JP2002220739A - Easily dyeable meta-aramid fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an easily dyeable meta-aramid fiber having excellent flame retardance after dying and washing. SOLUTION: This easily dyeable meta-aramid fiber is obtained by including an alkylbenzenesulfonic acid onium salt and a nonhalogenated aromatic phosphoric ester in the fiber comprising the meta-aramid in which >=85 mol% of the whole repeating units are meta-phenylene isophthalamide units.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an easily dyeable meta-type aromatic polyamide fiber which can be easily dyed with a cationic dye and has excellent flame retardancy and excellent washing durability. .

[0002]

2. Description of the Related Art A meta-type aromatic polyamide fiber has excellent heat resistance and dimensional stability because its molecular skeleton is mostly composed of aromatic rings. The meta-type aromatic polyamide fiber utilizing this property is suitably used for industrial applications and applications where heat resistance, flame resistance and flame resistance are important.
In particular, applications in the field of bedding, clothing, and interiors utilizing its heat resistance and flame resistance are rapidly expanding. In these fields, it is common to use colored fibers.However, meta-type aromatic polyamide fibers have excellent physical properties, but the dyeing is difficult with ordinary methods because the polymer molecular chains are rigid. There is a problem that there is.

[0003] Therefore, various improvement methods have been proposed to solve this problem. For example, JP
JP-A-59522 proposes a colored fiber in which a specific pigment is contained in a meta-type aromatic polyamide fiber. However, since the pigment is contained in the fiber production process, loss during production increases, and therefore, There are problems such as difficulty in production for small lots and difficulty in obtaining fibers of various required hues.

As a means for improving the dyeing properties, Japanese Patent Application Laid-Open No. 55-21406 proposes a method of mixing a polymer obtained by copolymerizing xylylenediamine. In the production of a polymer obtained by copolymerizing the third component, there is a problem of a decrease in efficiency such as a decrease in the operation rate of a polymerization apparatus.

Further, as another means for improving the dyeing properties, JP-A-8-81827 discloses a method of adding an alkylbenzenesulfonic acid onium salt and a halogen-containing alkyl (phenyl) phosphate, and JP-A-2000-81827.
JP-A-328450 proposes a method of adding an alkylbenzenesulfonic acid onium salt and a condensed halogenated phosphoric acid ester. Certainly, according to these methods, good dyeability can be obtained, but in the former method, 13
Most of the halogen-containing alkyl (phenyl) phosphate ester is eluted into the dyeing solution by the dyeing treatment performed at a temperature of 0 ° C., and the flame retardancy is greatly reduced. Even if it shows good flame retardancy, there is a problem that toxic gas is easily generated when it is burned by being exposed to high temperatures.

In recent years, environmental issues have been emphasized worldwide, and there is a growing momentum for technical improvement to non-halogenation in a wide range of technical fields.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made on the background of the above-mentioned prior art, and has as its object the purpose of being able to easily dye, and the fiber after dyeing is soft and has excellent washing durability. It is to propose an easily dyeable meta-type aromatic polyamide fiber having flame retardancy.

[0008]

According to the study of the present inventors, the object of the present invention is to provide a fiber comprising a meta-type aromatic polyamide in which at least 85 mol% of all the repeating units are metaphenylene isophthalamide units. It has been found that this is achieved by an easily dyeable meta-type aromatic polyamide fiber in which an onium alkylbenzenesulfonate and a non-halogenated aromatic phosphate are included.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The meta-type aromatic polyamide used in the present invention is one in which the aromatic ring constituting the main skeleton is bonded to the meta-type by an amide bond, and at least 85 mol% of all repeating units of the polymer are meta-phenylene isophthalamide. The target is a unit, and a polymetaphenylene isophthalamide homopolymer is particularly preferable. 15 mol% of all repeating units
The third component, which can be copolymerized in an amount of preferably 5 mol% or less, includes, as a diamine component, for example, paraphenylenediamine, 3,4′-diaminodiphenyl ether,
4,4′-diaminodiphenyl ether, paraxylylenediamine, biphenylenediamine, 3,3′-dichlorobenzidine, 3,3′-dimethylbenzidine, 3,
Aromatic diane such as 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,5-naphthalenediamine and the like as an acid component such as terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-
And aromatic dicarboxylic acids such as 2,7-dicarboxylic acid. In these aromatic diamines and aromatic dicarboxylic acids, a part of the hydrogen atoms of the aromatic ring may be substituted with a halogen atom or an alkyl group such as a methyl group.

In addition, at least 20% of all terminals of the polymer are:
Blocking with a monovalent diamine such as aniline or a monovalent carboxylic acid component is preferable because the decrease in fiber strength is reduced even when the fiber is kept at a high temperature for a long time.

Such a meta-type aromatic polyamide can be produced by, for example, a conventionally known method of interfacial polymerization or solution polymerization of an aromatic diamine and an aromatic dicarboxylic acid dihalide. As the degree of polymerization of the polymer, N-methyl-2-pyrrolidone as a solvent is 30
0.8 to 3.0, preferably 1.0 to 2.0, particularly preferably 1.3 to 1.9, measured at 100C.
Are preferred.

The onium alkylbenzenesulfonate salt contained in the above-mentioned meta-type aromatic polyamide is necessary so that the fiber can be easily dyed with a cationic dye. The carbon number is suitably in the range of 6 to 18, especially 8 to 16. On the other hand, as the onium salt, a quaternary onium salt, particularly a quaternary phosphonium salt or a quaternary ammonium salt, is preferable in that good dyeing properties can be obtained. Among them, a tetrabutylphosphonium salt or a benzyltrimethylammonium salt is preferable because of good availability and good thermal stability.

The onium salts preferably used include:
For example, hexylbenzenesulfonic acid tetrabutylphosphonium salt, hexylbenzenesulfonic acid tributylbenzylphosphonium salt, dodecylbenzenesulfonic acid tetraphenylphosphonium salt, dodecylbenzenesulfonic acid tributyltetradecylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzene Tributyl benzyl ammonium sulfonate, tetrabutyl ammonium octyl benzene sulfonate, dimethyl dibenzyl ammonium dodecyl benzene sulfonate and the like can be mentioned. Among them, tetrabutylphosphonium dodecylbenzenesulfonate and tributylbenzylammonium dodecylbenzenesulfonate have excellent dyeing properties and a good fastness of the dyed product, and also have a property against N-methyl-2-pyrrolidone. It is particularly preferred because of its high solubility.

The content of such an alkylbenzene sulfonic acid onium salt in the meta-type aromatic polyamide fiber varies depending on the degree of coloring by dyeing. 2.8 mol% or more, preferably 2.8 to 8.0, based on the repeating units of the aromatic polyamide fiber (based on all repeating units).
Molar%, particularly preferably in the range of 3.5 to 7.0 molar%.

Next, the non-halogenated aromatic phosphate ester, which is another component contained in the meta-type aromatic polyamide, improves the dyeability of the fiber with cationic dyes and imparts washing durability to the fiber after dyeing. It is necessary to impart a certain flame retardancy and to reduce the generation of toxic gas even if burned.

Examples of the non-halogenated aromatic phosphate ester include monomer-type aromatic phosphate compound such as tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, etc .; Examples thereof include, but are not limited to, condensed aromatic phosphates such as phosphates.

If the content of the non-halogenated aromatic phosphoric acid ester is too small, the effect of improving the dyeability is reduced, and the flame retardancy of the colored fiber after dyeing is also reduced. 0.0% by weight or more, preferably 5.0%
It is appropriate that the content be not less than weight%. If the amount is too large, the effect of improving the dyeability and the flame retardancy does not become so large, and conversely, the heat resistance is reduced or the phosphorus compound bleeds out at the time of dyeing, so that the feeling is impaired.
It is desirable that the content be 10.0% by weight or less, particularly 8.0% by weight or less. Especially, the range of 5.0-8.0 weight% is suitable.

In the present invention, the method of incorporating the above-mentioned onium alkylbenzenesulfonate and non-halogenated aromatic phosphate into the fiber comprising the above-mentioned meta-type aromatic polyamide is not particularly limited. A solution (dope) in which a meta-type aromatic polyamide such as phenylene isophthalamide is dissolved in a solvent together with an alkylbenzenesulfonic acid onium salt and a non-halogenated aromatic phosphate ester may be fiberized by a conventionally known molding method.

For example, as an example of a typical molding method, an onium alkylbenzenesulfonate and a non-halogenated aromatic phosphate are added to a solution of polymetaphenylene isophthalamide in N-methyl-2-pyrrolidone. Prepare dope. There is a method in which the dope is extruded from a nozzle into an aqueous solution of an inorganic salt containing calcium chloride as a main component, coagulated, washed with water, and then drawn in boiling water to obtain a fiber.

When the fiber of the present invention is used as a short fiber in a spun yarn or the like, the fiber obtained as described above may be crimped and then cut to a predetermined length.

The fibers of the present invention described above may be dyed in the state of fibers such as raw cotton, tow, and yarn.
It may be dyed after being made into a fabric such as a nonwoven fabric.

[0022]

The present invention will be described below in more detail with reference to examples. In addition, each characteristic value in an Example and a comparative example is:
The following measurement method was used. <Intrinsic viscosity (IV)> The polymer was converted to NMP (N-methyl-
2-pyrrolidone) and measured at a temperature of 30 ° C. using an Ostwald viscometer. <Dyeability> Using a Macbeth Color Eye color measuring device manufactured by Macbeth Co., Ltd., a 2 degree field of view, D65 light source, wavelength 3
L * value was determined by measuring under the condition of 60 to 740 nm.

<Content of (Non-Halogenated Aromatic) Phosphate Ester> From a standard sample of (Non-halogenated aromatic) phosphate ester of known concentration, a calibration curve was prepared by X-ray fluorescence analysis, Was determined for the concentration of phosphorus atoms. Assuming that all of the phosphorus atoms were derived from (non-halogenated aromatic) phosphate, the content of the phosphate was calculated and calculated. <Retention ratio of phosphate ester> It was calculated from the amount of phosphate ester in the fibers before and after dyeing by the following formula. Retention (%) = phosphate content after dyeing / phosphate content before dyeing × 100

<Flame retardancy> LOI of JISL K7201
The LOI value was determined according to the measurement method. <Washing Durability> Water washing was performed 50 times according to the JIS L1091 method, and then the LOI value was determined. <Hand feeling> By a sensory test, in comparison with an ordinary meta-type aromatic polyamide fiber fabric to which an alkylbenzene sulfonate onium salt as an easy dyeing agent and a (non-halogenated aromatic) phosphate ester are not added. An equivalent was determined to be good, and a harder than the standard fabric was determined to be hard.

Examples 1 and 2 Intrinsic viscosity is 1.35 dl
/ G of polymetaphenylene isophthalamide of 30 g / N
The content of 3.6 g of tetrabutylphosphonium dodecylbenzenesulfonate and non-halogenated aromatic phosphate [CR741] manufactured by Daihachi Chemical Co., Ltd. in the dope dissolved in 110 g of -methyl-2-pyrrolidone is shown in the table. The components were mixed and dissolved so as to have the ratio described in 1, and defoamed under reduced pressure to obtain a spinning dope.

The obtained spinning dope was heated to 85 ° C. and extruded from a spinneret having a hole diameter of 0.07 mm and 200 holes into a coagulation bath and wet-spun. The composition of the coagulation bath was 40% by weight of calcium chloride, 5% by weight of NMP, the balance was 55% by weight of water, and the temperature of the coagulation bath was 85 ° C. The discharged yarn traveled about 10 cm in the coagulation bath, and was 6.2 m /
Withdrawn at a speed of minutes. Next, the drawn yarn is washed with water,
The film was drawn 2.3 times in hot water at 95 ° C., dried through a heating roll at 200 ° C., and further drawn 1.5 times on a hot plate at 285 ° C. to obtain a drawn yarn.

The obtained drawn yarn was crimped through a crimper and then cut with a cutter to obtain 2.2 dtex.
× 51 mm short fiber, then the short fiber was converted into a spun yarn having a cotton count of 30 / − according to a conventional method, and the spun yarn was used for warp and weft to prepare a plain woven fabric having a basis weight of 200 g / m ² . .

The obtained woven fabric is scoured according to a standard method,
After drying and heat setting, Esterol Navy Blue N
-2RL (Cation dyes manufactured by Sumitomo Chemical Co., Ltd.) 8% ow
f, acetic acid 0.3 g / liter, sodium nitrate 25 g /
Using a liter of dyeing liquor, a bath ratio of fiber to dyeing liquor of 1:20
For 60 minutes at 130 ° C. After dyeing, hydrosulfite 1.0 g / liter, amylazine D
(Daiichi Kogyo Seiyaku Co., Ltd.) Using a treatment solution containing 1.0 g / L and sodium hydroxide 1.0 g / L at a bath ratio of 1:40 and reduction washing at 80 ° C. for 30 minutes,
After washing with water, it was dried. Table 1 shows the evaluation results of the obtained treated cloth.

[Example 3] In Example 1, a non-halogenated aromatic phosphate [CR74 manufactured by Daihachi Chemical Co., Ltd.]
Example 1 except that a non-halogenated aromatic phosphate [CR733S] manufactured by Daihachi Chemical Co., Ltd. was used in place of [1].
And treated exactly the same. Table 1 shows the evaluation results of the obtained treated cloth.

Comparative Example 1 In Example 1, a non-halogenated aromatic phosphate [CR74 manufactured by Daihachi Chemical Co., Ltd.]
The procedure of Example 1 was repeated except that a non-halogenated aliphatic phosphate [TEH: triethyl phosphate] manufactured by Daihachi Chemical Co., Ltd. was used instead of [1]. Table 1 shows the evaluation results of the obtained treated cloth.

[Comparative Examples 2 and 3] In Example 1, a non-halogenated aromatic phosphate ester [CR
741] was carried out in the same manner as in Example 1 except that the content was as shown in Table 1. Table 1 shows the evaluation results of the obtained treated cloth.

[0032]

[Table 1]

[0033]

The easily dyeable meta-type aromatic polyamide fiber of the present invention described above has excellent properties such as heat resistance, flame resistance and flame resistance inherently possessed by the meta-type aromatic polyamide fiber. It has excellent dyeability of cationic dyes without impairment, and can be effectively used in the fields of bedding, clothing, and interior requiring coloring.

Further, since a non-halogenated aromatic phosphate ester is used as the phosphate ester, no toxic gas is generated even if it is burned. Since there is almost no elution,
It has the characteristic of being extremely excellent in durability such as flame retardancy and little deterioration of feeling.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) D01F 6/60 371 D01F 6/60 371 (72) Inventor Akihiro Oba 2-1 Hinodemachi, Iwakuni-shi, Yamaguchi Prefecture Teijin Co., Ltd. Iwakuni Office F-term (reference) 4J001 DA01 DB01 DB04 EB36 EB37 EB46 EC45 EC46 EC48 EC54 EC66 EC67 EE43E EE72E EE74E EE75E GA13 GA16 HA02 JA10 JB19 JB35 JC04 4J002 CL031 EV256 EW047 FD00 EE037 EB00

Claims (4)

[Claims] 1. A fiber comprising a meta-type aromatic polyamide in which 85 mol% or more of all repeating units are metaphenylene isophthalamide units, wherein the fibers include an onium alkylbenzene sulfonate and a non-halogenated aromatic phosphoric acid. An easily dyeable meta-type aromatic polyamide fiber comprising an ester. 2. The easily dyeable meta-type aromatic polyamide fiber according to claim 1, wherein the alkylbenzenesulfonic acid onium salt is a quaternary onium salt. 3. The easily dyeable meta-type aromatic polyamide fiber according to claim 2, wherein the quaternary onium salt of alkylbenzenesulfonic acid is a tetrabutylphosphonium salt or a tributylbenzylammonium salt. 4. The content of the onium alkylbenzene sulfonate is 2.8 to 8.0 mol% based on the repeating unit of the meta-type aromatic polyamide, and the content of the non-halogenated aromatic phosphate is meta-type. The easily dyeable meta-type aromatic polyamide fiber according to claim 1, wherein the amount is 4.0 to 10.0% by weight based on the weight of the aromatic polyamide.