JP3295129B2 - Method for producing cationic dyed meta-aramid fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION A meta-aramid fiber comprising a cationic dye and an aromatic dicarboxylic acid ester, which can be used for general clothing, interior and industrial purposes.

[0002]

2. Description of the Related Art Polymetaphenylene isophthalamide (hereinafter abbreviated as meta-type aramid) fibers have high heat resistance, flame resistance, and chemical resistance, but their molecular chains are extremely rigid. And high crystallinity, it was extremely difficult to dye.

Conventional methods for dyeing meta-type aramid fibers include: (1) dyeing under high temperature and high pressure using a large amount of a carrier such as acetophenone and paraphenylphenol (for example, JP-A-58-87376). (2) A method of pre-treatment with a solvent such as dimethylformaldehyde or dimethyl sulfoxide at room temperature and then dyeing (for example, JP-A-52-25178). (3) A method of dyeing by heating in a solvent such as dimethyl sulfoxide ( For example, JP-A-62-268877) can be mentioned.

[0004] However, the method (1) uses a large amount of carrier, so that it is difficult to remove the carrier after dyeing, which significantly affects the flame resistance. In the method (2), ring dyeing is liable to occur, not only the original hue is not obtained, but also the light fastness is extremely poor. The method (3) uses a large amount of flammable hazardous organic solvents and thus cannot be produced at present because a closed dyeing apparatus is required. Further, the methods disclosed therein tend to pollute the environment in terms of drainage and the like, and are not necessarily appropriate from the standpoint of environmental protection.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cation-dyeing meta-type dye which is dyed with a cationic dye in a dark color and with good light fastness using an organic substance which is easily decomposed biochemically. It is to provide an aramid fiber.

[0006]

Means for Solving the Problems Here, the present invention relates to a " dye mother "
Dyeing using a dye bath containing a cationic dye having a molecular weight of 250 to 500 and a benzenedicarboxylic acid ester
Cationic dyeing meta-aramid fibers, characterized in that that
Manufacturing method ”.

The meta-type aramid fiber in the present invention is a fiber made of polymetaphenylene isophthalamide or a copolymer containing the same as a main component (a registered trademark of Conex, manufactured by Teijin Limited). Further, the fabric of the present invention may be blended with natural fibers such as cotton, wool, regenerated fibers such as rayon and acetate, and other synthetic fibers, mixed weave, cross-woven, etc., in addition to the meta-aramid fibers, if necessary. Used as

The cationic dye is a dye which is soluble in water and is used for dyeing synthetic fibers, and is often used for dyeing and coloring cationic dyeable polyester fibers and acrylic fibers. It is broadly classified into two structural types. First, conjugated cationic dyes include methine-based, polymethine-based, azamethine-based, azo-based, triazoleazo-based, thiazoleazo-based, benzothiazoleazo-based, and triphenylmethane-based dyes. System, anthraquinone system, etc., but in the present invention, the molecular weight of the pigment base is 250 to
500 or less. The positive ion of the dye matrix of the cationic dye is one. If the molecular weight of the pigment base exceeds 500, it becomes hardly soluble in water and cannot be dyed without unevenness. Further, the thermal decomposition resistance of the dye is such that the residual ratio of the dye after treatment at 130 ° C. for 60 minutes is at least 9%.
It is preferably 0% or more. If the residual ratio is less than 90%, the hue becomes unclear and the color fastness is adversely affected.

Next, the dyeing temperature is required to be 110 ° C. or higher, preferably 130 ° C. or higher. If the dyeing temperature is lower than 110 ° C., sufficient dyeing cannot be performed. The higher the dyeing temperature is, the higher the dyeing property is, but on the other hand, problems such as decomposition of the dye also begin to occur. Therefore, it is not always necessary to set the temperature to a high temperature. On the other hand, in the present invention, it is important to use a benzenedicarboxylic acid ester similar to the basic skeleton structure of the polymetaphenylene isophthalamide-based fiber as the carrier as the dye diffusing agent. Since this carrier is an aromatic dicarboxylic acid ester, it has no ionic bond with the cationic dye, has good compatibility with the meta-type aramid fiber, and facilitates diffusion and adsorption of the cationic dye into the fiber. Specific examples of the organic compound include dimethyl terephthalate, dimethyl isophthalate, and dimethyl phthalate. Examples of the alkyl residue of the ester group include ethyl and propyl other than methyl.
In the case of dyeing using a benzenedicarboxylic acid ester, the BOD and COD of a 1% dispersion solution of this carrier are both 500 mg / liter or less, so that drainage load is reduced and environmental pollution is reduced. Where BOD,
COD refers to the amount of oxygen consumption (COD Mn) and the amount of biochemical oxygen consumption (BOD) of potassium permanganate at 100 ° C specified in JIS-K-0102-1986 (Factory drainage test method), respectively. is there. Although the residual amount of such organic substances in the fiber is almost completely eliminated by reduction washing and heat treatment after dyeing, the final amount is 50 mg / g-fiber or less (measured by gas chromatography).

[0010]

According to the present invention, a cationic dye and benzene
Dyeing using a dye bath containing rubonic acid ester
Because, resulting meta-aramid fiber is the effect of high coloring property can be obtained by containing an aromatic dicarboxylic acid ester traces of a particular molecular weight of the cationic dye. Since this benzene dicarboxylic acid ester has a structure almost identical to the dicarboxylic acid component of the polymetaphenylene isophthalamide fiber, it diffuses into the fine region inside the fiber with a small amount of addition to the dyeing bath. The dye is strongly dyed. When the dyeing is completed, the fine structure of the fiber returns to the original dense state, so that the dyed dye does not easily fall off, and high fastness is obtained.

Next, the present invention will be described in detail with reference to examples. The evaluation method described in the examples is as follows.

The evaluation of the cationic dyeing property was represented by the L * value, which was obtained from the tristimulus values X, Y, and Z obtained from the diffuse reflectance according to JIS-Z-8701. It shows that it is dyed darker.

[0013]

Examples 1 to 6 As a meta-type aramid fiber, Conex (registered trademark) having a spun yarn count of 40/2 obtained from 2 denier × 38 mm bias cut souff was used. 2 with a weft density of 58 lines / inch
/ 1 twill. The basis weight of the obtained fabric is 220 g.
/ M ² . Next, this woven fabric is score roll 90
0 (nonionic surfactant, manufactured by Kao) and heated to 80 ° C. in a bath containing 2 g / l of sodium carbonate and 1 g / l of sodium carbonate,
After scouring for 30 minutes, heat treatment was performed at 190 ° C. for 1 minute.

The obtained woven fabric is heated at 130 ° C. and 1
Stained at 70 ° C. for 60 minutes. Dye 6% owf Acetic acid 0.4 cc / l Benzenedicarboxylic acid ester 25 g / l Bath ratio 1:30 The dyed fabric was reduced and washed as follows to remove the cationic dye adhering to the fiber surface. Caustic soda (flakes) 1 g / liter Hydrosulfite 1 g / liter Amylazine D 1 g / liter (nonionic activator, Dai-ichi Kogyo Seiyaku Co., Ltd.) 80 ° C for 20 minutes Dye 1) Aizen Cathilon Red BLH (CI Basic Red 39: molecular weight of pigment base) 429) 2) Diacryl Blue GRL-N (manufactured by Mitsubishi Kasei Co., Ltd.) (CI Basic Blue 41: molecular weight of pigment base 323) benzenedicarboxylic acid ester 1) dimethyl terephthalate 2) dimethyl phthalate Heat treatment was performed at 170 ° C. for 1 minute. Table 1 shows the results.

[0015]

Comparative Example 1 The same procedure as in Example 1 was carried out except that dimethyl terephthalate was not added. Table 1 shows the results.

[0016]

Comparative Example 2 The same procedure as in Example 1 was carried out except that acetophenone was used in place of dimethyl terephthalate. Table 1 shows the results.

[0017]

Comparative Example 3 The same procedure as in Example 1 was carried out except that dichlorophenol was used in place of dimethyl terephthalate. Table 1 shows the results.

[0018]

Comparative Example 4 A copolymer of paraphenylene terephthalamide and 3,4'-oxydiphenyl terephthalamide (registered as Technora, manufactured by Teijin Limited) in place of the meta-type aramid fiber (Conex, registered trademark) of Example 1. All procedures were performed in the same manner as in Example 1 except that aromatic polyamide fibers having a paraphenylene group incorporated in the main chain thereof, such as (trademark), were used. Table 1 shows the results.

[0019]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D06P 3/26 D06P 1/62 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A dye matrix containing a cation dye having a molecular weight of 250 to 500 and a benzenedicarboxylic acid ester .
A method for producing a cationically dyed meta-type aramid fiber , characterized by dyeing using a dye bath .