KR960006554B1 - New blue reactive dye, process for producing it and for dyeing process by using the same - Google Patents

Abstract

Light blue reactive dye(fig. I) for cellulose fiber contains quinoxiline functional group. It is obtained from condensation reaction of 2,3-dichloroquinoxiline-6-carbonylchloride(fig. V) with condensation product(fig. IV) which is produced by the condensation reaction between 1-amino-4-bromoantraquinone-3-sulfonic acid(fig. II) and 1,3-diamino-2,4,6-trimethylbenzene-5-sulfonic acid(fig. III). It is dyeing at relatively low temperature(40 deg.C) because of quinoxiline derivative. It also has higher color strength and build-up property.

Description

New reactive blue dyes, preparation method thereof and dyeing method thereof

The present invention relates to a novel reactive blue dye having a quinoxaline-based reactor suitable for dyeing cellulose fiber materials in light blue, a preparation method thereof and a dyeing method thereof.

Most of the existing reactive blue dyes used for dyeing cellulose fiber materials are dyed at a high temperature of about 60 ° C to 80 ° C. Therefore, when used for on-site dyeing, there is a large amount of waste water such as energy consumption and dye balance due to elevated temperatures. In addition to the high cost of dyeing, when dyeing the cellulose-based fibers, the physical properties such as build up, water washing, daylight and washing fastness were weak.

Accordingly, the present inventors have made numerous studies and experiments to improve the above-mentioned disadvantages of the existing blue dyes, and thus, have developed a new reactive blue dye represented by the following structural formula (I).

The reactive blue dye of formula (I) according to the present invention is characterized by the introduction of a quinoxarine-based reactor in the dye molecule. In addition, the dye compound of the present invention may exist in the form of a free acid or a metal salt.

The dye compound of the general formula (I) according to the present invention comprises 1-amino-4-bromo-anthraquinone-2-sulfonic acid of the following formula (II) and 1,3-diamino-2 of the following formula (III), Condensation reaction of 4,6-trimethylbenzene-5-sulfonic acid to obtain a condensation reactant of the following structural formula (IV), and the condensation reactant (IV) is 2,3-dichloroquinoxarine 6-car of the following formula (V) It can be prepared by condensation reaction with carbonyl chloride.

Referring to the preparation method of the reaction blue dye according to the present invention in detail.

Condensation reaction product (IV) is obtained by condensation reaction at 65 ° C. to 70 ° C. for 12 to 15 hours using cuprous chloride (CuC1) as a catalyst in aqueous solution, followed by calcination with hydrochloric acid or concentrated sulfuric acid. The condensation reactant (IV) obtained here was dissolved in water, and then 2,3-nickeltoquinoxaline 6-carbonyl chloride (V) was added and stirred for about 2 hours, and the temperature was raised to 40 to 50 ° C. After stirring for about an hour, the pH was adjusted to about 6.5, salted with sodium chloride, filtered and dried to give the desired reactive blue dye (I).

Since the reactive dye compound (I) according to the present invention uses 2,3-dichloro-quinoxaline-6-carbonylchloride in its preparation, it is dyed at a relatively lower temperature than other conventional reactive dyes, for example, about 40 ° C. This is possible, so there is no need to increase the temperature, so when used in the field dyeing plant can greatly save the energy according to the elevated temperature. In addition, since the dyeing process is excellent, almost no dye residues remain in the dyeing process, the amount of waste generated is reduced, which can greatly reduce the cost of wastewater treatment.

When the blue dye compound (I) according to the present invention is dyed to a cellulose fiber material, it is possible to obtain a bright yellow dye having excellent washing, sunlight and fastness to washing. In addition, it has excellent buildup properties and has been found to be particularly suitable as a dye for cold batches.

The reactive dye (I) according to the present invention is present in the form of a free acid or metal salt and can be dyed to cellulose fibers such as cotton, hemp, and viscose according to a conventional dyeing method. That is, an acid binder, such as sodium carbonate, which adsorbs the reactive dye (I) of the present invention to the cellulose fiber material by using a neutral inorganic salt such as sodium chloride or sodium sulfate and assists the binding between the cellulose fiber and the dye. Alternatively, when the dyeing is carried out by adding sodium hydroxide, a bright yellow dyeing material having excellent dyeing fastnesses such as sweat, friction, washing and daylight fastness can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples.

(Example 1)

1-amino-4-bromoanthraquinone-2-sulfonic acid was adjusted with 19.1 parts by weight of a neutral aqueous solution, and 16.1 parts by weight of 1,3-diamino-2,4,6-trimethylbenzene-5-sulfonic acid was added as an aqueous solution. 20.16 parts by weight of sodium bicarbonate was added, 10.5 parts by weight of cuprous chloride was added and reacted at 65 ° C. to 70 ° C. for 12 to 15 hours. The reaction was completed, filtered, concentrated with hydrochloric acid, and salted to obtain a condensation reaction product (IV). 14.3 parts by weight of the condensation reactant (IV) was dissolved in 250 parts by weight of water, and then 8.3 parts by weight of 2,3-dichloroquinoxaline-6-carbonyl chloride was added thereto, stirred for 2 hours, and the temperature was raised to 40 to 50 ° C. After stirring for 2 hours, the pH was adjusted to 6.5 with sodium carbonate, and 20 g of sodium chloride was added thereto for salting, filtration, and drying to obtain the target reactive dye compound (I) (color blue). When the obtained reactive dye compound was developed by thin layer chromatography (TLC), the Rf value was 0.88.

Dyeing Application Example 1

The reactive dye (I) of the present invention was weighed to prepare a 0.4% solution, and in the case of 2% dyeing (ow f), 20cc of 0.4% dye solution, 32cc of water, and 20cc of 20% sodium sulfate solution were placed in a dyeing vessel and 4g of cotton cloth. Pour the dye at 40 ° C. After 30 minutes, 8cc of 20% sodium carbonate solution was added to adjust the pH to 10-11, and fixed for 60 minutes. The dyed cloth was washed in boiling water for 10 minutes, washed with water and dried to obtain a light blue dye.

Dyeing Application Example 2

A 0.4% solution was prepared by weighing the reactive dye (I) of the present invention, and in the case of 4% dyeing (ow f), 40cc of 0.4% dye solution, 12cc of water, 20cc of 20% sodium sulfate solution were placed in a dyeing vessel, and soaked therein. Dyeing The same dyeing procedure as in Application Example 1 yields a bright yellow dye.

The dip dyeing dye applied Examples 1 and 2 bar, perspiration fastness (KSK0715) who measured the color fastness of the dye obtained by the 4-5 class, water fastness (KSK 0645) 4-5 grade, washing fastness (KSK 0430 A ₄ ) 4-5 grade showed excellent dyeing fastness.

Claims (10)

Novel reactive blue dye compounds and salts thereof, represented by the following structural formula (I). The reactive blue dye compound of formula (I) according to claim 1, in the form of a free acid or metal salt. Condensation reaction of an aromatic compound of formula (II) with a compound of formula (III) yields a condensation reactant of formula (IV), and the condensation reactant (IV) is condensed with a quinoxaline compound of formula (V) A reactive blue dye compound of formula (I) characterized by the following formula and a process for preparing the salts thereof. 4. A process for the preparation of a compound of formula (I) according to claim 3, characterized in that it is in the form of a free acid or metal salt. The process for preparing the compound of formula (I) according to claim 3, wherein the aromatic compound of formula (II) and the compound of formula (III) are reacted at a temperature of 65 ° C to 70 ° C. The process for preparing the compound of formula (I) according to claim 3, wherein the condensation reactant of formula (IV) and the quinoxaline compound of formula (V) are reacted at a temperature of 40 ° C to 50 ° C. Cellulose-based fiber, characterized in that the reactive blue dye of formula (I) as defined in claim 1 or 2 is mixed with neutral inorganic salts and water, immersed in cellulose-based fiber material and then fixed with an acid binder. Method of dyeing material. 8. The dyeing method according to claim 7, wherein the neutral inorganic salt is sodium chloride or sodium sulfate. 8. The dyeing method according to claim 7, wherein the acid binder is sodium carbonate or sodium hydroxide. The dyeing method according to claim 7, wherein the dyeing temperature is about 40 ° C.