefore, it is difficult to reduce the amount of residual solvent of the fiber. Further, the immersion time of the fibers in the coagulation bath is preferably in the range of 0.1 to 30 seconds.

Next, preferably, the amide-based solvent is preferably an aqueous solution having a concentration of NMP of 45 to 60% by mass and a bath temperature of 10 to 50 ° C. The plastic stretching bath is extended at a stretching ratio of 3 to 4 times. After the extension, it is preferably passed through an aqueous solution having a NMP concentration of 20 to 40% by weight at 10 to 30 ° C, followed by thorough washing through a warm water bath at 50 to 70 ° C.

The washed fiber can be subjected to dry heat treatment at a temperature of 270 to 290 ° C to obtain a wholly aromatic melamine fiber having a range satisfying the above crystallization degree 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, when blended with other fibers, short fibers having a fiber length of 25 to 200 mm are preferred. Further, the single fiber fineness of the organic fiber is preferably from 1 to 5 dtex.

In the colored organic fiber of the present invention, as a coloring method, a dyeing method using a carrier is preferred. In particular, a dyeing method using a cationic dye is preferred in terms of obtaining excellent color tone. The conditions of the dyeing step are not particularly limited.

In the colored organic fiber, the content of the carrier must be 1.8% by mass or less (preferably 0.1 to 1.8% by mass, more preferably 0.1 to 1.0% by mass, still more preferably 0.3 to 0.9% by mass). When the content is more than 1.8% by mass, the flame retardancy is impaired. On the other hand, when the content is less than 0.1% by mass, excellent coloring property cannot be obtained, and the hot water washing step described later is complicated.

The method for reducing the content of the carrier is exemplified by reducing the dyed cloth as needed, and then washing the hot water at a temperature of 90 to 140 ° C (more preferably 110 to 140 ° C) for 10 to 30 minutes. method.

Next, the cloth of the present invention comprises the aforementioned colored organic fiber The fabric of the dimension. The cloth may be composed only of the above-mentioned colored organic fibers, but may further comprise polyester fibers, cellulose fibers, polyamide fibers, polyolefin fibers, acrylic fibers, ray fibers, cotton fibers, animal hair fibers, and poly Other fibers such as urethane fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, acetate fibers, and polycarbonate fibers.

In this case, when the type of the wholly aromatic polyamide fiber contained in the fabric is 50% by mass or more based on the mass of the fabric, excellent flame retardancy can be obtained. The above-mentioned flame retardant fiber, synthetic fiber, recycled fiber, and natural fiber may be arbitrarily mixed according to the use or use requirements. More specifically, the ratio of the type of the wholly aromatic polyamide fiber is 50 to 98% by mass, the polyester fiber is 2 to 50% by mass, and the cellulose fiber is 0 to 50% by mass, and the dyeing property is also possible. With comfort. The ratio can also be adjusted based on the performance that is valued.

Further, it is also preferable to contain a flame retardant, a UV-containing absorbent or an ultraviolet reflective agent in any of the fibers constituting the cloth. In this case, in the ultraviolet absorber, the solubility in water is preferably 0.04 mg/L or less. When the solubility in water is more than 0.04 mg/L, when the carrier is dyed, the ultraviolet absorber is eluted, and the light resistance after dyeing is lowered.

The method of manufacturing the aforementioned fabric is not particularly limited. For example, after the above-mentioned organic fiber (or the above-mentioned organic fiber and other fiber) is used to obtain a woven yarn, it is woven or woven with a monofilament or a double yarn, and then dyed with a carrier and washed with hot water by the aforementioned method.

At this time, the structure of the cloth is preferably a plain weave, a weave, a satin weave, a double weave, or the like, but it may be a knitted or non-woven fabric. Fabric manufacturing There are no particular restrictions on the method. For example, a conventional weaving machine such as a rapier loom or a gripper loom can be used.

The obtained fabric is excellent in color density and flame retardancy by using the above-mentioned organic fibers. In this case, the darkness is preferably 80 or less (more preferably 52.5 or less, still more preferably 10 to 52.3) in terms of the brightness index L value. Further, the LOI as the flame retardancy is preferably 26 or more (more preferably 26 to 40). Further, in the vertical burning test (JIS L1091 A-4 method, 3 seconds of inflammation), the residual inflammation time is preferably 25 seconds or less (more preferably 1 second or less).

Further, in the above-mentioned fabric, the basis weight is preferably 300 g/m ² or less (preferably 50 to 250 g/m ² ). When the basis weight is more than 300 g/m ² , the weight of the fabric is impaired.

Next, the clothing of the present invention is a cloth material of the aforementioned cloth. The clothing includes protective clothing, firefighting clothes, fireproof clothing, rescue clothing, sportswear, duty clothes, racing suits, work clothes, gloves, hats, vests, and the like. Moreover, the aforementioned work clothes include work clothes worn during operation in a steelworks or iron and steel factory, work clothes for welding operations, and work clothes in an explosion-proof area. Further, the glove includes work gloves used in the aircraft industry, the information equipment industry, the precision equipment industry, and the like in which precision parts are mounted.

Moreover, the above-mentioned fabric can also be used for a fiber product such as a curtain, a car seat, or a school bag.

Example

Hereinafter, the present invention will be described in detail by way of examples. The present invention is not limited by this. Further, each physical property in the examples was measured by the following method.

(1) Flame retardancy of fabrics (vertical burning test)

The residual time (seconds) was evaluated based on the JIS L1091 A-4 method (3 seconds of inflammation).

(2) Amount of residual solvent

A fiber of 8.0 g was sampled, and after drying at 105 ° C for 120 minutes, it was allowed to cool in a dryer, and the fiber mass (M1) was weighed. Next, the fiber was subjected to reflux extraction in methanol using a Soxhlet extractor for 1.5 hours to extract a guanamine-based solvent contained in the fiber. The fiber was extracted and taken out, dried under vacuum at 150 ° C for 60 minutes, and then allowed to cool in a dryer, and the fiber mass (M2) was weighed. The amount of the solvent remaining in the fiber (the mass of the guanamine-based solvent) was calculated by the following formula using the obtained M1 and M2.

Residual solvent amount (%) = [(M1-M2) / M1] × 100

(3) Degree of crystallization

Using a X-ray measuring apparatus (RINT TTRIII, manufactured by RIGAKU Co., Ltd.), the fibrils were drawn into a fiber bundle having a diameter of about 1 mm and attached to a fiber sample stage to measure a diffraction distribution. The measurement conditions were Cu-Kα line source (50 kV, 300 mA), scanning angle range of 10 to 35°, and continuous measurement of 0.1° amount measurement: scanning 1°/min. From the measured diffraction distribution, the air scattering and non-interference scattering are corrected in an approximate straight line to obtain a full scattering distribution. Next, the amorphous scattering distribution is subtracted from the total scattering distribution to obtain a crystal scattering distribution. The degree of crystallization is the area intensity of the crystal scattering distribution (strong crystal scattering) The area intensity (total scattering intensity) of the total scattering distribution and the total scattering distribution were obtained by the following formula.

Crystallization degree (%) = [crystal scattering intensity / total scattering intensity] × 100

(4) Residual loading dose

Assay: A GC/MS sample from a fiber sample was inserted into a sample tube and measured by ATD. After confirming the carrier by qualitative analysis, quantitative analysis was carried out under the following conditions.

Calibration line: DOWANOL PPH 10.180mg/mL (n-hexane) 0.50‧0.75‧1.00μL

Column: DB-5ms 0.25mm×28m

Carrier: He

Injection: ATD 350 ° C × 20 min (sample heating) 300 ° C × 10 min (forcing)

Cold trap: 10 ° C

Interface valve switching: 250°C Mass Range 94 108 152

Detector: GCMS-QP2010

Ion source: 200 ° C

Voltage: 1.35KV (-0.48KV)

Oven: 110 ° C × 2 min 110 ~ 190 ° C (10 ° C / min)

Gas flow 1 time = 10:90 2 times = 1:4 2.0%

(5) rich color (L value)

Color measurement was performed with a Macbeth spectrophotometer Color-Eye 3100.

(6) Unit weight

The basis weight (g/m ² ) was measured in accordance with JIS L1096.

[Example 1]

A meta-type wholly aromatic linoleamide fiber was produced in the following manner.

According to the method described in Japanese Patent Publication No. Sho 47-10863, 20.0 parts by mass of poly(phenylisophthalamide) powder having an intrinsic viscosity (IV) of 1.9, which was produced by an interfacial polymerization method, was suspended and cooled to -10 ° C. N-methyl-2-pyrrolidone (NMP) was slurried in 80.0 parts by mass. Next, the suspension was heated to 60 ° C to be dissolved to obtain a transparent polymer solution. The polymer solution was mixed and dissolved in a polymer of 3.0% by mass of 2-[2H-benzotriazol-2-yl]-4-6-bis(1-methyl-1-phenylethyl)phenol. The ultraviolet absorber formed by the powder (solubility to water: 0.01 mg/L) was subjected to a vacuum decompression method to prepare a spinning solution (spinning dope).

[spinning ‧ coagulation step]

The spinning dope was spun from a spinning die having a pore size of 0.07 mm and a number of holes of 500 to a coagulation bath having a bath temperature of 30 ° C, and was spun. The composition of the coagulating liquid is water/NMP = 45/55 (parts by mass). Spinning was carried out in a coagulation bath at a wire speed of 7 m/min.

[plastic extension bath extension step]

Next, the stretching was carried out at a stretching ratio of 3.7 times in a plastic extension bath having a composition of water/NMP=45/55 at a temperature of 40 °C.

[washing step]

After stretching, it was washed with a water/NMP=70/30 bath (immersion length 1.8 m) at 20 ° C, followed by an ice bath (immersion length 3.6 m) at 20 ° C, and then passed through a warm water bath at 60 ° C (impregnation). Full length 5.4m) Wash.

[dry heat treatment step]

The washed fiber was subjected to dry heat treatment at a surface temperature of 280 ° C to obtain a meta-type aromatic melamine fiber.

[cutting step]

The inter-type wholly aromatic linoleamide fiber was subjected to crimping and cutting to obtain a staple fiber (original cotton) having a length of 51 mm.

[original cotton property]

The physical properties of the obtained inter-type wholly aromatic linalylamine fiber were a single fiber fineness of 1.7 dtex, a residual solvent amount of 0.08% by mass, and a degree of crystallization of 19%.

On the other hand, the following fibers are prepared as the other fiber primary cotton: a pair of arylamine fibers; "TOWARON (registered trademark)" and conductive yarn (nylon) manufactured by Teijin Aramid Co., Ltd.: "NO SHOCK (registered trademark)" manufactured by SOLCIAS Co., Ltd. (Mixed conductive filaments of conductive carbon particles).

Next, each of the inter-type wholly aromatic linalamide fiber (MA) (length 51 mm), the para-type wholly aromatic polyamine (PA) (length 50 mm), and the nylon conductive yarn (AS) (length 51 mm) were short. The fibers are blended at a ratio of MA/PA/AS=93/5/2 to become the yarn count/double yarn of the textile yarn 40, and the weaving density is woven by 65 strips/25.4 mm and latitude 55 strips/25.4 mm to obtain the weight per unit area. Flat tissue of 170 g/m ² .

Next, the fabric is treated with the following dyeing prescription and hot water washing prescription.

(staining prescription)

First, the dyeing was carried out in the following places.

‧Cationic dye: Made by Nippon Kayaku Co., Ltd., trade name: Kayacryl Red GL-ED 6.0%owf

‧ Carrier: Propylene glycol phenyl ether (DOWANOL PPH made by Dow Chemical) 40g/L

The so-called "40g/L" means "40 grams of water for 1 liter".

‧ acetic acid 0.3cc / L

‧Dispersant 0.5cc/L

‧Nitrate 25g/L

‧ bath ratio; 1:20

‧ Temperature × time: 135 ° C × 60 minutes

Next, the obtained colored cloth was washed in the following reduction bath.

‧ bath ratio; 1:20

‧ Temperature × time: 90 ° C × 20 minutes

‧Reduction bath: hydrogen sulfate 1g/L, soda ash 1g/L

(hot water wash prescription)

Next, the cloth was washed with hot water at a temperature of 130 ° C for 20 minutes. Next, the fabric was fixed by dry heat at a temperature of 180 ° C for 2 minutes.

The evaluation results of the obtained cloth are shown in Table 1.

[Example 2]

Change the above hot water washing prescription to 130 ° C × 20 minutes once to The same operation as in Example 1 was carried out except that 130 ° C × 20 minutes twice. The evaluation results are shown in Table 1.

[Example 3]

The same operation as in Example 1 was carried out except that the hot water washing prescription was changed once at 130 ° C for 20 minutes to 120 ° C × 20 minutes. The evaluation results are shown in Table 1.

[Example 4]

The same operation as in Example 1 was carried out except that the DOWANOL PPH 40g/ of the above dyeing prescription was changed to 60 g/L of benzyl alcohol. The evaluation results are shown in Table 1.

[Example 5]

Except that the DOWANOL PPH 40g/L of the above dyeing prescription was changed to 60 g/L of benzyl alcohol, and the hot water washing prescription was changed to 130 ° C × 20 minutes twice to 120 ° C × 20 minutes. 1 the same operation. The evaluation results are shown in Table 1.

[Example 6]

Except that the DOWANOL PPH 40g/L of the above dyeing prescription was changed to 60 g/L of benzyl alcohol, and the hot water washing prescription was changed to 130 ° C × 20 minutes twice to 120 ° C × 20 minutes. 1 the same operation. The evaluation results are shown in Table 1.

[Example 7]

Except that the DOWANOL PPH 40g/L of the above dyeing prescription was changed to 60 g/L of benzyl alcohol, and the hot water washing prescription was changed to 130 ° C × 20 minutes twice to 120 ° C × 20 minutes. 1 the same operation. The evaluation results are shown in Table 1.

[Comparative Example 1]

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

[Example 8]

The same operation as in Example 1 was carried out except that 130 ° C × 20 minutes of the hot water washing prescription was changed to 90 ° C × 20 minutes five times. The evaluation results are shown in Table 1.

[Example 9]

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

[Example 10]

In addition to changing the DOWANOL PPH of the above dyed prescription to 30g/L The same operations as in the first embodiment were carried out except for the rest. The evaluation results are shown in Table 1.

[Example 11]

The same operation as in Example 1 was carried out except that the DOWANOL PPH of the above 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 carried out except that the DOWANOL PPH of the above dyeing prescription was changed to 10 g/L. The evaluation results are shown in Table 1.

[Industrial Applicability]

According to the present invention, there is provided an organic fiber which is colored with an organic fiber and which is rich in color and excellent in flame retardancy, and a cloth and a clothing which use the organic fiber, and a method for producing the cloth, which are extremely industrially valuable.

Claims (20)

A colored organic fiber which is a colored organic fiber characterized in that the content of the carrier is set to be 1.8% by mass or less based on the mass of the fiber. The colored organic fiber of claim 1, wherein the content of the carrier is in the range of 0.1 to 1.8% by mass of the fiber mass. The colored organic fiber of claim 1, wherein the carrier is selected from any one of the group consisting of 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-iodobenzyl alcohol, cinnamyl alcohol, p-anisitol, benzhydrol, benzyl alcohol, propylene glycol phenyl ether, B Glycol phenyl ether, and N-methylformanilide. The colored organic fiber according to claim 1, wherein the organic fiber is selected from the group consisting of: a type of wholly aromatic polyamide fiber, a p-type wholly aromatic polyamide fiber, and a polybenzoxazole. (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzothiazole (PBTZ) fiber, polyimine (PI) fiber, polyamine (PSA), polyetheretherketone (PEEK) fiber, poly Ether quinone imine (PEI) fiber, polyacrylate (PAr) fiber, melamine fiber, phenol fiber, fluorine fiber, polyphenylene sulfide (PPS) fiber. The colored organic fiber of claim 1, wherein the organic fiber is a type of wholly aromatic polyamide fiber having a degree of crystallization of 15 to 25%. The colored organic fiber of claim 1, wherein the organic fiber is It is a type of wholly aromatic polyamide fiber having a residual solvent amount of 1.0% by mass or less. The colored organic fiber according to claim 1, wherein the organic fiber is a type of wholly aromatic polyamide fiber having a residual solvent amount of 0.1% by mass or less. The colored organic fiber of claim 6 or 7, wherein the residual solvent is selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone a group of dimethyl adenine. The colored organic fiber of claim 1, wherein the organic fiber is a meta-type wholly aromatic polyamide fiber, and the type of wholly aromatic polyamine which forms the inter-type wholly aromatic polyamide fiber is contained in the following In the aromatic polyamine skeleton represented by the formula (1), an aromatic diamine component different from the main constituent unit of the repeating structure or an aromatic dicarboxylic acid halide component with respect to the aromatic component as the third component The aromatic polyamine which is copolymerized in such a manner that the total amount of the repeating structural unit of the polyamine is 1 to 10 mol%, -(NH-Ar1-NH-CO-Ar1-CO)-...(1) wherein, Ar1 It is a divalent aromatic group having a coordination group or a bonding group other than the parallel axis direction. The colored organic fiber according to claim 9, wherein the aromatic diamine which is the third component is the formula (2), (3), or the aromatic dicarboxylic acid halide is the formula (4), (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, and 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. A fabric comprising the colored organic fiber of claim 1. The fabric of claim 11, wherein the cloth is free of polyester fiber, cellulose fiber, polyamide fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, One or more selected from the group consisting of polyvinyl chloride fibers, polyvinylidene chloride fibers, acetate fibers, and polycarbonate fibers. The fabric of claim 11, wherein any of the fibers constituting the cloth comprises a flame retardant. The fabric of claim 11, wherein any of the fibers constituting the cloth comprises an ultraviolet absorber or an ultraviolet reflector. The fabric of claim 11, wherein the fabric has a basis weight of 300 g/m ² . The fabric of claim 11, wherein the LOI is 26 or more. The fabric of claim 11, wherein the residual burning time in the vertical burning test (JIS L1091 A-4 method 3s) is 1 second or less. The fabric of claim 11, wherein the brightness index L is 80 or less. A cloth material obtained by using the cloth of claim 11. A method for producing a fabric comprising the method of producing a fabric of colored organic fibers according to claim 11, wherein the cloth containing the organic fibers is dyed with a carrier, and the cloth is heated in a hot water at a temperature of 90 to 140 °C. After washing for 10 to 30 minutes, the content of the carrier contained in the organic fiber is 1.8% by mass or less.