KR930006930B1 - Preparation of trisazo direct dyes - Google Patents

Abstract

The direct dye of formula (I) is prepared by (1) tetrazolating a benzidine-based compound, (2) primary coupling the tetrazolated with 1-amino-8-naphtol-3,6-disulfonic acid, (3) secondary coupling the primary coupling solution with the diazolated product of aniline compound, (4) finally coupling the secondary coupling solution with benzene-based compound, (5) mixing active carbon or a mixture of active carbon and siliceous earth into the solution (4), and (6) salting out the residual solution (5). In formula, R1 and R2 are H, CH3 or OCH3, R3 is H, SO3H, NO2 or OH, X and Y are H, OH, NH2 or CH3.

Description

[Name of invention]

Improved manufacturing method of tris azo direct dye

Detailed description of the invention

The present invention relates to an improved method for preparing tris azo direct dyes.

The tris-azo dye represented by the following general formula (I) is known as a high-quality direct dye mainly used for dyeing black, cotton, leather and silk in high concentration.

이다.Where R ₁ and R ₂ are H, CH ₃ , or OCH ₃ , R ₃ is H, SO ₃ H, NO ₂ or OH and X, Y are H, OH, NH ₂ , CH ₃ , or

to be.

However, when dyeing with tris azo dye of the general formula (I) prepared by a conventional method, there is a problem that the sweat fastness in acid and alkali is poor, and the contamination to other fibers is not satisfactory.

The present inventors conducted a research experiment to solve such a problem, and the problem is that the tris-azo dye of general formula (I) prepared by a conventional method is a by-product (by product) produced during the manufacturing process as impurities. The present invention was completed by finding out that it exists.

That is, according to the present invention, after the benzidine-based compound is tetra-coated, the first coupling is performed by adding sodium of 1-amino-8-naphthol-3,6-disulfonic acid, and then the second aniline-based diazo-ized product is coupled. Activated carbon and diatomaceous earth were added to a conventional coupling completion solution to which the benzene-based compound was finally coupled, and then stirred for 1-2 hours, followed by salting or calcination of the filtrate to prepare tris-azo dye of general formula (I). It is a way.

According to this method of the present invention, impurities, which are by-products generated during the third coupling reaction, are adsorbed and removed from activated carbon and diatomaceous earth, so that the fastness of sweat in acids and alkalis, which appear during dyeing by these impurities, is applied to other fibers. Pollution is significantly reduced.

At this time, activated carbon and diatomaceous earth to be added may be added alone, or two materials may be mixed and added.

In general, the purification of organic compounds using activated carbon is common knowledge.In such dye synthesis, although activated carbon may be purified before the formation of the chromophore, it is forbidden to use activated carbon once the chromophore is formed to show color. . The reason is that activated carbon adsorbs the dye itself, which significantly reduces the yield of the dye.

In the present method, however, dye yield is the same as in the conventional manufacturing method, since only a main color (which is a disazo and monoazo compound that lowers the fastness of the triszo dye) is adsorbed and removed using an appropriate amount of activated carbon.

The present invention will be described in more detail with reference to the following Examples. In the examples, parts indicate parts by weight.

Example 1

15.3 parts of benzidine are added to 150 parts of water and 60 parts of concentrated hydrochloric acid, and dissolved. Then, 100 parts of ice and 12 parts of sodium nitrite are added thereto, and the mixture is stirred at 5-10 ° C. for 1 hour to be tetrazolated.

20 parts of 1-amino-8-naphthol-3,6-dasulfonic acid (86% purity) are completely dissolved by adding 150 parts of water and 56.3 parts of caustic soda, and then slowly added to the above-mentioned tetrazo solution for 2-3 hours. Calcium carbonate is added to the solution and primary coupling is performed while maintaining the pH slightly weak.

4.8 parts of aniline is added to 150 parts of water and 60 parts of concentrated hydrochloric acid, and 100 parts of ice and 6 parts of sodium nitrite are added to diazotize while maintaining the temperature below 5 ° C.

The diazo solution was slowly added to the primary coupling solution over 1 hour, followed by adding 3 parts of sodium carbonate (20%) to the center of the Congo red, and then adding about 100 parts of sodium carbonate over 30 minutes and adjusting the pH with weak alkali to form a secondary coupling. Let's do it.

After stirring this secondary coupling liquid for about 7 hours, the solution which melt | dissolved 5.7 parts of meta-phenylenediamine completely in 100 parts of water is added to the said secondary coupling liquid, and it stirs for 4 hours or more, maintaining PH as weak alkali.

When the reaction is completed, 85 parts of 35% hydrochloric acid is added to keep the pH slightly acidic, and stirred for about 30 minutes to form a third coupling. 12 parts of 50% caustic soda is added to the coupling complete solution, the temperature is raised to 70 ° C, 10 parts of activated carbon is added, stirred for about 1 hour, filtered, and salted with about 20% by weight of salt to the filtrate. After filtration, drying was performed to obtain a black tris azo direct dye having excellent sweat fastness.

Example 2

15.3 parts of benzidine are added to 150 parts of water and 60 parts of concentrated hydrochloric acid, and dissolved. Then, 100 parts of ice and 12 parts of sodium nitrite are added thereto, and the mixture is stirred at 5-10 ° C. for 1 hour to be tetrazolated.

20 parts of 1-amino-8-naphthol-3,6-disulfonic acid (86% purity) are completely dissolved by adding 150 parts of water and 6.3 parts of caustic soda, and then slowly added to the tetrazole solution for 2-3 hours. Calcium carbonate is added to the solution and primary coupling is performed while maintaining the pH slightly weak.

4.8 parts of aniline is added to 150 parts of water and 60 parts of concentrated hydrochloric acid, and 100 parts of ice and 6 parts of sodium nitrite are added to diazotize while maintaining the temperature below 5 ° C.

The diazo solution was slowly added to the primary coupling solution over 1 hour, followed by 3 parts of sodium carbonate (20%), centered on Congo red, and about 100 parts of sodium carbonate over 30 minutes. Let's do it. After stirring this secondary coupling liquid for about 7 hours, the solution which melt | dissolved 5.7 parts of meta-phenylenedinine completely in 100 parts of water is added to the said reaction liquid, and it stirs for 4 hours or more, maintaining PH about weak alkali.

When the reaction is completed, 85 parts of 35% hydrochloric acid is added to keep the pH slightly acidic, and then stirred for about 30 minutes to form a third coupling. 12 parts of 50% caustic sodium is added to the complete coupling solution, and the temperature is raised to 70 ° C., 5 parts of activated carbon and 5 parts of diatomaceous earth are added, stirred for about 1 hour, filtered, and salted with about 20% by weight of salt to the filtrate. . After filtration, drying was performed to obtain a black tris azo direct dye having excellent sweat fastness.

Comparative Example 1

(Method by conventional manufacturing method)

15.3 parts of benzidine are added to 150 parts of water and 60 parts of concentrated hydrochloric acid, and dissolved. Then, 100 parts of ice and 12 parts of sodium nitrite are added thereto, and the mixture is stirred at 5-10 ° C. for 1 hour to be tetrazolated.

20 parts of 1-amino-8-naphthol-3,6-disulfonic acid (86% purity) are completely dissolved by adding 150 parts of water and 6.3 parts of caustic soda, and then slowly added to the tetrazole solution for 2-3 hours. Calcium carbonate is added to the solution and primary coupling is performed while maintaining the pH slightly weak.

4.8 parts of aniline is added to 150 parts of water and 60 parts of concentrated hydrochloric acid, and 100 parts of ice and 6 parts of sodium nitrite are added to diazotize while maintaining the temperature below 5 ° C.

The diazo solution was slowly added to the primary coupling solution over 1 hour, followed by 3 parts of sodium carbonate (20%), centered on Congo red, and then about 100 parts of sodium carbonate over 30 minutes to adjust the pH to weak alkali for secondary coupling. Let's do it.

After stirring this secondary coupling liquid for about 7 hours, the solution which melt | dissolved 5.7 parts of meta-phenylenediamine completely in 100 parts of water is added to the said secondary coupling liquid, and it stirs for 4 hours or more, maintaining PH as weak alkali.

When the reaction is completed, 85 parts of 35% hydrochloric acid is added, the pH is kept weakly acidic, stirred for about 30 minutes, and the third coupling is performed. After filtration and drying to give a black tris azo direct dye.

The sweat fastnesses of the black tris-azo direct dyes prepared by the methods of Examples 1 and 2 and Comparative Example 1 were as follows.

As shown in the above table, it can be seen that the dyes prepared by the method of the present invention (Examples 1 and 2) have improved sweat fastnesses 0.5 to 1 degree compared to the dyes prepared by the conventional methods (Comparative Example 1).

Example 3

12.2 parts of ortho- dianicithin are added to 150 parts of water and 60 parts of concentrated hydrochloric acid, followed by stirring. Then, 100 parts of ice is added to maintain the temperature at 0-5 ° C. 12 parts of sodium nitrite was added thereto, followed by tetrazolation with stirring for about 1 hour.

After dissolving 20 parts of 1-amino-8-naphthol-3,6-disulfonic acid in 150 parts of water and 6 parts of caustic soda to adjust the pH, the tetrazonium solution was added slowly for 2 hours, and sodium acetate was added to the pH. Maintain coupling at 3.5-4.

8.6 parts of 4-aminobenzenesulfonic acid are added to 150 parts of water and 60 parts of concentrated hydrochloric acid, 100 parts of ice is added, cooled to 5 ° C or lower, and 6 parts of nitrous acid are added to diazotize. This diazo solution was added to the first coupling reaction solution, and then 100 parts of sodium carbonate was slowly added, followed by stirring for about 7 hours for secondary coupling.

A solution obtained by dissolving 5.4 parts of para-aminophenol in 100 parts of water is added to the secondary coupling solution described above, followed by stirring for at least 4 hours to carry out tertiary coupling. 12 parts of 50% caustic soda was added to the complete coupling solution, and the temperature was raised to 70 ° C, 10 parts of activated carbon was added, stirred for about 1 hour, filtered, and 20% salt was added to the filtrate. Direct dye was obtained.

Example 4-7

Benzidine-based Compound Aniline Compound of Formula (I) A tris-azo direct dye having a high concentration of sweat fastness was obtained in the same manner as in Example 1 except that the benzene-based compound and the additive were described in the following table.

Claims (1)

Tetra-coated the benzidine-based compound to carry out a first coupling with 1-amino-8-naphthol-3,6-disulfonic acid, followed by secondary coupling of the diazotized product of the aniline compound and benzene in the second coupling reaction solution. In the final coupling to prepare a black direct dye of the following general formula (I), activated carbon or activated carbon and diatomaceous earth are added to the final coupling complete solution, stirred, and the filtrate is salted out again according to a known method. Improved manufacturing method of tris azo direct dye represented by general formula (I)

Wherein R ₁ and R ₂ are H, CH ₃ or OCH ₃ , R ₃ is H, SO ₃ H, NO ₂ or OH, and X and Y are H, OH, NH ₂ , CH ₃ or

to be.