JP2000328364A - Easily dyeable, meta type aromatic polyamide fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject fiber, easily dyed with a cationic dye to be highly flame-retarded and resistant to washing by including an onium salt of alkyl benzene sulfonate and specific condensed type halogenated phosphate ester in the meta type aromatic polyamide fiber. SOLUTION: This fiber of meta type aromatic polyamide has a metaphenylene isophthalamide unit (preferably polymetaphenylene isophthalamide homopolymer) which accounts for at least 85 mol% of the total repeating units, and is incorporated with an onium salt of alkyl benzene sulfonate and condensed type halogenated phosphate ester shown by the formula [R is a 2-6C halogenated alkyl; X is a direct bond or 1-4C alkylene; and (n) is 1 to 10].

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 dyeability, 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 dyeability, Japanese Patent Application Laid-Open No. 8-81827 proposes a method of adding an onium alkylbenzenesulfonate and a halogen-containing alkyl (phenyl) phosphate. Certainly, although good dyeing properties can be obtained according to this method, most of the halogen-containing alkyl (phenyl) phosphate esters are eluted into the dyeing solution by the dyeing treatment carried out at a temperature of 130 ° C., so that the flame retardant property is obtained. However, at present, meta-type aromatic polyamide fibers having both good dyeability and flame retardancy have not been obtained.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the above-mentioned meta-type aromatic polyamide fiber, and can be easily dyed, and the dyed fiber is flame-retardant having excellent washing durability. It is an object of the present invention to propose an easily dyeable meta-type aromatic polyamide fiber having property.

[0007]

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 containing an onium alkylbenzenesulfonate and a condensed halogenated phosphoric ester represented by the following general formula (Formula 2). Was.

[0008]

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[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The meta-type aromatic polyamide used in the present invention has an aromatic ring constituting a main skeleton bonded to a meta-type by an amide bond, and 85 moles of all repeating units of the polymer. % Or more are metaphenylene isophthalamide units, and polymetaphenylene isophthalamide homopolymer is particularly preferable. As a third component which can be copolymerized in an amount of 15 mol% or less, preferably 5 mol% or less of all repeating units, a diamine component
For example, paraphenylenediamine, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether, paraxylylenediamine, biphenylenediamine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,4 ' -Diaminodiphenylmethane,
Aromatic diane such as 4,4'-diaminodiphenylmethane, 1,5-naphthalenediamine, and as an acid component,
Examples thereof include aromatic dicarboxylic acids such as terephthalic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-2,7-dicarboxylic acid. In these aromatic diamines and aromatic dicarboxylic acids, a part of hydrogen atoms in the aromatic ring may be substituted by 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 interfacially polymerizing an aromatic diamine and an aromatic dicarboxylic acid dihalide. As the degree of polymerization of the polymer, N-methyl-2
Those having an intrinsic viscosity (IV) of 0.8 to 3.0, particularly 1.0 to 2.0 measured at 30 ° C. using pyrrolidone as a solvent 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, tetradecylphosphonium dodecylbenzenesulfonate and tributylbenzylammonium dodecylbenzenesulfonate have excellent dyeability and good fastness of the dyed product, and 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. 2.5 mol% or more, preferably from 2.5 to 10%, based on the repeating units of the aromatic polyamide fiber (based on all repeating units).
0 mol%, particularly preferably in the range of 3.0 to 7.0 mol%.

Next, a condensed halogenated phosphoric acid ester represented by the following general formula (3), which is another component contained in the meta-type aromatic polyamide, improves the cationic dye dyeability of the fiber. In addition to the above, it is necessary for imparting washing-resistant flame retardancy to the dyed fiber.

[0016]

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In the formula, R represents a halogenated alkyl group having 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms, wherein the halogen atom represents chlorine or bromine, and the number of halogen substitution in the halogenated alkyl group is It may be one or two or more. Among them, 2-chloroethyl group, 2-chloropropyl group, 2,
A 3-dichloropropyl group, a 2-bromoethyl group, or a 2,3-dibromopropyl group is preferable because the colored fiber obtained by dyeing has good flame retardancy and good washing durability. X represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylmethylene group. Also, n is 1 to
It is an integer of 10, particularly preferably an integer in the range of 2 to 4.

As the condensed halogenated phosphoric acid ester, R is a chloroethyl group, X is a methylmethylene group,
A compound in which n is 3 can be preferably exemplified.

If the content of the condensed halogenated phosphoric acid ester in the meta-type aromatic polyamide fiber is too small, the effect of improving the dyeability is reduced, and the flame retardancy of the colored fiber after dyeing is also reduced. It is desirably at least 1.8% by weight, preferably at least 3.0% by weight, based on the weight of the fiber. If the amount is too large, the effect of improving the dyeing properties and the flame retardancy does not become so large, and conversely, the spots at the time of dyeing become conspicuous.
It is desirable that the content be 0% by weight or less.

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

For example, as an example of a typical molding method, an onium alkylbenzenesulfonate and a condensed halogenated phosphoric acid ester are added to a solution of polymetaphenylene isophthalamide in N-methyl-2-pyrrolidone for doping. Is prepared. 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 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 form of fibers such as raw cotton, tow, and yarn.
It may be dyed after being made into a fabric such as a nonwoven fabric.

[0024]

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)>
(N-methyl-2-pyrrolidone) and measured at a temperature of 30 ° C. using an Ostwald viscometer.

<Dyeability> Using a color measuring device "Macbeth Color Eye" manufactured by Macbeth Co., Ltd., visual field twice, D65
Measured under the conditions of a light source and a wavelength of 360 to 740 nm, L *
The value was determined.

<Content of Condensed Halogenated Phosphate Ester (Flame Retardant)> From a standard sample of a condensed halogenated phosphoric acid ester having a known concentration, a calibration curve was prepared by X-ray fluorescence analysis to determine the phosphorus content in the fiber. The atomic concentration was determined. Assuming that all of the phosphorus atoms were derived from the condensed halogenated phosphoric acid ester, the content of the flame retardant was calculated and calculated.

<Flame retardant retention> The flame retardant retention in the fiber before and after dyeing was calculated by the following equation. Retention rate of flame retardant (%) = content of flame retardant after dyeing / content of flame retardant before dyeing × 10
0

<Flame retardancy> LOI of JISL K7201
The LOI value was determined according to the measurement method.

<Washing Durability> Water washing was carried out 50 times in accordance with the JIS L1091 method, and then the LOI value was determined.

Examples 1 and 2 Intrinsic viscosity is 1.35 dl
/ G of polymetaphenylene isophthalamide of 30 g / N
To a dope dissolved in 110 g of -methyl-2-pyrrolidone, 3.6 g of tetrabutylphosphonium dodecylbenzenesulfonate and a condensed halogenated phosphoric acid ester manufactured by Daihachi Chemical Co., Ltd. [CR387: R is a chloroethyl group, X Is a methylmethylene group, and the condensed halogenated phosphoric acid ester having an average of n of 3] is mixed and dissolved, and the mixture is 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 form a 2.0 de × 5.
A 1 mm short fiber was formed, then the short fiber was formed into a spun yarn having a cotton count of 30 /-according to a conventional method, and the spun yarn was used as a warp and a 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 conventional 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
And dyeing treatment at 130 ° C. for 60 minutes. 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 The procedure of Example 1 was repeated, except that tributylbenzylammonium dodecylbenzenesulfonate was used instead of tetrabutylphosphonium dodecylbenzenesulfonate. Table 1 shows the evaluation results of the obtained treated cloth.

Example 4 The procedure of Example 1 was repeated except that a condensed halogenated phosphate [CR38, manufactured by Daihachi Chemical Co., Ltd.] was used.
7] was replaced with a condensed halogenated phosphoric ester [CR505] manufactured by Daihachi Chemical Co., Ltd. Table 1 shows the evaluation results of the obtained treated cloth.

[Comparative Example 1] In Example 1, a condensed halogenated phosphate [CR38 manufactured by Daihachi Chemical Co., Ltd.]
[7], except that a monomer type halogenated phosphoric ester [TMCPP: tris (chloropropyl) phosphate] manufactured by Daihachi Chemical Co., Ltd. was used. Table 1 shows the evaluation results of the obtained treated cloth.

[0038]

[Table 1]

[0039]

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. Furthermore, since the condensed halogenated phosphoric ester used in combination hardly elutes from the fiber during dyeing, the resulting dyed fiber not only exhibits excellent flame retardancy, but also has extremely excellent flame retardant washing durability. It has the feature of being.

Claims (4)

[Claims] 1. A fiber comprising a meta-type aromatic polyamide in which at least 85 mol% of all the repeating units are metaphenylene isophthalamide units, wherein the fiber comprises an onium salt of alkylbenzenesulfonic acid and the following general formula (1).
An easily dyeable meta-type aromatic polyamide fiber comprising a condensed halogenated phosphoric acid ester represented by the formula: Embedded image 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 2.5 to 10.0 mol% based on the repeating unit of the meta-type aromatic polyamide, and the content of the condensed halogenated phosphoric acid ester is based on the weight of the fiber. 1.8-6.0
2. The easily dyeable meta-type aromatic polyamide fiber according to claim 1, which is contained in a weight percent.