JP2012154002A - Meta-wholly aromatic polyamide fiber fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fabric made of meta-wholly aromatic polyamide fiber with a light resistant property that may be dyed in various colors by carrier dyeing and may suppress removal of a light resisting agent during dyeing.SOLUTION: A fabric is produced from meta-wholly aromatic polyamide fiber including a UV absorber with high hydrophobicity and having specific physical properties. Specifically, the fabric is produced from meta-wholly aromatic polyamide fiber including a UV absorber with solubility in water less than 0.04 mg/L, having a degree of exhaustion of 90% or more in dyed fiber and having a light resistance retaining rate of 80% or more kept through carrier dyeing.

Description

  The present invention relates to a fabric containing a meta-type wholly aromatic polyamide fiber. More specifically, the present invention relates to a fabric including a meta-type wholly aromatic polyamide fiber having light resistance capable of suppressing the falling off of the light resistance during carrier dyeing.

  Meta-type wholly aromatic polyamide fibers such as polymetaphenylene terephthalamide fiber exhibit excellent heat resistance and dimensional stability because most of the molecular skeleton is composed of aromatic rings. Taking advantage of these properties, meta-type wholly aromatic polyamide fibers are suitably used as fabrics in applications where heat resistance, flame resistance, and flame resistance are important. Applications to fields requiring aesthetics and visual properties such as bedding, clothing, and interior are rapidly expanding.

  As a method for obtaining colored fibers used for these apparel applications and the like, generally, there are a method by dyeing and a method by dyeing by using a dyed pigment. As a method of coloring the wholly aromatic polyamide fiber, for example, a method of dyeing using a basic dye and a dyeing assistant (carrier) such as benzyl alcohol or acetophenone is generally known.

  However, when the wholly aromatic polyamide fiber is dyed with a basic dye such as that used for dyeing aliphatic polyamide fiber, there is a problem that the light resistance of the obtained colored fiber is extremely deteriorated and the fading due to light is remarkable. .

  Therefore, for the purpose of improving the light resistance of the colored wholly aromatic polyamide fiber, Japanese Patent Application Laid-Open No. 49-75824 (Patent Document 1) cleans the resulting fiber by dry- or wet-spinning the aromatic polyamide solution. Then, before drying, a method for impregnating the fiber with an aqueous dispersion of an ultraviolet shielding material has been proposed. However, this method has a problem that the ultraviolet shielding material is likely to fall off due to the influence of the carrier during carrier dyeing.

  In addition, as a wholly aromatic polyamide fiber having light resistance and capable of non-carrier dyeing, JP-A No. 2003-239136 (Patent Document 2) contains an alkylbenzene sulfonic acid onium salt as a dyeing assistant and a hindered amine light stabilizer. A meta-type wholly aromatic polyamide fiber is disclosed. Since the fiber can be dyed non-carrier, it is difficult for the light-resistant agent to fall off during dyeing. However, the addition of the onium salt increases the production cost of the fiber, and also reduces the flame retardancy of the resulting fiber. Further, it was necessary to add a flame retardant and the like.

  Furthermore, a colored meta-type wholly aromatic polyamide fiber having a light resistance in which a specific pigment that does not fade by light is blended has been proposed (Japanese Patent Laid-Open No. 50-59522, Patent Document 3). However, in this method, since the pigment is contained in the fiber production process, the loss during production increases, it is difficult to deal with small lots, and it is difficult to obtain fibers of various required hues. There was a problem.

JP-A-49-75824 JP 2003-239136 A JP 50-59522 A

  The present invention has been made in view of the above-described background art, and the object of the present invention is that it can be dyed in various hues by carrier dyeing, and can suppress the fallout of the light-resistant agent at the time of dyeing. The object is to provide a meta-type wholly aromatic polyamide fiber fabric having light resistance.

  The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above-mentioned problems can be solved by forming a meta-type wholly aromatic polyamide fiber having specific properties using a highly hydrophobic ultraviolet absorber, and have completed the present invention.

  That is, the present invention is a fabric comprising a meta-type wholly aromatic polyamide fiber, wherein the meta-type wholly aromatic polyamide fiber contains an ultraviolet absorber having a solubility in water of less than 0.04 mg / L, and is dyed. A meta-type wholly aromatic polyamide fiber fabric having a fiber dyeing rate of 90% or more and a light resistance retention rate of 80% or more before and after carrier dyeing.

  The meta-type wholly aromatic polyamide fiber cloth of the present invention is a light-resistant meta-type wholly aromatic polyamide fiber cloth that can be dyed in various hues by carrier dyeing and that can suppress the removal of the light-resistant agent during dyeing. Become. For this reason, the fabric of the present invention expresses the excellent heat resistance, flame resistance, and flame resistance inherent in the meta-type wholly aromatic polyamide fiber, has good dyeability for dyes, and has excellent light resistance. It becomes the cloth which has the property. Therefore, the meta-type wholly aromatic polyamide fiber fabric of the present invention has extremely great industrial value in the field where these characteristics are required.

  Hereinafter, the present invention will be described in detail.

<Meta-type wholly aromatic polyamide fiber fabric>
[Constituent components of fabric]
The meta-type wholly aromatic polyamide fabric of the present invention includes meta-type wholly aromatic polyamide fibers described later. The content of the meta-type wholly aromatic polyamide fiber in the fabric is 50% by mass or more, preferably 80% by mass or more, more preferably from the viewpoint of dyeability and texture, based on the total mass of the fibers constituting the fabric. It is 90% by mass or more, particularly preferably 100%.

  In addition, in the meta-type wholly aromatic polyamide fiber fabric of the present invention, examples of fibers mixed with the meta-type wholly aromatic polyamide fiber described below include, for example, polybenzimidazole fiber, polyimide fiber, polyamideimide fiber, polyetherimide fiber, Examples include polyarylate fiber, polyparaphenylene benzobisoxazole fiber, novoloid fiber, flame retardant acrylic fiber, polyclar fiber, flame retardant polyester fiber, flame retardant cotton fiber, flame retardant wool fiber, and para type wholly aromatic polyamide fiber. Of these, para-type wholly aromatic polyamide fibers are preferably used from the viewpoint of fiber strength and heat resistance.

[Fabric form]
The form of the meta-type wholly aromatic polyamide fiber fabric of the present invention is not particularly limited, and may be appropriately selected depending on the purpose, use, etc. required for the fabric. In this invention, any form, such as a nonwoven fabric, a textile fabric, and a knitted fabric, may be sufficient.

  When fibers other than meta-type wholly aromatic polyamide fibers are included, for example, fibers mixed with meta-type wholly aromatic polyamide fibers are mixed by a conventional method to form a spun yarn, and then the spun yarn And a method of forming a fabric using.

When the form of the fabric is a woven fabric, the filament yarn, the spun yarn, or the like may be a woven configuration such as a plain weave, a twill weave, or a satin weave. In this case, the fabric weight is preferably 100 to 700 g / m ² , more preferably 200 to 400 g / m ² . When the fabric weight is less than 100 g / m ² , the strength of the fabric is low, while when it exceeds 700 g / m ² , the flexibility of the fabric is impaired.

  Moreover, when making the form of a fabric into a nonwoven fabric, in order to improve the intensity | strength of a fabric, it is also possible to use a base fabric. As a base fabric to be used, a woven fabric composed of yarn (filament yarn or spun yarn) having a total fineness of 200 to 1,700 dtex, more preferably 275 to 1,100 dtex, for example, a woven fabric structure such as plain weave, twill weave and satin weave Among them, a scrim that is a plain woven fabric, particularly a mesh-shaped plain woven fabric is preferable. The method for integrally forming the felt made of the fibers (short fibers) on the base fabric is not particularly limited. For example, the web made of the fibers is laminated on the upper and lower sides of the base fabric, and a conventional method, for example, The method of needle punching from both sides is mentioned.

Basis weight in the case of a non-woven fabric is preferably 200~1,500g / ^{m 2,} more preferably from 400-600 g / ^{m 2.} When the basis weight of the nonwoven fabric is less than 200 g / m ² , the strength of the fabric is lowered, whereas when it exceeds 1,500 g / m ² , the flexibility of the fabric is impaired.

[Physical properties of fabric]
[Dyeing rate of dyed fabric]
The meta-type wholly aromatic polyamide fiber fabric of the present invention preferably has a dyeing rate of 90% or more of the fabric dyed by the following dyeing method. The dyeing rate of the dyed fabric is preferably 90% or more, and more preferably 92% or more. When the dyeing rate of the dyed fabric is less than 90%, the loss amount of the dye in the dyeing process increases, which is not preferable because the cost in the dyeing process increases.

“Dyeing” for obtaining “dyeing rate” is dyeing by the following dyeing method.
(Dyeing method)
Cationic dye (product name: Kayacryl Blue GSL-ED (B-54), manufactured by Nippon Kayaku Co., Ltd.) 6% owf, acetic acid 0.3 mL / L, sodium nitrate 20 g / L, benzyl alcohol 70 g / L as a carrier agent, dispersion A dyeing solution containing 0.5 g / L of a dyeing assistant (manufactured by Meisei Chemical Co., Ltd., trade name: Disper TL) is prepared as an agent.

  Subsequently, a dyeing treatment is performed at 120 ° C. for 60 minutes with a bath ratio of the fabric and the dyeing solution being 1:40. After the dyeing treatment, hydrosulfite 2.0 g / L, amylazine D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: amirazine D) 2.0 g / L, treatment solution containing sodium hydroxide 1.0 g / L The dyed fabric is obtained by carrying out reduction washing at 80 ° C. for 20 minutes at a bath ratio of 1:20 and drying after washing with water.

The “dyeing rate” in the present invention refers to a value obtained by the following method.
(Dyeing rate)
The same amount of dichloromethane as this dyeing residual liquid is added to the dyeing residual liquid dyeing the fabric to extract the residual dye. Subsequently, with respect to the extract, the absorbance at wavelengths of 670 nm, 540 nm, and 530 nm was measured, respectively, and the dye concentration of the extract was determined from the calibration curve of the above three wavelengths prepared from a dichloromethane solution with a known dye concentration in advance. Let the average value of density | concentration be the dye density | concentration (C) of an extract. Using the dye concentration (Co) before dyeing, the value obtained by the following equation is defined as the dyeing rate (U).
Dyeing rate (U) = [(Co−C) / Co] × 100

[Light resistance retention before and after carrier dyeing]
The meta-type wholly aromatic polyamide fiber fabric of the present invention preferably has a light resistance retention of 80% or more before and after carrier dyeing. More preferably, it is 85% or more, and particularly preferably 90% or more. A low light fastness retention before and after carrier dyeing means that the light-proofing agent is frequently removed during carrier dyeing. When the weather resistance retention before and after dyeing is less than 80%, the light resistance effect of the product after dyeing is not sufficiently exhibited, which is not preferable.

The “light resistance retention” in the present invention refers to a value obtained by the following method.
(How to obtain light resistance retention)
In order to obtain the light fastness retention, the light fastening color change (ΔE *) is obtained by using an unirradiated fabric and a light irradiated fabric irradiated with a carbon arc fade meter at 63 ° C. for 24 hours. For the light fast discoloration (ΔE *), first, the diffuse reflectance in a -10 degree field of view is measured using the light source D65, and the lightness index L * value, chromaticness index a *, b * are obtained by normal calculation processing. The value is calculated, and the obtained value is used in accordance with JIS Z-8730 to be obtained by the following formula.
[Formula 1]
ΔE * = ((ΔL *) ² + (Δa *) ² + (Δb *) ² ) ^1/2
The “light fastness retention” is the value calculated by the following equation by obtaining the above light fast discoloration (ΔE *) for the fabric before and after dyeing.
[Formula 2]
Lightfastness retention (%) = 100− (post-staining ΔE * −pre-staining ΔE *) / pre-staining ΔE * x100

“Dyeing” in the evaluation of “light resistance retention” is dyeing without using a dye by the following method.
(Dyeing method)
Without using dye, acetic acid 0.3 mL / L, sodium nitrate 20 g / L, benzyl alcohol 70 g / L as a carrier agent, dyeing assistant (manufactured by Meisei Chemical Industry Co., Ltd., trade name: Disper TL) 0.5 g / A staining solution containing L is prepared.

  Subsequently, a dyeing treatment is performed at 120 ° C. for 60 minutes with a bath ratio of the fabric and the dyeing solution being 1:40. After the dyeing treatment, hydrosulfite 2.0 g / L, amylazine D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: amirazine D) 2.0 g / L, treatment solution containing sodium hydroxide 1.0 g / L The dyed fabric is obtained by carrying out reduction washing at 80 ° C. for 20 minutes at a bath ratio of 1:20 and drying after washing with water.

[Use of fabric]
Examples of the use of the meta-type wholly aromatic polyamide fiber fabric of the present invention include blankets, curtains, chair upholstery and the like. The use of the meta-type wholly aromatic polyamide fiber fabric of the present invention is not limited to these.

(blanket)
When the meta-type wholly aromatic polyamide fiber fabric of the present invention is a blanket, for example, the meta-type wholly aromatic polyamide fiber is a bulky processed yarn having at least one nap selected from fluff and loop on the yarn surface. And a method of forming a fabric (blanket) using the bulky processed yarn as a pile yarn. That is, a pile yarn made of meta-type wholly aromatic polyamide fiber is applied to a fabric cloth by flocking means such as tufting to obtain a blanket.

  Here, as the bulky processed yarn having at least one nap selected from fluff and loop on the yarn surface, spun yarn and chenille yarn made of short fibers, and yarn made of long fibers having a shrinkage difference are shrunk. Examples thereof include bulky processed yarns having raised ends formed by known means, such as processed yarns having looped raised ends on the surface and those further raised.

(curtain)
When the meta-type wholly aromatic polyamide fiber fabric of the present invention is a curtain, the form of the fabric is particularly preferably a woven fabric or a knitted fabric. As the woven structure of the woven fabric, a three-layer structure such as plain weave, twill weave and satin weave, changed structure, velvet and the like are preferable. The type of the knitted fabric may be either a weft knitted fabric or a warp knitted fabric. Examples of the weft knitting structure include flat knitting, double-sided knitting, pearl knitting, and lace knitting, and examples of the warp knitting structure include single atlas knitting and jacquard knitting.

(Chair upholstery)
When the meta-type wholly aromatic polyamide fiber fabric of the present invention is a chair upholstery for a vehicle such as an aircraft, ship, or train, it is mixed with the meta-type wholly aromatic polyamide fiber for the purpose of imparting flame retardancy. The fibers are preferably flame retardant fibers such as flame retardant polyester fibers, flame retardant cotton fibers, and flame retardant wool fibers. By using a flame retardant fiber together with an aromatic polyamide fiber having high heat resistance, it is possible to block the flame even when a flame is generated.
The form of the fabric constituting the chair upholstery is not particularly limited, and may be appropriately selected depending on the purpose and application, and may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric.

It is preferable that the weight per unit area of the chair stretch is in the range of 150 to 350 g / m ² . If the basis weight is less than 150 g / m ² , sufficient heat resistance may not be obtained. On the other hand, if the basis weight exceeds 350 g / m ² , it becomes heavy when used as a chair tension fabric. This is not preferable because the weight reduction of the vehicle is hindered.

  Since the meta-type wholly aromatic polyamide fiber fabric of the present invention has light resistance, when the fabric is used as a chair upholstery, it is possible to suppress a decrease in the appearance of the entire chair upholstery due to discoloration. In addition, since it is not necessary to form the chair upholstery fabric by double weaving or knitting so that fibers do not appear on the surface, the design of the chair upholstery fabric is not limited, and the chair upholstery fabric can be made thin. Can be reduced in weight.

<Meta type wholly aromatic polyamide fiber>
The meta-type wholly aromatic polyamide fiber fabric of the present invention contains the meta-type wholly aromatic polyamide fiber described below. The physical properties, configuration, production method and the like of the meta-type wholly aromatic polyamide fiber used in the present invention will be described below.

[Physical properties of meta-type wholly aromatic polyamide fibers]
[Dyeing rate of dyed fiber]
The meta-type wholly aromatic polyamide fiber used in the present invention has a dyed fiber dyeing rate of 90% or more, preferably 92% or more. When the dyeing rate of the dyed fiber is less than 90%, it is not preferred in terms of aesthetics required in the clothing field, and it cannot be dyed to a desired hue.

“Dyeing” for obtaining “dyeing rate” is dyeing by the following dyeing method.
(Dyeing method)
Cationic dye (product name: Kayacryl Blue GSL-ED (B-54), manufactured by Nippon Kayaku Co., Ltd.) 6% owf, acetic acid 0.3 mL / L, sodium nitrate 20 g / L, benzyl alcohol 70 g / L as a carrier agent, dispersion A dyeing solution containing 0.5 g / L of a dyeing assistant (manufactured by Meisei Chemical Co., Ltd., trade name: Disper TL) is prepared as an agent.

  Subsequently, the dyeing treatment is performed at 120 ° C. for 60 minutes with the bath ratio of the fiber and the dyeing solution being 1:40. After the dyeing treatment, hydrosulfite 2.0 g / L, amylazine D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: amirazine D) 2.0 g / L, treatment solution containing sodium hydroxide 1.0 g / L The dyed fiber is obtained by carrying out reduction washing at 80 ° C. for 20 minutes at a bath ratio of 1:20, and drying after washing with water.

The “dyeing rate” in the present invention refers to a value obtained by the following method.
(Dyeing rate)
Add the same volume of dichloromethane as this dyeing residual solution to the dyeing residual solution dyed fibrils to extract the residual dye. Subsequently, with respect to the extract, the absorbance at wavelengths of 670 nm, 540 nm, and 530 nm was measured, respectively, and the dye concentration of the extract was determined from the calibration curve of the above three wavelengths prepared from a dichloromethane solution with a known dye concentration in advance. Let the average value of density | concentration be the dye density | concentration (C) of an extract. Using the dye concentration (Co) before dyeing, the value obtained by the following equation is defined as the dyeing rate (U).
Dyeing rate (U) = [(Co−C) / Co] × 100

  In the fiber used in the present invention, the dyeing rate of the dyed fiber of the meta-type wholly aromatic polyamide fiber is adjusted by adjusting the conditions of the coagulation bath so as to form a coagulation form having no skin core in the coagulation step in the production method described later. And it can control by optimizing the degree of crystallinity of a fiber by carrying out dry heat treatment at specific temperature in a dry heat treatment process. In order to set the dyeing rate of the dyed fiber to 90% or more, the coagulation liquid is an aqueous solution having an NMP concentration of 45 to 60% by mass, the bath liquid temperature is 10 to 35 ° C., and the dry heat treatment temperature is the glass transition temperature of the fiber ( The temperature may be in the range of 260 to 330 ° C., which is equal to or higher than Tg).

[Light resistance retention before and after carrier dyeing]
The meta-type wholly aromatic polyamide fiber used in the present invention has a light resistance retention of 80% or more before and after carrier dyeing. It is preferably 85% or more, and particularly preferably 90% or more. A low light fastness retention before and after carrier dyeing means that the light-proofing agent is frequently removed during carrier dyeing. When the weather resistance retention before and after dyeing is less than 80%, the light resistance effect of the product after dyeing is not sufficiently exhibited, which is not preferable.

The “light resistance retention” in the present invention refers to a value obtained by the following method.
(How to obtain light resistance retention)
In order to obtain the light resistance retention rate, the light resistance color change (ΔE *) is obtained using unirradiated cotton and light irradiated cotton irradiated at 63 ° C. for 24 hours with a carbon arc fade meter. For the light fast discoloration (ΔE *), first, the diffuse reflectance in a -10 degree field of view is measured using the light source D65, and the lightness index L * value, chromaticness index a *, b * are obtained by normal calculation processing. The value is calculated, and the obtained value is used in accordance with JIS Z-8730 to be obtained by the following formula.
[Formula 1]
ΔE * = ((ΔL *) ² + (Δa *) ² + (Δb *) ² ) ^1/2
The “light fastness retention” is the value calculated by the following equation by obtaining the above light fast discoloration chromaticity (ΔE *) for cotton before and after dyeing.
[Formula 2]
Lightfastness retention (%) = 100− (post-staining ΔE * −pre-staining ΔE *) / pre-staining ΔE * x100

“Dyeing” in the evaluation of “light resistance retention” is dyeing without using a dye by the following method.
(Dyeing method)
Without using dye, acetic acid 0.3 mL / L, sodium nitrate 20 g / L, benzyl alcohol 70 g / L as a carrier agent, dyeing assistant (manufactured by Meisei Chemical Industry Co., Ltd., trade name: Disper TL) 0.5 g / A staining solution containing L is prepared.

  Subsequently, the dyeing treatment is performed at 120 ° C. for 60 minutes with the bath ratio of the fiber and the dyeing solution being 1:40. After the dyeing treatment, hydrosulfite 2.0 g / L, amylazine D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: amirazine D) 2.0 g / L, treatment solution containing sodium hydroxide 1.0 g / L The dyed fiber is obtained by carrying out reduction washing at 80 ° C. for 20 minutes at a bath ratio of 1:20, and drying after washing with water.

[Residual solvent amount]
Since the meta-type wholly aromatic polyamide fiber is usually produced from a spinning stock solution in which a polymer is dissolved in an amide solvent, the solvent necessarily remains in the fiber. However, in the meta-type wholly aromatic polyamide fiber used in the present invention, the amount of the solvent remaining in the fiber is preferably 0.1% by mass or less with respect to the fiber mass. The content is preferably 0.1% by mass or less, and more preferably 0.08% by mass or less.

  When the solvent remains in the fiber in excess of 0.1% by mass with respect to the fiber mass, the residual solvent volatilizes during processing and use in a high temperature atmosphere exceeding 200 ° C. Inferior to environmental safety. Moreover, since the strength is remarkably reduced by destroying the molecular structure, it is not preferable.

  In the production of the fiber used in the present invention, in order to reduce the residual solvent amount of the fibrils to 0.1% by mass or less, the components or conditions of the coagulation bath are adjusted so that the coagulation form does not have a skin core, and Perform plastic stretching at a specific magnification.

In addition, the “residual solvent amount of the fibril” in the present invention refers to a value obtained by the following method.
(Measurement method of residual solvent amount)
About 8.0 g of fibrils are collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and the fiber mass (M1) is weighed. Subsequently, this fiber is 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 is taken out, vacuum-dried at 150 ° C. for 60 minutes, allowed to cool in a desiccator, and the fiber mass (M2) is weighed. The amount of solvent (amide solvent mass) N (%) remaining in the fiber is calculated by the following formula using M1 and M2 obtained.
N (%) = [(M1-M2) / M1] × 100

[Strength retention of dyed fiber]
The meta-type wholly aromatic polyamide fiber used in the present invention preferably has a strength retention of 65% or more after dyeing in a 20 mass% sulfuric acid aqueous solution at 50 ° C. for 150 hours. The strength retention is preferably 65% or more, more preferably 70% or more, and most preferably 75% or more.
The strength retention rate of the dyed fiber is an index of acid resistance. If the strength retention rate is less than 65%, the acid resistance when used as a fabric is insufficient, and safety is lowered, which is not preferable.

In the fiber used in the present invention, in order to make the strength retention of the dyed fiber 65% or more, in the fiber production process, the components or conditions of the coagulation bath are adjusted so that the coagulation form does not have a skin core, and After the cleaning process, a dry heat treatment is performed at a specific temperature.
The dyed fiber used for the evaluation of the “strength retention” is a fiber dyed by the same method as the dyeing method for obtaining the “dyeing rate” described above, and the “strength retention” in the present invention is The value obtained by the following method.

(How to obtain strength retention (acid resistance test))
A 20 mass% sulfuric acid aqueous solution is put into a separable flask, and 51 mm of dyed fibers are immersed therein. Subsequently, the separable flask is immersed in a constant temperature water bath, maintained at a temperature of 50 ° C., and immersed for 150 hours. For each of the fibers before and after the immersion, the breaking strength is measured, and the strength retention of the fibers after the immersion is obtained.

The “breaking strength” in the present invention refers to a value obtained by measurement under the following conditions using a model number 5565 manufactured by Instron, based on JIS L 1015.
(Measurement condition)
Grasp interval: 20mm
Initial load: 0.044 cN (1/20 g) / dtex
Tensile speed: 20 mm / min

[Fracture strength and elongation at break of fibrils]
The breaking strength of the fibril (fiber before dyeing) used in the meta-type wholly aromatic polyamide fabric of the present invention is preferably 2.5 cN / dtex or more. It is more preferably 2.7 cN / dtex or more, and particularly preferably 3.0 cN / dtex or more. When the breaking strength is less than 2.5 cN / dtex, the fiber is broken in a post-processing step such as spinning, and the passability is deteriorated.

Moreover, it is preferable that the elongation at break of the fibrils (fibers before dyeing) of the meta-type wholly aromatic polyamide fibers used in the present invention is 30% or more. It is more preferably 35% or more, and particularly preferably 40% or more. When the elongation at break is less than 30%, passability in post-processing steps such as spinning deteriorates, which is not preferable.
Here, “breaking strength” and “breaking elongation” refer to values obtained by measurement under the above-mentioned “breaking strength” measurement conditions based on JIS L 1015.

  In the fiber used in the present invention, the “breaking strength” of the meta-type wholly aromatic polyamide fiber is obtained by optimizing the draw ratio in the plastic drawing bath drawing step and the heat treatment temperature in the dry heat treatment step in the production method described later. Can be controlled. In order to set the breaking strength to 2.5 cN / dtex or more, the draw ratio may be set to 3.5 to 5.0 times, and the dry heat treatment temperature may be set to a range of 260 to 330 ° C.

  In the fiber used in the present invention, the “breaking elongation” of the meta-type wholly aromatic polyamide fiber can be controlled by optimizing the coagulation bath conditions in the coagulation step in the production method described later. In order to achieve 30% or more, the coagulating liquid may be an aqueous solution having an NMP concentration of 45 to 60% by mass, and the bath liquid temperature may be 10 to 35 ° C.

[Configuration of meta-type wholly aromatic polyamide]
The meta-type wholly aromatic polyamide constituting the meta-type wholly aromatic polyamide fiber used in the present invention is composed of a meta-type aromatic diamine component and a meta-type aromatic dicarboxylic acid component. Other copolymer components such as the para type may be copolymerized within a range not impairing the above.

Particularly preferred for use in the present invention is a meta-type wholly aromatic polyamide mainly composed of a metaphenylene isophthalamide unit from the viewpoints of mechanical properties, heat resistance and flame retardancy.
As the meta-type wholly aromatic polyamide composed of metaphenylene isophthalamide units, the metaphenylene isophthalamide units are preferably 90 mol% or more of the total repeating units, more preferably 95 mol% or more, particularly preferably. 100 moles.

[Raw material for meta-type wholly aromatic polyamide]
(Meta-type aromatic diamine component)
Examples of the meta-type aromatic diamine component used as a raw material for the meta-type wholly aromatic polyamide include metaphenylene diamine, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, and the like, halogens in these aromatic rings, Examples of derivatives having a substituent such as an alkyl group having 1 to 3 carbon atoms, such as 2,4-toluylenediamine, 2,6-toluylenediamine, 2,4-diaminochlorobenzene, 2,6-diaminochlorobenzene, etc. can do. Of these, metaphenylenediamine alone or a mixed diamine containing metaphenylenediamine in an amount of 85 mol% or more, preferably 90 mol% or more, particularly preferably 95 mol% or more is preferable.

(Meta-type aromatic dicarboxylic acid component)
Examples of the raw material of the meta type aromatic dicarboxylic acid component constituting the meta type wholly aromatic polyamide include a meta type aromatic dicarboxylic acid halide. Examples of the meta-type aromatic dicarboxylic acid halide include isophthalic acid halides such as isophthalic acid chloride and isophthalic acid bromide, and derivatives having substituents such as halogen and alkoxy groups having 1 to 3 carbon atoms on the aromatic ring, such as 3 -Chloroisophthalic acid chloride etc. can be illustrated. Of these, isophthalic acid chloride itself or a mixed carboxylic acid halide containing isophthalic acid chloride in an amount of 85 mol% or more, preferably 90 mol% or more, particularly preferably 95 mol% or more is preferable.

[Method for producing meta-type wholly aromatic polyamide]
The production method of the meta-type wholly aromatic polyamide is not particularly limited. For example, it is produced by solution polymerization or interfacial polymerization using a meta-type aromatic diamine component and a meta-type aromatic dicarboxylic acid chloride component as raw materials. be able to.

  In addition, the molecular weight of the meta-type wholly aromatic polyamide used in the present invention is not particularly limited as long as it can form fibers. In general, in order to obtain a fiber having sufficient physical properties, a polymer having an intrinsic viscosity (IV) measured in a concentrated sulfuric acid at 30 ° C. with a polymer concentration of 100 mg / 100 mL sulfuric acid is in a range of 1.0 to 3.0. Appropriate polymers in the range of 1.2 to 2.0 are particularly preferred.

<Method for producing meta-type wholly aromatic polyamide fiber>
The meta-type wholly aromatic polyamide fiber used in the present invention uses the meta-type wholly aromatic polyamide obtained by the above production method, for example, a spinning solution preparation process, spinning / coagulation process, plastic drawing described below. It is manufactured through a bath stretching process, a washing process, a relaxation process, and a heat treatment process.

[Spinning liquid preparation process]
In the spinning solution preparation step, the meta type wholly aromatic polyamide is dissolved in an amide solvent, and an ultraviolet absorber is added to prepare a spinning solution (meta type wholly aromatic polyamide polymer solution). In the production of the fiber used in the present invention, it is important to include a specific ultraviolet absorber in the spinning solution in the spinning solution preparation step. By forming fibers from a spinning solution containing a specific ultraviolet absorbent, elution of the ultraviolet absorbent during carrier dyeing can be suppressed.

  In preparing the spinning solution, an amide solvent is usually used, and examples of the amide solvent used include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and dimethylacetamide (DMAc). be able to. Of these, NMP or DMAc is preferably used from the viewpoints of solubility and handling safety.

  The concentration of the solution may be appropriately selected from the viewpoint of the coagulation rate and the solubility of the polymer in the next spinning and coagulation step. For example, the polymer is polymetaphenylene isophthalamide and the solvent is NMP. In the case of, it is usually preferred to be in the range of 10 to 30% by mass.

(UV absorber)
The ultraviolet absorber used in the present invention is highly hydrophobic and needs to have a solubility in water of less than 0.04 mg / L. If it is 0.04 mg / L or more, the ultraviolet absorber is eluted during carrier dyeing, and the light resistance after dyeing is undesirably lowered.

  In addition, the ultraviolet absorber used in the present invention is a compound that efficiently shields light around 360 nm, which is the photodegradation characteristic wavelength of the meta wholly aromatic polyamide, and has almost no absorption in the visible region. preferable.

  Accordingly, the ultraviolet absorber used in the present invention is preferably a specific substituted benzotriazole, specifically, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- [5-Chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2- [2H-benzotriazol-2-yl] -4-6-bis ( 1-methyl-1-phenylethyl) phenol, 2- [2H-benzotriazol-2-yl] -4- (1,1,3,3-tetramethylbutyl) phenol, and the like. Among these, 2- [2H-benzotriazol-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol has high hydrophobicity and small absorption in the visible region. Is particularly preferred.

  The content of the ultraviolet absorber with respect to the meta-type wholly aromatic polyamide fiber is preferably in the range of 3.0% by mass to 6.5% by mass with respect to the total mass of the meta-type wholly aromatic polyamide fiber. Preferably it is the range of 4.5 mass% or more and 6.5 mass% or less. When the amount is less than 3.0% by mass, the light resistance effect is not sufficiently exhibited, which is not preferable. When the amount is more than 6.5% by mass, the physical properties of the obtained raw cotton are deteriorated, which is not preferable.

  The mixing method of the meta type wholly aromatic polyamide and the UV absorber is a method of mixing and dissolving the UV absorber in the solvent and adding the meta type wholly aromatic polyamide solution thereto, or the UV absorber is added to the meta type wholly aromatic. The method of dissolving in a polyamide solution is not particularly limited. The spinning solution thus obtained is formed into a fiber through the following steps.

[Spinning and coagulation process]
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. Moreover, the number of spinning holes, the arrangement state, the hole shape and the like of the spinneret are not particularly limited as long as they can be stably wet-spun. For example, the number of holes is 500 to 30,000, and the spinning hole diameter is 0.05. A multi-hole spinneret for ˜0.2 mm sufu may be used.
The temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) when spinning from the spinneret is suitably in the range of 10 to 90 ° C.

  As a coagulation bath used for obtaining the fiber used in the present invention, an aqueous solution containing an inorganic salt and having an NMP concentration of 45 to 60% by mass is used in the temperature range of the bath solution of 10 to 35 ° C. If the NMP concentration is less than 45% by mass, the skin has a thick structure, the cleaning efficiency in the cleaning process is lowered, and it becomes difficult to make the residual solvent amount of the fibrils 0.1% by mass or less. Further, when the NMP concentration exceeds 60% by mass, uniform solidification cannot be performed until reaching the inside of the fiber, and therefore, it becomes difficult to make the residual solvent amount of the fibrils 0.1% by mass or less, Moreover, acid resistance is also insufficient. In addition, the range of 0.1-30 seconds is suitable for the immersion time of the fiber in a coagulation bath.

  When obtaining the fiber used in the present invention, by setting the components or conditions of the coagulation bath as described above, the skin formed on the surface of the fiber can be made thin, and a uniform structure can be obtained up to the inside of the fiber. As a result, the dyeability can be further improved, and the breaking elongation of the resulting fiber can be further improved.

[Plastic stretching bath stretching process]
In the plastic drawing bath drawing step, the fiber is drawn in the plastic drawing bath while the fiber obtained by coagulation in the coagulation bath is in a plastic state.
It does not specifically limit as a plastic drawing bath liquid, A conventionally well-known bath liquid can be employ | adopted.

  In order to obtain the fiber used in the present invention, the draw ratio in the plastic drawing bath needs to be in the range of 3.5 to 5.0 times, more preferably in the range of 3.7 to 4.5 times. And In the production of the fiber used in the present invention, the solvent removal from the coagulated yarn can be promoted by plastic drawing in a plastic drawing bath within a specific magnification range. It can be 1 mass% or less.

When the draw ratio in the plastic drawing bath is less than 3.5 times, the solvent removal from the coagulated yarn becomes insufficient, and it is difficult to reduce the residual solvent amount of the fibrils to 0.1% by mass or less. It becomes. Further, the breaking strength becomes insufficient, and handling in a processing process such as a spinning process becomes difficult. On the other hand, when the draw ratio exceeds 5.0 times, single yarn breakage occurs, resulting in poor production stability.
The temperature of the plastic stretching bath is preferably in the range of 10 to 90 ° C. When the temperature is preferably in the range of 20 to 90 ° C, the process condition is good.

[Washing process]
In the washing step, the fiber drawn in the plastic drawing bath is thoroughly washed. Washing is preferably performed in multiple stages because it affects the quality of the resulting fiber. In particular, the temperature of the cleaning bath in the cleaning step and the concentration of the amide solvent in the cleaning bath liquid affect the state of extraction of the amide solvent from the fibers and the state of penetration of water from the cleaning bath into the fibers. For this reason, it is preferable to control the temperature condition and the concentration condition of the amide solvent by setting the washing process in multiple stages for the purpose of bringing them into an optimum state.

  The temperature condition and the concentration condition of the amide solvent are not particularly limited as long as the quality of the finally obtained fiber can be satisfied, but if the initial washing bath is at a high temperature of 60 ° C. or higher, water Intrusion into the fiber occurs at a stretch, generating huge voids in the fiber, leading to quality degradation. For this reason, it is preferable that the first washing bath has a low temperature of 30 ° C. or lower.

  When the solvent remains in the fiber, environmental safety in processing of the product using the fiber and use of the product formed using the fiber is not preferable. For this reason, the amount of solvent contained in the fiber used in the present invention is 0.1% by mass or less, more preferably 0.08% by mass or less.

[Dry heat treatment process]
In the dry heat treatment step, the fiber that has undergone the washing step is dried and heat treated. Although it does not specifically limit as a method of dry heat processing, For example, the method of using a hot roller, a hot plate, etc. can be mentioned. By performing the dry heat treatment, finally, the meta type wholly aromatic polyamide fiber used in the present invention can be obtained.

  In order to obtain the fiber used for this invention, it is necessary to make the heat processing temperature in a dry heat treatment process into the range of 260-330 degreeC, and it is more preferable to set it as the range of 270-310 degreeC. When the heat treatment temperature is less than 260 ° C., the crystallization of the fibers becomes insufficient, the shrinkage of the fibers becomes high, and the handling in the dyeing process becomes difficult. On the other hand, when the temperature exceeds 330 ° C., the crystallization of the fibers becomes too large, and the dyeability is greatly reduced. Moreover, making dry-heat-treatment temperature into the range of 260-330 degreeC contributes to the improvement of the breaking strength of the fiber obtained.

[Crimping process, etc.]
The meta-type wholly aromatic polyamide fiber that has been subjected to the dry heat treatment may be further crimped as necessary. Further, after the crimping process, it may be cut into an appropriate fiber length and provided to the next step. In some cases, it may be wound up as a multifilament yarn.

<Dyeing process>
When dyeing the meta-type wholly aromatic polyamide fiber used in the present invention or the meta-type wholly aromatic polyamide fiber fabric of the present invention, existing dyeing equipment can be used. The dye used for the dyeing treatment is preferably a cationic dye that easily penetrates into a dense structure and has a high dyeing rate.

  Further, in order to dye the meta-type wholly aromatic polyamide fiber used in the present invention or the meta-type wholly aromatic polyamide fiber fabric of the present invention, it is necessary to use a carrier which is a dyeing aid. When the carrier is not used, the dye cannot sufficiently penetrate into the dense structure of the fiber, and the dyeing rate is lowered, which is not preferable.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to these examples and the like.

<Measurement method>
Each physical property value in Examples and Comparative Examples was measured by the following method.

[Fineness]
Based on JIS L 1015, the measurement based on the A method of positive fineness was implemented, and it described with the apparent fineness.

[Break strength, elongation at break]
Based on JIS L1015, it measured on condition of the following using the model number 5565 by Instron.
(Measurement condition)
Grasp interval: 20mm
Initial load: 0.044 cN (1/20 g) / dtex
Tensile speed: 20 mm / min

[Dyeing rate]
Dichloromethane having the same volume as that of the dyeing residual solution was added to the dyeing residual solution obtained by dyeing the raw cotton or the fabric to extract the residual dye. Subsequently, with respect to the extract, the absorbance at wavelengths of 670 nm, 540 nm, and 530 nm was measured, respectively, and the dye concentration of the extract was determined from the calibration curve of the above three wavelengths prepared from a dichloromethane solution with a known dye concentration in advance. The average value of the concentration was defined as the dye concentration (C) of the extract. Using the dye concentration (Co) before dyeing, the value obtained by the following formula was used as the dyeing rate (U).
Dyeing rate (U) = [(Co−C) / Co] × 100

In addition, as the “dyeing” for obtaining the “dyeing rate”, the following dyeing method was carried out.
(Dyeing method of raw cotton or fabric)
Cationic dye (product name: Kayacryl Blue GSL-ED (B-54), manufactured by Nippon Kayaku Co., Ltd.) 6% owf, acetic acid 0.3 mL / L, sodium nitrate 20 g / L, benzyl alcohol 70 g / L as a carrier agent, dispersion A dyeing solution containing 0.5 g / L of a dyeing assistant (made by Meisei Chemical Co., Ltd., trade name: Disper TL) was prepared as an agent.
Subsequently, a dyeing treatment was performed at 120 ° C. for 60 minutes with a bath ratio of the raw cotton or fabric and the dyeing solution being 1:40. After the dyeing treatment, hydrosulfite 2.0 g / L, amylazine D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: amirazine D) 2.0 g / L, treatment solution containing sodium hydroxide 1.0 g / L Was used for reducing washing at a bath ratio of 1:20 at 80 ° C. for 20 minutes, followed by washing with water and drying to obtain dyed raw cotton or dyed fabric.

[Strength retention (acid resistance test)]
A 20% by mass sulfuric acid aqueous solution was put into a separable flask, and the raw cotton dyed by the same method as the dyeing method for obtaining the above-mentioned “dyeing rate” was immersed therein. Subsequently, the separable flask was immersed in a constant temperature water bath, maintained at a temperature of 50 ° C., and immersed for 150 hours. With respect to the raw cotton before and after the immersion, the breaking strength was measured by the above measuring method, and the strength retention of the raw cotton after the immersion was obtained.

[Remaining solvent amount of fibrils]
About 8.0 g of fibrils were collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and the fiber mass (M1) was weighed. Subsequently, this fibril 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 (amide solvent mass) N (%) remaining in the fiber was calculated by the following formula using the obtained M1 and M2.
N (%) = [(M1-M2) / M1] × 100

[Intrinsic viscosity (IV)]
After the aromatic polyamide polymer was isolated from the polymer solution and dried, it was measured in concentrated sulfuric acid at a polymer concentration of 100 mg / 100 mL sulfuric acid at 30 ° C.

[Light resistance retention]
In order to obtain the light fastness retention rate of raw cotton or fabric, non-irradiated cotton (unirradiated fabric) and light irradiated cotton (light irradiated fabric) irradiated at 63 ° C. for 24 hours with a carbon arc fade meter were used. Degree (ΔE *) was obtained. For the light fast discoloration (ΔE *), first, the diffuse reflectance in a -10 degree field of view is measured using the light source D65, and the lightness index L * value, chromaticness index a *, b * are obtained by normal calculation processing. The value was calculated, and the obtained value was used in accordance with JIS Z-8730 to obtain the value.
[Formula 1]
ΔE * = ((ΔL *) ² + (Δa *) ² + (Δb *) ² ) ^1/2
The “light fastness retention” was calculated from the following formula by obtaining the above light fast discoloration (ΔE *) for the raw cotton or fabric before and after dyeing.
[Formula 2]
Lightfastness retention (%) = 100− (post-staining ΔE * −pre-staining ΔE *) / pre-staining ΔE * x100
The “dyeing” in the evaluation of light resistance retention was dyeing without using a dye by the following method.

(Dyeing method)
Without using dye, acetic acid 0.3 mL / L, sodium nitrate 20 g / L, benzyl alcohol 70 g / L as a carrier agent, dyeing assistant (manufactured by Meisei Chemical Industry Co., Ltd., trade name: Disper TL) 0.5 g / A staining solution containing L was prepared.
Subsequently, a dyeing treatment was performed at 120 ° C. for 60 minutes with a bath ratio of the raw cotton or fabric and the dyeing solution being 1:40. After the dyeing treatment, hydrosulfite 2.0 g / L, amylazine D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: amirazine D) 2.0 g / L, treatment solution containing sodium hydroxide 1.0 g / L Was used for reducing washing at a bath ratio of 1:20 at 80 ° C. for 20 minutes, followed by washing with water and drying to obtain dyed raw cotton or dyed fabric.

<Example 1>
[Production of meta-type wholly aromatic polyamide fiber]
[Spinning fluid adjustment process]
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 under reduced pressure 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 was water / NMP = 45/55 (parts by mass), and was spun by discharging into the 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.

[Physical properties of fibrils]
The physical properties of the obtained fibrils were a fineness of 1.7 dtex, a breaking strength of 2.7 cN / dtex, a breaking elongation of 50.0%, and a residual solvent amount of 0.08% by mass, showing good mechanical properties. Table 1 shows the physical properties of the obtained fibrils.

[Crimping and cutting process]
After imparting crimps to the fiber obtained through the crimper, raw fiber was obtained by cutting with a cutter into a short fiber of 51 mm.

[Dyeing process 1]
Cationic dye (product name: Kayacryl Blue GSL-ED (B-54), manufactured by Nippon Kayaku Co., Ltd.) 6% owf, acetic acid 0.3 mL / L, sodium nitrate 20 g / L, benzyl alcohol 70 g / L as a carrier agent, dispersion A dyeing solution containing 0.5 g / L of a dyeing assistant (made by Meisei Chemical Co., Ltd., trade name: Disper TL) was prepared as an agent.
The obtained raw cotton was dyed for 60 minutes at 120 ° C. with a bath ratio of the raw cotton to the dyeing solution of 1:40. After the dyeing treatment, hydrosulfite 2.0 g / L, amylazine D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: amirazine D) 2.0 g / L, treatment solution containing sodium hydroxide 1.0 g / L Was used for reduction washing at 80 ° C. for 20 minutes at a bath ratio of 1:20, and dyed cotton was obtained by drying after washing with water.

[Physical properties of dyed cotton, etc.]
The dyeing rate of dyed cotton was 92.4%, indicating good dyeability. The breaking strength of the dyed cotton was 2.7 cN / dtex, the breaking strength of the dyed cotton after the acid resistance test was 2.3 cN / dtex, and the strength retention was 85%, indicating good acid resistance. . The results are shown in Table 1.

[Dyeing process 2]
Without using dye, acetic acid 0.3 mL / L, sodium nitrate 20 g / L, benzyl alcohol 70 g / L as a carrier agent, dyeing assistant (manufactured by Meisei Chemical Industry Co., Ltd., trade name: Disper TL) 0.5 g / A staining solution containing L was prepared.
The obtained raw cotton was dyed for 60 minutes at 120 ° C. with a bath ratio of the raw cotton to the dyeing solution of 1:40. After the dyeing treatment, hydrosulfite 2.0 g / L, amylazine D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: amirazine D) 2.0 g / L, treatment solution containing sodium hydroxide 1.0 g / L Was used for reduction washing at 80 ° C. for 20 minutes at a bath ratio of 1:20, and dyed cotton was obtained by drying after washing with water.

[Light resistance retention]
The light fastness retention of the obtained raw cotton was 89%. The results are shown in Table 1.

[Production of non-woven fabric]
The meta-type wholly aromatic polyamide short having a basis weight of 101 g / m ² and a thickness of 0.8 mm is subjected to needle punching on the above-described raw cotton cut to 51 mm under the conditions of a needle density of 150 pieces / cm ² and a needle depth of 14 mm. A non-woven fabric consisting only of fibers was produced.

[Nonwoven fabric dyeing process]
Similarly to the above-described raw cotton, the obtained nonwoven fabric was dyed under the conditions of the dyeing process 1 and the dyeing process 2.

[Physical properties of non-woven fabric]
The dyeing rate and the light fastness retention rate were evaluated by the measurement method using the nonwoven fabric and the dyeing solution before and after dyeing. The dyeing rate of the nonwoven fabric was 93.1%, and the light resistance retention rate was 86%. The results are shown in Table 1.

<Example 2>
[Production of meta-type wholly aromatic polyamide fiber]
In the same manner as in Example 1, meta-type wholly aromatic polyamide fibers and raw cotton were produced.

[Production of woven fabric]
A woven fabric (weight per unit: 239 g / m ² , thickness: 0.8 mm) in which the raw cotton cut to 51 mm is made into a spun yarn (count: 30/2) through a normal spinning process and woven into a 2/1 twill weave from the spun yarn. Was made. Scouring treatment was performed by a known method to remove the paste and oil on the fabric surface.

[Textile dyeing process]
In the same manner as in Example 1, the obtained fabric was dyed under the conditions of the dyeing process 1 and the dyeing process 2.

[Physical properties of textiles]
The dyeing rate and the light fastness retention rate were evaluated by the above measuring method using the fabric and dyeing solution before and after dyeing. The dyeing rate of the woven fabric was 92.5%, and the light resistance retention rate was 90%. The results are shown in Table 1.

<Comparative Example 1>
[Production of meta-type wholly aromatic polyamide fiber]
Highly hydrophilic methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate (solubility in water: 0.05 mg / L) as UV absorber A meta-type wholly aromatic polyamide fiber was obtained in the same manner as in Example 1 except that was used.

[Physical properties of fibrils]
The physical properties of the obtained fiber were a fineness of 1.7 dtex, a breaking strength of 2.9 cN / dtex, a breaking elongation of 49.8%, and a residual solvent amount of 0.10% by mass. Table 1 shows the physical properties of the obtained fiber.

[Crimping and cutting process]
The obtained fiber was crimped and cut in the same manner as in Example 1 to obtain a short fiber of 51 mm, thereby obtaining a raw cotton.

[Dyeing process 1]
The obtained raw cotton was dyed under the conditions of the dyeing step 1 in the same manner as in Example 1 to obtain dyed cotton.

[Physical properties of dyed cotton, etc.]
The dyeing rate was 91.2%, indicating good dyeability. Moreover, the breaking strength of the dyed cotton was 2.9 cN / dtex, the breaking strength of the dyed cotton after the acid resistance test was 2.2 cN / dtex, and the strength retention rate was 76%, indicating good acid resistance. The results are shown in Table 1.

[Dyeing process 2]
The obtained raw cotton was dyed under the conditions of the dyeing step 2 in the same manner as in Example 1 to obtain dyed cotton.

[Light resistance retention]
The obtained raw cotton had a light resistance retention of 52%, and the ultraviolet absorbent was highly hydrophilic, so that the ultraviolet absorbent was eluted during dyeing. The results are shown in Table 1.

[Production of non-woven fabric]
A nonwoven fabric was prepared under the same conditions as in Example 1 using raw cotton cut to 51 mm.

[Nonwoven fabric dyeing process]
In the same manner as in Example 1, the obtained nonwoven fabric was dyed under the conditions of the dyeing process 1 and the dyeing process 2.

[Physical properties of non-woven fabric]
The dyeing rate and the light fastness retention rate were evaluated by the measurement method using the nonwoven fabric and the dyeing solution before and after dyeing. The dyeing rate of the nonwoven fabric was as good as 91.8%, but the light resistance retention rate was as low as 48%, and a large amount of the ultraviolet absorber was eluted. The results are shown in Table 1.

<Comparative Example 2>
[Production of meta-type wholly aromatic polyamide fiber]
In the same manner as in Comparative Example 1, meta-type wholly aromatic polyamide fibers and raw cotton were produced.

[Production of woven fabric]
A woven fabric was prepared under the same conditions as in Example 2 using raw cotton cut to 51 mm.

[Physical properties of textiles]
The dyeing rate and the light fastness retention rate were evaluated by the above measuring method using the fabric and dyeing solution before and after dyeing. The dyeing rate of the woven fabric was as good as 91.0%, but the light resistance retention rate was as low as 50%, and a large amount of the ultraviolet absorber was eluted. The results are shown in Table 1.

<Comparative Example 3>
[Production of meta-type wholly aromatic polyamide fiber]
[Spinning fluid adjustment process]
A spinning solution was prepared in the same manner as in Example 1 except that 2- [2H-benzotriazol-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol powder was not added.

[Spinning / coagulation process, plastic stretching bath stretching process, washing process, dry heat treatment process]
In the same manner as in Example 1, spinning / coagulation, plastic stretching bath stretching, and washing were performed to obtain an undried wet meta-type wholly aromatic polyamide fiber immediately after the washing step.

[Impregnation process of UV absorber]
(Adjustment of UV absorber dispersion)
2- [2H-benzotriazol-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol powder (solubility in water: 0.01 mg / L) in 10 mL of methylene chloride 7% by mass was dissolved, and the solution was poured into 100 mL of an aqueous solution in which 0.3 g of an emulsifier “EMCOL P10-59” was dissolved, with stirring. Stir until all the methylene chloride has evaporated, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate (solubility in water: 0.05 mg / L ) Aqueous dispersion.

(Impregnation with UV absorber)
The undried meta-type wholly aromatic polyamide fiber obtained above was put into 20 g of the aqueous dispersion prepared above and held at room temperature for 1 hour with stirring. Subsequently, it was diluted with 100 mL of water, heated to the boiling point and kept at that temperature for an additional hour. The meta-type wholly aromatic polyamide fiber was taken out, washed with water, and subjected to dry heat treatment with a hot roller at 310 ° C.

[Physical properties of fibrils]
The obtained fibrils had physical properties of a fineness of 1.7 dtex, a breaking strength of 2.6 cN / dtex, a breaking elongation of 47.8%, and a residual solvent amount of 0.03% by mass. Table 1 shows the physical properties of the obtained fibrils.

[Crimping and cutting process]
The obtained fiber was crimped and cut in the same manner as in Example 1 to obtain a short fiber of 51 mm, thereby obtaining a raw cotton.

[Dyeing process 1]
The obtained raw cotton was dyed under the conditions of the dyeing step 1 in the same manner as in Example 1 to obtain dyed cotton.

[Physical properties of dyed cotton, etc.]
The dyeing rate was 91.5%. The breaking strength of the dyed cotton was 2.6 cN / dtex, the breaking strength of the dyed cotton after the acid resistance test was 1.9 cN / dtex, and the strength retention was 73%. The results are shown in Table 1.

[Dyeing process 2]
The obtained raw cotton was dyed under the conditions of the dyeing step 2 in the same manner as in Example 1 to obtain dyed cotton.

[Light resistance retention]
The obtained raw cotton had a light resistance retention of 64%, and a large amount of the ultraviolet absorber was eluted. The results are shown in Table 1.

[Production of non-woven fabric]
A nonwoven fabric was prepared under the same conditions as in Example 1 using raw cotton cut to 51 mm.

[Nonwoven fabric dyeing process]
In the same manner as in Example 1, the obtained nonwoven fabric was dyed under the conditions of the dyeing process 1 and the dyeing process 2.

[Physical properties of non-woven fabric]
The dyeing rate and the light fastness retention rate were evaluated by the measurement method using the nonwoven fabric and the dyeing solution before and after dyeing. The dyeing rate of the nonwoven fabric was as good as 91.2%, but the light resistance retention rate was as low as 58%, and a large amount of the ultraviolet absorber was eluted. The results are shown in Table 1.

<Comparative Example 4>
[Production of meta-type wholly aromatic polyamide fiber]
In the same manner as in Comparative Example 3, meta-type wholly aromatic polyamide fibers and raw cotton were produced.

[Production of woven fabric]
A woven fabric was prepared under the same conditions as in Example 2 using raw cotton cut to 51 mm.

[Physical properties of textiles]
The dyeing rate and the light fastness retention rate were evaluated by the above measuring method using the fabric and dyeing solution before and after dyeing. Although the dyeing rate of the fabric was as good as 90.9%, the light resistance retention rate of the fabric was as low as 61%, and a large amount of the ultraviolet absorber was eluted. The results are shown in Table 1.

  The meta-type wholly aromatic polyamide fiber cloth of the present invention is a light-resistant meta-type wholly aromatic polyamide fiber cloth that can be dyed in various hues by carrier dyeing and that can suppress the removal of the light-resistant agent during dyeing. Become. For this reason, the fabric of the present invention expresses the excellent heat resistance, flame resistance, and flame resistance inherent in the meta-type wholly aromatic polyamide fiber, has good dyeability for dyes, and has excellent light resistance. It becomes the cloth which has the property. Therefore, the meta-type wholly aromatic polyamide fiber fabric of the present invention has extremely great industrial value in the field where these characteristics are required.

Claims (8)

A fabric comprising a meta-type wholly aromatic polyamide fiber,
The meta-type wholly aromatic polyamide fiber contains an ultraviolet absorber having a solubility in water of less than 0.04 mg / L, the dyeing rate of the dyed fiber is 90% or more, and the light fastness retention before and after the carrier dyeing A meta-type wholly aromatic polyamide fiber fabric having a ratio of 80% or more.   In the meta-type wholly aromatic polyamide fiber, the residual solvent amount of the fibril is 0.1 mass% or less, and the strength retention of the dyed fiber after being immersed in a 20 mass% sulfuric acid aqueous solution at 50 ° C. for 150 hours is 65%. The meta-type wholly aromatic polyamide fiber fabric according to claim 1, which is as described above.   The meta-type wholly aromatic polyamide fiber fabric according to claim 1 or 2, wherein the blending amount of the ultraviolet absorber is 3.0 parts by mass or more and 6.5 parts by mass or less with respect to the entire fiber mass.   4. The meta-type wholly aromatic polyamide according to claim 1, wherein the ultraviolet absorber is at least one selected from the group consisting of a salicylic acid ultraviolet absorber, a benzophenone ultraviolet absorber, and a benzotriazole ultraviolet absorber. Fiber fabric.   The meta-type wholly aromatic polyamide fiber fabric according to any one of claims 1 to 4, wherein the fabric is in any form selected from the group consisting of a nonwoven fabric, a woven fabric, and a knitted fabric.   A blanket comprising the meta-type wholly aromatic polyamide fiber fabric according to any one of claims 1 to 5.   A curtain comprising the meta-type wholly aromatic polyamide fiber fabric according to any one of claims 1 to 5.   A chair upholstery fabric comprising the meta-type wholly aromatic polyamide fiber fabric according to any one of claims 1 to 5.