JPS6218674B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the formula (In formula (1), benzene nucleus B is a nitro group, a rhodan group,
It may have one or two substituents selected from halogen and alkylsulfonyl groups. A represents lower alkylene, and R' represents a lower alkyl group or alkenyl group. ) The present invention relates to a method for dyeing or printing hydrophobic fibers using the novel water-insoluble monoazo dye shown in (1) or a mixture thereof.

An object of the present invention is to provide a method for dyeing hydrophobic fibers, particularly fibers made of polyethylene terephthalate (hereinafter referred to as polyester fibers), to make them bright and strong.

As is clear from formula (1), the azo dye of the present invention uses a 2-aminobenzothiazole derivative as the diazo component and an aniline derivative having a carboxylic acid ester group as the coupling component. The coupling component is an aniline derivative having a carboxylic acid ester group. Known azo dyes include, for example, Japanese Patent Publication No. 5949 of 1973,
-No. 26397, JP-A-51-119722 and JP-A-52-
No. 16527, etc., but in these azo dyes, the diazo component is a derivative of aniline or aminothiazole, and dyes such as the dye of the present invention, in which the diazo component is a 2-aminobenzothiazole derivative, are new. Moreover, the azo dye of the present invention has the advantage of having a clearer hue and higher color value than the dye of the above-mentioned literature.

The novel dye of formula (1) is of the formula (In the formula, benzene nucleus B represents the same meaning as above.) A compound represented by the formula is diazotized in a mineral acid, optionally in the presence of a lower fatty acid such as acetic acid or propionic acid, to give the formula (In the formula, A and R' have the same meanings as above.) It can be easily obtained by coupling the compound represented by the following in an acidic medium.

Specific examples of the compound represented by formula (2) include the following.

2-Aminobenzothiazole 4-chloro-2-aminobenzothiazole 4,6-dichloro-2-aminobenzothiazole 4-bromo-6-chloro-2-aminobenzothiazole 4-bromo-6-nitro-2-aminobenzo Thiazole 5,6-dichloro-2-aminobenzothiazole 6-nitro-2-aminobenzothiazole 6-thiocyano-2-aminobenzothiazole 6-sulfomethyl-2-aminobenzothiazole 6-sulfomethyl-4-bromo-2-amino Benzothiazole 6-bromo-2-aminobenzothiazole 6-sulfoethyl-2-aminobenzothiazole 6-sulfoethyl-4-bromo-2-aminobenzothiazole Specific examples of the coupler represented by formula (3) include These couplers are easily manufactured, for example, by the following method.

(1) Acrylic acid ester is allowed to act on the raw material aniline derivative in the presence of a catalyst such as copper acetate and a polymerization inhibitor such as hydroquinone.

(2) A dicyanoethyl derivative of an amine such as di-(β-cyanoethyl)aniline is reacted with sulfuric acid, water, and alcohol to cause an esterification reaction at the same time as hydrolysis of the cyano group.

(3) The raw material aniline derivative is reacted with propiolactone or acrylic acid, and then esterified with an alcohol in the presence of an acid (which acts as a catalyst).

(4) React the aniline derivative as a raw material with a halogenoacetic acid ester.

In order to dye hydrophobic fibers according to the present invention, a dyeing bath or printing paste is prepared in which the novel azo dye represented by formula (1) is dispersed in water by a conventional method, and dyeing is carried out by a method known per se. Perform textile printing or thermosol dyeing. In addition to the above-mentioned polyester fibers, examples of hydrophobic fibers include acetate fibers and nylon fibers.

All of the dyes of the present invention give red to purple dyed products, and the dyed products obtained have excellent fastness to sunlight and sublimation, and are extremely fast to processing after dyeing.

The present invention will be explained below with reference to Examples.

Example 1 Formula 3 g of the dye shown (melting point 148-151°C) was mixed with 4 g of Demol N (product of Kao Atlas Co., Ltd.) and Demol C.
(Kao Atlas product) 3g in a wet state
After being treated for a period of time, it was dried to obtain a finely divided dye. Disperse and dissolve 0.04g of this micronized dye in 100c.c. of water, add 0.2g of Polyescar DL (SsangYong Chemical Products, methylnaphthalene-based Chiaria), add 2g of polyester fiber cloth, and keep at 98-100℃ for 60 minutes. Reduction cleaning was performed in the same manner as in Example 1. The dyed product was then washed with water and dried to obtain a slightly yellowish red dyed product with excellent sublimation fastness.

The dye used in this example was produced as follows.
Dissolve 5.3 g of 4-bromo-6-chloro-2-aminobenzothiazole in 80 g of 55% (weight ratio) sulfuric acid, cool to below 5°C with ice, and add 1.9 g of sodium nitrite in small portions over approximately 1 hour. I added it in passing. Subsequently, the temperature was maintained at 5° C. or lower for 2 hours. The transparent diazo liquid thus obtained is N,N-di-
The mixture was gradually added to a solution containing 5.6 g of (β-methoxycarboethyl)aniline, 1 g of sulfamic acid, 30 c.c. of concentrated hydrochloric acid, and 100 g of ice water while cooling to below 5°C. The mixture was added dropwise over about 30 minutes and then stirred at room temperature overnight. The precipitated crystals were separated, washed with water, and dried to obtain 8.5 g of the dye represented by formula (4).

Example 2 A mixture of dyes represented by formulas (5) and (6) in a weight ratio of 1:1 (melting point 113 to 118°C) was made into fine particles in the same manner as in Example 1. When polyester fibers were dyed with the obtained finely divided dye in the same manner as in Example 1, a slightly bluish red dyed product was obtained, and the dyed product had excellent sunlight fastness, sublimation fastness and washing fastness.

Example 3 Formula A finely divided dye was prepared in the same manner as in Example 1 using the dye shown below. A colored paste having the following composition was prepared using this finely divided dye.

Micronized dye of formula (9) 10g Carboxymethyl cellulose paste 60g Sodium chlorate 0.5g Tartaric acid 0.2g Leveling agent 2.0g Warm water 25g This colored paste was printed on a polyester fiber cloth at 80℃.
After drying, divide the cloth into three equal parts and divide them into the following
Color development was performed by method (iii).

(i) The sample was kept in steam at 130°C for 30 minutes, then washed with water, and subjected to the same reduction washing as in Example 1, washed with water and dried.

(ii) It was kept in superheated steam at 175°C for 5 minutes, then washed with water and reduced, and washed with water and dried.

(iii) Dry heat treatment was performed at 190° C. for 1 minute, followed by water washing and reduction washing, followed by water washing and drying.

All methods (i), (ii), and (iii) gave dyed products of deep red color with a slight bluish tinge. This product had excellent white light fastness, sublimation fastness, and washing fastness after antistatic treatment.

Examples 4 to 6 Polyester fiber cloth was dyed using the dye represented by the following formula in substantially the same manner as in Examples 1 to 3 to obtain dyed products having the hues shown in parentheses.

Example 4 Example 5 Example 6

Claims (1)

[Claims] 1 Formula (1) (In formula (1), benzene nucleus B is a nitro group, a rhodan group,
It may have one or two substituents selected from halogen and alkylsulfonyl groups. A represents lower alkylene, and R' represents a lower alkyl group or alkenyl group. ) A method for dyeing or printing hydrophobic fibers, characterized by using a water-insoluble monoazo dye or a mixture thereof.