JPH0995870A - Aromatic polyamide-containing dyed textile fabric and dyeing of aromatic polyamide-containing textile fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dyed fabric with desired any hue and good in color fastness by dyeing a fabric comprising aromatic polyamide fibers and flame- retardant polyester fibers with a cationic dye followed by further dyeing with a disperse dye. SOLUTION: First, a fabric such as twill is produced by using spun yarns made by blending 95-60wt.% of poly-m-phenylene isophthalamide fibers containing alkylbenzene sulfonic acid onium salt and haloalkyl(phenyl) phosphate with 5-40wt.% of flame-retardant polyester fibers copolymerized with a phosphorus compound containing 0.3-1.5wt.%, based on the polymer, of elemental phosphorus. Next, the fabric is singed, scoured, dried, and heat-treated, and then dyed at 160 deg.C for 60min in a cationic dye bath followed by further dyeing in a disperse dye bath for 60min at such a temperature as not to dye the aromatic polyamide fibers (e.g. 130 deg.C) to effect dyeing the polyester fibers, thus affording the objective dyed fabric.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to firefighters, aviators,
TECHNICAL FIELD The present invention relates to a fabric and a dyeing method used for flame resistant clothes suitable for being worn by people engaged in work that may be exposed to flames such as race drivers, workers of electric power companies or chemical companies.

[0002]

2. Description of the Related Art Flame-retardant cotton, wool, flame-retardant vinylon, flame-retardant rayon, etc. are known as fibers that do not burn easily even when exposed to a flame and do not melt by heat.
It is provided as a flame resistant garment material. However,
These fibers did not have flame resistance enough to withstand a high temperature of 200 ° C. or higher for a long time. In addition, since a fabric made of these fibers is inherently poor in heat-setting property, pleats disappear or wrinkles occur while washing or wearing, which makes it difficult to wear. It was

Carbonized rayon, polybenzimidazole fiber and the like have been developed as materials having sufficient heat resistance and flame resistance and are provided as heat and flame resistant clothing materials. However, although these fibers are excellent in flame resistance and heat resistance, they are not satisfactory as a clothing material because they are poor in dyeability, lack in aesthetics, and inferior in texture and strength.

On the other hand, polymetaphenylene isophthalamide fiber is excellent in heat resistance, flame resistance and strength, but it is poor in heat setting property, and a cloth made of the fiber is poor in shape retention. On the other hand, there has been proposed a fabric in which polymetaphenylene isophthalamide fiber is used in combination with polyester fiber having a good heat setting property, and the shape retention property is improved without impairing heat resistance, flame retardancy and flame resistance. (Japanese Patent Laid-Open No. 4-50340), the problem of shape retention is solved by using the polyester fiber together. However, polymetaphenylene isophthalamide fiber has poor dyeability and cannot be dyed at the temperature for dyeing normal polyester fiber.Therefore, it is desired to develop a method for dyeing a fabric combined with polyester fiber without uneven color. It is rare. In response to this, a method for coloring the stock solution with a pigment (such as British Patent No. 1,438,067),
Method of introducing a functional group to improve dyeability (Japanese Patent Publication No. 44
No. 3,168,42), a method of simultaneously dyeing polymetaphenylene isophthalamide fiber and polyester fiber using a carrier (US Pat. No. 3,674,42).
Many methods have been proposed, such as No. 0 specification). However, undiluted solution coloring with pigments has the problems that the range of hues is limited and that it is not possible to cope with small lots and quick response.On the other hand, functional groups are introduced to improve dyeability, and carrier is used. When it is attempted to dye the polyester fiber mixed together, the disperse dye used for dyeing the polyester fiber also dyes the polymetaphenylene isophthalamide fiber, so that there is a problem that the disperse dye reduces dyeing fastness.

[0005]

The object of the present invention is to provide a desired hue without impairing the heat resistance, flame retardancy, flame resistance of aromatic polyamide fibers and the shape retention of polyester fibers. It is intended to obtain a fiber cloth containing an aromatic polyamide which is dyed in a dye and is excellent in dyeing fastness and a dyeing method thereof.

[0006]

The present invention is a cloth comprising at least 95 to 60% by weight of aromatic polyamide fiber and 5 to 40% by weight of polyester fiber, and the aromatic polyamide fiber is substantially a cationic dye. A fiber cloth containing a dyed aromatic polyamide, wherein the dyed polyester fiber is dyed with a disperse dye.

The present invention is also based on at least 95 to 69% by weight of aromatic polyamide fiber and 5 to 40 polyester fiber.
Dyeing of a fiber fabric containing aromatic polyamide, characterized in that a fabric consisting of wt% is first dyed with a cationic dye and then with a disperse dye at a temperature at which the disperse dye does not substantially dye the aromatic polyamide fiber. Is the way.

The aromatic polyamide fiber referred to in the present invention is mainly composed of
Meta-aramid fiber, i.e., a fiber consisting of poly-m-phenylene isophthalamide. The polymetaphenylene isophthalamide may be a fiber made of a polymer in which the following aromatic polyamides (a) to (c) are mixed.

(A) The amine component is xylenediamine 3
An aromatic polyamide containing 5 to 100 mol% of aromatic diamine, 65 to 0 mol% of aromatic diamine, and an aromatic dicarboxylic acid as an acid component (JP-A-55-21406). (B) The amine component is a phenylenediamine having at least one alkyl substituent having 1 to 4 carbon atoms or an aromatic diamine having no substituent, and the acid component is an aromatic polyamide (specifically, an aromatic dicarboxylic acid). 55-21
No. 407). (C) The amine component is composed of 40 to 100 mol% of phenylenediamine having 1 to 4 halogen substituents, and 60 to 0 mol% of an aromatic diamine having no substituent, and the acid component is an aromatic dicarboxylic acid. An aromatic polyamide comprising (JP-A-55-29516).

Further, up to about 20% by weight of copolymerized para-aramid fiber may be mixed with the aromatic polyamide fiber. The copolymerized para-aramid fiber is a fiber composed of a repeating unit represented by the following structural formula (I), and
r ₁ and Ar ₂ are aromatic compounds represented by the following (Chemical Formula 1). Ar ₁ and Ar ₂ may be the same or different.

--N--Ar ₁ --N--CO--Ar ₂ --CO --... (I)

[0012]

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[0013]

In the present invention, it is preferable that the aromatic polyamide fiber is an easily dyeable polymetaphenylene isophthalamide in which polymetaphenylene isophthalamide contains an onium alkylbenzenesulfonate. Examples of the alkylbenzene sulfonic acid onium salt include hexyl benzene sulfonic acid tetrabutyl phosphonium salt, hexyl benzene sulfonic acid tributyl benzene phosphonium salt, dodecyl benzene sulfonic acid tetraphenyl phosphonium salt, and dodecyl benzene sulfonic acid tributyl tetradecyl phosphonium salt. Examples thereof include compounds such as aluminum salts, tetrabutylphosphonium dodecylbenzene sulfonate, and tributylbenzylammonium dodecylbenzene sulfonate. Among them, dodecylbenzenesulfonic acid tetrabutylphosphonium salt or dodecylbenzenesulfonic acid tributylbenzylammonium salt is easily available, has good thermal stability, and has high solubility in N-methyl-2-pyrrolidone. Particularly preferred.

The ratio of the alkylbenzenesulfonic acid onium salt to the polymetaphenylene isophthalamide is preferably 2.8 to 7.0 mol%, more preferably 3.5 to 7.0 mol%. When the proportion of the onium salt of alkylbenzene sulfonic acid is less than 2.8 mol%, a sufficient effect of improving the dyeability is not observed, while 7.0
When it exceeds mol%, the number of single yarn breakages increases during yarn production.

Further, the polymetaphenylene isophthalamide used in the present invention more preferably contains a halogen-containing alkyl (phenyl) phosphate together with an alkylbenzenesulfonic acid onium salt. Examples of halogen-containing alkyl (phenyl) phosphates include tris (β-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, trichloroethylphosphate, phenyldichloropropylphosphate, tris (dichlorophenyl) phosphate. Examples of such compounds include tris (dichlorophenyl) phosphate, and among them, tris (dichlorophenyl) phosphate is preferable.

The proportion of the halogen-containing alkyl (phenyl) phosphate with respect to the polymetaphenylene isophthalamide is preferably 0.5 to 5.0% by weight, more preferably 1.8 to 5.0% by weight, and It is preferably 3.0 to 5.0% by weight. When the proportion of the halogen-containing alkyl (phenyl) phosphate is less than 0.5% by weight, no specific improvement in dyeability can be obtained. On the other hand, when it exceeds 5.0% by weight, the dyeability is not so improved. In addition to that, uneven dyeing may occur.

The intrinsic viscosity of the meta-aramid fiber is 0.5.
The value measured with a g / 100 ml concentrated sulfuric acid solution (30 ° C.) is preferably 0.8 to 4.0, particularly 1.0 to 3.0. Further, additives such as a flame retardant, a colorant, a light resistance improver, a matting agent and a conductive agent may be contained within a range not impairing the object of the invention.

The copolymerized para-aramid fiber may also contain additives such as a flame retardant, a colorant, a light resistance improver and a matting agent to the extent that the object of the invention is not impaired. The fiber lengths of the meta-aramid fiber and the copolymerized para-aramid fiber are preferably 25 to 200 mm, respectively.

The polyester fiber in the present invention means polyethylene terephthalate fiber, polybutylene terephthalate fiber, polynaphthalene terephthalate fiber and the like which are generally used for clothing or industrial materials, and do not impair the characteristics of polyester fiber. Copolymerized polyester fiber obtained by copolymerizing other dicarboxylic acid or other diol component to a degree or flame retardant for modification,
It includes so-called modified polyester fibers such as polyester fibers to which various additives such as antistatic agents are added, but modified polyester fibers copolymerized with a phosphorus compound are particularly preferable.
Examples of the phosphorus compound of the present invention include compounds represented by the following general formula (II).

[0021] [Wherein R is a saturated, open-chain or cyclic alkylene,
Indicates an arylene or alkylene residue. R ₁ is 1 to
An alkyl group, an aryl group or an alkyl group having 6 C atoms is shown. In addition, the residue R and / or R ₁ is 1
Or it may contain two or more heteroatoms, in particular F, Cl, Br, O or S. R ₂ and R ₃ represent an alkyl group having 1 to 18 carbon atoms, an aryl group or a hydrogen atom. ]

Specific examples of the phosphorus compound include 2-carboxy-ethyl-methyl-phosphinic acid represented by the following (Chemical Formula 2) or a cyclic anhydride thereof.

[0023]

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The mixing ratio of aromatic polyamide fiber and polyester fiber is preferably 95 to 60% by weight of aromatic polyamide fiber and 5 to 40% by weight of polyester fiber. The aromatic polyamide fiber should be dyed substantially with a cationic dye, and the polyester fiber should be dyed with a disperse dye. Aromatic polyamide fibers are substantially cationic dyes, and polyester fibers are dyed with disperse dyes. First, a cloth made of aromatic polyamide and polyester fibers is dyed with a cationic dye, and then only polyester fibers are dyed with a disperse dye. It is necessary to dye. The cationic dye is a water-soluble dye that is soluble in water and has a basic group, and is often used for dyeing acrylic fibers, natural fibers, cationic dyeable polyester fibers and the like. The cationic dye can be appropriately selected, and examples thereof include diacrylmethane type and triacrylmethane type, quinonimine (azine, oxazine, thiazine) type, xanthene type, methine type (polymethine, azamethine), heterocyclic azo type (thiazole). Azo, triazole azo, benzothiazole azo), and anthraquinone series. Also, recently
There are cationic dyes which are dispersed by blocking a basic group, but both can be used. In any case, it is preferable that the cationic dye is a dye that causes less contamination of the polyester fiber.

The disperse dye is a dye which is hardly soluble in water and is used for dyeing hydrophobic fibers from a system dispersed in water.
It is often used for dyeing polyester fibers and acetate fibers. The disperse dye can be appropriately selected, for example, benzeneazo (monoazo, disazo, etc.), heterocyclic azo (thiazole azo, benzothiazole azo, quinoline azo, pyrizone azo, imidazole azo, thiophene azo, etc.), anthraquinone type,
Examples thereof include condensed systems (quinophthaline, styryl, coumarin, etc.).

Usually, when dyeing a fabric in which different kinds of materials are mixed, in order to sufficiently dye each fiber and maintain the dyeing fastness, for example, in the case of a fabric made of polyester fiber and nylon, first, a disperse dye is used. Two-bath dyeing is generally carried out by dyeing polyester fibers with, then decolorizing the disperse dye dyed with nylon and then dyeing nylon with an acid dye.

Even in a fabric composed of aromatic polyamide fiber and polyester fiber, the disperse dye is dyed on any of the fibers, and the disperse dye dyed on the aromatic polyamide fiber hinders the dyeing fastness. Similarly to the cloth made of nylon and nylon, even if an attempt is made to decolorize the disperse dye dyed to the fiber side that inhibits the dyeing fastness, the disperse dye dyed to the aromatic polyamide fiber is difficult to decolorize,
When bleaching is performed under strict conditions, the polyester fiber is decolorized more than the aromatic polyamide fiber, and therefore a treatment such as a cloth of polyester fiber and nylon cannot be adopted.

Therefore, in the present invention, first, a cloth made of aromatic polyamide fiber and polyester fiber is dyed by raising the temperature of a dyeing bath containing a cationic dye to a temperature sufficient for dyeing the aromatic polyamide fiber, and then dispersing. It has been found that dyeing at a temperature at which only the polyester fiber can be dyed without dyeing the aromatic polyamide fiber with the dye, is sufficient for dyeing each fiber and maintaining dyeing fastness.

After the dyeing with the cationic dye is completed,
Dyeing with a disperse dye is carried out. At this time, the bath containing the cationic dye may be cooled to 80 ° C. or lower and then the disperse dye may be added to raise the temperature, or the bath containing the cationic dye may be once drained and newly prepared. Dyeing may be started for the first time after re-adjusting the dyeing bath containing the disperse dye.

As described above, in order to dye each fiber with a dye suitable for each fiber, in the case of a fabric composed of polymetaphenylene isophthalamide and polyester fiber,
It may be dyed with a cationic dye at a temperature of 150 ° C. or higher, and then with a disperse dye at 130 ° C. When the dyeing temperature with a cationic dye is lowered with the easily dyed polymetaphenylene isophthalamide, the polyester fiber is 130 ° C. By using a flame-retardant polyester that is copolymerized with a phosphorus compound that can be dyed at a lower temperature, the dyeing temperature of the disperse dye can be lowered to prevent dyeing of the polymetaphenylene isophthalamide with the disperse dye. There is a way.

[0031]

The present invention will be described with reference to the following examples. The following properties were evaluated as the dye fastness evaluation.

Rubbing fastness was carried out based on JIS L-0849-71 II type method. Washing fastness was performed based on JIS L-0844-73 A-2 method.

Example 1 100 parts of polymetaphenylene isophthalamide having an intrinsic viscosity of 1.8 was mixed with 5 parts of tris (dichlorophenyl) phosphate, and after wet spinning and drawing heat treatment in the usual manner,
Crimped, single yarn fineness 2.0 de, fiber length 51 mm,
A meta-aramid short fiber having 11 crimps / 2.5 cm was obtained. This short fiber and single yarn fineness 2.0 de, fiber length 51 m
m, crimp number 12 / 2.5 cm polyethylene terephthalate short fibers (semi-dal) are mixed at a weight ratio of 80/20 to make a 2/68 spun yarn with a wool count, and then a warp density of 88 / A twill weave having an inch density and a weft density of 74 threads / inch was woven. The obtained woven fabric is usually fried, refined, dried,
After the heat treatment, the dye bath shown in Table 1 was heated from room temperature to dye at 160 ° C. for 60 minutes. Then, the dye bath shown in Table 2 is newly heated from room temperature to dye at 130 ° C. for 60 minutes,
Reduction cleaning was performed by a standard method.

[0034]

[Table 1]

[0035]

[Table 2]

* 1; manufactured by BASF * 2: manufactured by Sandoz * 3: manufactured by Meisei Chemical Co., Ltd.

Example 2 100 parts of polymetaphenylene isophthalamide having an intrinsic viscosity of 1.8 was mixed with 12 parts of phosphonium dodecylbenzenesulfonate and 5 parts of tris (dichlorophenyl) phosphate, and wet spinning was carried out by a conventional method. , After drawing heat treatment, crimped, single yarn fineness 2.0 de, fiber length 51
mm short crimps 11 / 2.5 cm were obtained. This short fiber, single yarn fineness 2.0 de, fiber length 5
2-carboxy with 1 mm and 12 crimps / 2.5 cm
A twill fabric was woven in the same manner as in Example 1 by mixing a flame-retardant polyester (semi-dal) having 0.65% of ethyl-methyl-phosphinic acid copolymerized therein at a weight ratio of 80/20. The woven fabric thus obtained was subjected to usual quilting, refining, drying and heat treatment, and then the temperature was raised from room temperature to 130 in the dyeing bath shown in Table 1.
After dyeing at 60 ° C. for 60 minutes, reduction washing was performed. Then, in the dye bath shown in Table 2, the temperature was raised from room temperature to dye at 110 ° C. for 60 minutes, and reduction washing was performed by a conventional method.

Comparative Example 1 As in Example 1, the woven, woven, scoured, dried, and heat-treated fabric was dyed in a dyeing bath shown in Table 3 at a temperature from room temperature to 160 ° C. for 60 minutes, Then, reduction cleaning was performed in the same manner as in Example 1.

[0039]

[Table 3]

Comparative Example 2 A woven fabric which was woven, fried, smelted, dried and heat-treated in the same manner as in Example 2 was heated in a dye bath shown in Table 3 from room temperature to 1
Dyeing was carried out at 60 ° C. for 60 minutes, and then reduction washing was carried out as in Example 1.

Example 3 In the same manner as in Example 1, the woven, woven, scoured, dried and heat-treated woven fabric was dyed in the dyeing bath shown in Table 4 at a temperature from room temperature to 160 ° C. for 60 minutes. Then, in the dyeing bath shown in Table 5, the temperature was raised from room temperature to dye at 130 ° C. for 60 minutes, and reduction washing was carried out by a conventional method.

[0042]

[Table 4]

[0043]

[Table 5]

* 4: Hodogaya Chemical Co., Ltd. * 5: Nippon Kayaku Co., Ltd.

Example 4 In the same manner as in Example 2, the woven fabric which was woven, fried, refined, dried and heat-treated was dyed in the dyeing bath shown in Table 4 from room temperature to 120 ° C. for 60 minutes. Then, the dye bath shown in Table 5 was heated from room temperature to dye at 110 ° C. for 60 minutes, and reduction washing was carried out by a conventional method.

Comparative Example 3 A woven fabric which was woven, fried, refined, dried and heat-treated in the same manner as in Example 1 was heated in a dye bath shown in Table 6 from room temperature to 1
Dyeing was carried out at 60 ° C. for 60 minutes, and then reduction washing was carried out as in Example 1.

[0047]

[Table 6]

Comparative Example 4 A woven fabric which was woven, fried, refined, dried and heat-treated in the same manner as in Example 2 was heated to 1 from room temperature in a dyeing bath shown in Table 6.
Dyeing was carried out at 30 ° C. for 60 minutes, and then reduction washing was carried out as in Example 1.

Table 7 shows the results of evaluation of the dyeing fastness of the dyed fabrics of Examples 1 to 4 and Comparative Examples 1 to 4.

[0050]

[Table 7]

[0051]

[Table 8]

[0052]

The fiber cloth containing the aromatic polyamide of the present invention is a combination of aromatic polyamide fiber having excellent heat resistance, flame retardancy, flame resistance and strength, and polyester fiber having excellent shape retention. Since the obtained fabric is dyed in a required hue with good dyeing fastness, it is suitable as a garment material and the like as an aesthetic fabric having the characteristics of the aromatic polyamide fiber and the characteristics of the polyester fiber. This provides flame resistant clothing suitable for wear by people who may be exposed to flames, such as firefighters, aviators, race drivers, workers of electric power companies or chemical companies. . According to the dyeing method of the present invention, even a fabric in which aromatic polyamide fibers and polyester fibers are used in combination can be dyed with a desired color freely and without color unevenness and with good dyeing fastness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichi Hosoyama 1-6-7 Minamihonmachi, Chuo-ku, Osaka-shi, Osaka Inside Teijin Limited

Claims (12)

[Claims] 1. At least an aromatic polyamide fiber 95 to
A fabric consisting of 60% by weight and 5 to 40% by weight of polyester fiber, which is characterized in that the aromatic polyamide fiber is substantially dyed with a cationic dye and the polyester fiber is dyed with a disperse dye. A fiber cloth containing an aromatic polyamide. 2. The fiber fabric containing a dyed aromatic polyamide according to claim 1, wherein the aromatic polyamide fiber is a polymetaphenylene isophthalamide fiber. 3. The fiber fabric containing a dyed aromatic polyamide according to claim 2, wherein the aromatic polyamide fiber is an easily dyeable polymetaphenylene isophthalamide fiber containing an alkylbenzenesulfonic acid onium salt. 4. The easily dyeable polymetaphenylene isophthalamide fiber comprising an aromatic polyamide fiber comprising a composition containing an alkylbenzenesulfonate onium salt and a halogen-containing alkyl (phenyl) phosphate. A textile fabric comprising the dyed aromatic polyamide according to any one of 1. 5. The fiber cloth containing the dyed aromatic polyamide according to claim 1, wherein the polyester fiber is a flame-retardant polyester fiber. 6. The dyed fragrance according to claim 5, wherein the flame-retardant polyester fiber comprises a polyester fiber copolymerized with a phosphorus compound, and the amount of elemental phosphorus is 0.3 to 1.5% by weight based on the polymer. A fiber cloth containing a group polyamide. 7. At least an aromatic polyamide fiber 95 to
A fabric composed of 69% by weight and 5 to 40% by weight of polyester fiber is first dyed with a cationic dye, and then with a disperse dye at a temperature at which the disperse dye does not substantially dye the aromatic polyamide fiber. A method for dyeing a fiber cloth containing an aromatic polyamide. 8. The method for dyeing a fiber cloth containing an aromatic polyamide according to claim 7, wherein the aromatic polyamide fiber is a polymetaphenylene isophthalamide fiber. 9. The dyeing of a fiber fabric containing an aromatic polyamide according to claim 7, wherein the aromatic polyamide fiber is an easily dyeable polymetaphenylene isophthalamide fiber containing an alkylbenzenesulfonic acid onium salt. Method. 10. The easily dyeable polymetaphenylene isophthalamide fiber comprising an aromatic polyamide fiber comprising a composition containing an alkylbenzenesulfonate onium salt and a halogen-containing alkyl (phenyl) phosphate. A method for dyeing a fiber cloth containing the aromatic polyamide according to any one of 1. 11. The method for dyeing a fiber cloth containing an aromatic polyamide according to claim 7, wherein the polyester fiber is a flame-retardant polyester fiber. 12. The aromatic polyamide according to claim 11, wherein the flame-retardant polyester fiber is a polyester fiber copolymerized with a phosphorus compound, and the amount of elemental phosphorus is 0.3 to 1.5% by weight relative to the polymer. A method for dyeing a fiber cloth containing the same. [0001]