JPH05331781A - Meta-type aramid fiber dyed with cationic dye - Google Patents

Abstract

PURPOSE:To obtain the subject meta-type aramid fiber deeply dyed and excellent in color fastness by adding a benzenecarboxylic acid ester to a cationic dye- containing dye liquor and dyeing the fiber with the resultant dye bath. CONSTITUTION:A dye bath is prepared by adding a benzenecarboxylic acid ester to a cationic dye-containing dye liquor and a meta-type aramid fiber (polymetaphenylene isophthalamide-based fiber) is dyed (130 to 170 deg.C) by using the dye bath. Thereby, a deep dyed fiber especially excellent in colorfastness to light is obtained. As the benzenecarboxylic acid ester, dimethyl terephthalate, dimethyl phthalate, etc., are preferably used.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Polymetaphenylene isophthalamide (hereinafter abbreviated as meta-aramid) fibers have excellent heat resistance, flame resistance, chemical resistance, etc., but their molecular chains are extremely rigid. Therefore, dyeing was extremely difficult because of high crystallinity.

The conventional method for dyeing meta-aramid fibers is as follows: (1) A method in which a large amount of a carrier such as acetophenone or paraphenylphenol is used and dyeing is carried out at high temperature and high pressure (for example, JP-A-58-87376). (2) Method of pretreatment with a solvent such as dimethylformaldehyde or dimethylsulfoxide at room temperature, followed by dyeing (for example, JP-A-52-25178) (3) Method of heating and dyeing in a solvent such as dimethylsulfoxide ( For example, JP-A-62-268877) can be mentioned.

However, since the method (1) uses a large amount of carrier, it is difficult to remove the carrier after dyeing, and the flameproofness is significantly adversely affected. In the method (2), ring dyeing is likely to occur, the original hue is not obtained, and the light fastness is extremely poor. The method (3) cannot be produced at present because of the use of a large amount of flammable dangerous substances organic solvent, which requires a closed dyeing device. 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]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a cationic dyeing meta type obtained by dyeing an organic substance which is easily biochemically decomposed with a cationic dye in a dark color and with good light fastness. To provide aramid fiber.

[0006]

The present invention is a "meta-aramid fiber characterized by containing a cationic dye and a benzenedicarboxylic acid ester".

The meta-aramid fiber in the present invention is a fiber (conex registered trademark manufactured by Teijin Ltd.) made of a polymetaphenylene isophthalamide fiber or a copolymer containing it as a main component. In addition to the meta-aramid fiber, the fabric of the present invention may optionally be blended with natural fibers such as cotton and wool, regenerated fibers such as rayon and acetate, and other synthetic fibers, mixed woven fabric, knitted fabric, etc. Used as.

The cationic dye is a dye that 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 roughly classified into two structural types. First, as a conjugated cationic dye, there are methine-based, polymethine-based, azamethine-based, azo-based, triazoleazo-based, thiazoleazo-based, benzothiazoleazo-based, triphenylmethane-based, etc. System, anthraquinone system, etc., but in the present invention, the molecular weight of the dye matrix is 250 to
It is 500 or less. Further, the cation base of the cationic dye has only one positive ion. When the molecular weight of the dye base exceeds 500, it becomes poorly soluble in water and it becomes impossible to dye it evenly. Furthermore, the thermal decomposition resistance of the dye is such that the residual rate of the dye after treatment for 60 minutes at 130 ° C is at least 9%.
It is preferably 0% or more. If the residual rate is less than 90%, the hue becomes unclear and the dyeing 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 less than 110 ° C, sufficient dyeing cannot be performed. The higher the dyeing temperature, the higher the dyeing property, but on the other hand, problems such as dye decomposition start to occur. Therefore, it is not always necessary to raise the temperature to 210 ° C. at the highest. On the other hand, benzenedicarboxylic acid ester, which is similar to the basic skeleton structure of polymetaphenylene isophthalamide fiber, is most suitable as the carrier as the dye diffusion agent. Since this carrier is an aromatic dicarboxylic acid ester, it does not have an ionic bond with the cationic dye and has good compatibility with the meta-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, and the alkyl residue of the ester group includes ethyl, propyl, and the like other than methyl. When dyeing with 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 the drainage load is reduced and environmental pollution is reduced. Here, BOD and COD are JIS-K-0, respectively.
102-1986 (Factory drainage test method) 1
It indicates the oxygen consumption (COD Mn) and biochemical oxygen consumption (BOD) by potassium permanganate at 00 ° C. The remaining amount of such organic substances in the fiber almost disappears after reduction washing and heat treatment after dyeing,
Final 50 mg / g-fiber or less (measured by gas chromatograph).

[0010]

INDUSTRIAL APPLICABILITY The present invention comprises a meta-aramid fiber containing a cationic dye having a specific molecular weight and an extremely small amount of an aromatic dicarboxylic acid ester, and is capable of producing a large effect of high color development. Since this benzenedicarboxylic acid ester has almost the same structure as the dicarboxylic acid component of the polymetaphenylene isophthalamide fiber, it diffuses into the fine region inside the fiber with a small amount added to the dyeing bath. The dye is strongly dyed. When the dyeing is finished, the fine structure of the fiber returns to the original dense state, and the dyed dye does not easily fall off, and the fastness is high.

Next, the present invention will be described in detail with reference to examples. The evaluation methods referred to in the examples are as follows.

The evaluation of the cation stainability is expressed by L * value, which is obtained from tristimulus values X, Y and Z obtained from diffuse reflectance according to JIS-Z-8701, and has a small number. It shows that it is dyed darkly.

[0013]

Examples 1 to 6 Conex (registered trademark) having a spun yarn count of 40/2 obtained from 2 denier × 38 mm bias cut staple fibers was used as the meta-aramid fiber, and the warp density was 113 yarns / inch on a normal loom. Weft density 58 lines / inch 2
/ 1 twill was woven. The resulting fabric has a basis weight of 220 g
/ M ² . The fabric is then score rolled 90
0 (non-ionic activator, manufactured by Kao) 2 g / l and sodium carbonate 1 g / l.
After scouring for 30 minutes, heat treatment was performed at a temperature of 190 ° C. for 1 minute.

The resulting fabric is dyed in the following dyebath at 130 ° C. and 1
Staining was carried out at 70 ° C. for 60 minutes. Dye 6% owf acetic acid 0.4 cc / liter benzenedicarboxylic acid ester 25 g / liter bath ratio 1:30 The dyed fabric was reduction washed by the following method 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) 80 ° C for 20 minutes Dye 1) Aizen Cathilon Red BLH (CI Basic Red 39: Molecular weight of dye base) 429) 2) Diacryl Blue GRL-N (manufactured by Mitsubishi Kasei Co., Ltd.) (CI Basic Blue 41: molecular weight of the dye matrix 323) Benzene dicarboxylic acid ester 1) Dimethyl terephthalate 2) Dimethyl phthalate After reducing and drying, It heat-processed at 170 degreeC for 1 minute. The results are shown in Table 1.

[0015]

Comparative Example 1 The procedure of Example 1 was repeated except that dimethyl terephthalate was not added. The results are shown in Table 1.

[0016]

[Comparative Example 2] The same procedure as in Example 1 was carried out except that acetophenone was used instead of dimethyl terephthalate in Example 1. The results are shown in Table 1.

[0017]

Comparative Example 3 The same procedure as in Example 1 was carried out except that dichlorophenol was used instead of dimethyl terephthalate in Example 1. The results are shown in Table 1.

[0018]

Comparative Example 4 Instead of the meta type aramid fiber (Conex, registered trademark) of Example 1, a copolymer of paraphenylene terephthalamide and 3,4′-oxydiphenyl terephthalamide (registered by Teijin Ltd. Technora). Example 1 was carried out in the same manner as in Example 1 except that an aromatic polyamide fiber in which a paraphenylene group was incorporated into the main chain was used. The results are shown in Table 1.

[0019]

[Table 1]

Claims (1)

[Claims] 1. A cationic dyeing meta-type aramid fiber comprising a cationic dye and a benzenedicarboxylic acid ester.