DE1152210B - Process for the preparation of substantive dyes - Google Patents

Description

Method of making noun dyes The invention relates to a method for producing nouns dyes, in particular of those obtained by treatment with metal-containing fixing agents on the fiber have excellent fastness properties.

The dyes are obtained by using substantive dyes of the general formula: in which X is an alkoxy group or a chlorine atom, R and R 'are different radicals of azo components, both of which have coordinative atomic groups in the o-position to the azo group and which contain at least one water-solubilizing group such as sulfonic and / or carboxylic acid group together with a metallizing agent treated and the metal complex dyes obtained in this way are freed from the metal by treatment with a demetallizing agent with elimination of the complex-bound metal.

As starting dyes of the given general formula come in Consideration: water-soluble disazo or polyazo dyes obtainable through Coupling of tetrazotized diaminodiphenyl compounds such as 4,4 = diamino-3,3 = dialkoxydiphenyl or 4,4'-diamino-3,3'-dichlorodiphenyl with two different azo components, the have coordinative atom groups after coupling in o-position to the azo group.

Examples of the azo component include: 1-naphthol-4-sulfonic acid, 1-naphthol-4,8-disulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, -1-amino-8-naphthol-2,4-disulfonic acid, 2-Amino-5-naphthol-7-sulfonic acid, 2-phenylamino-5-naphthol-7-sulfonic acid, 2- (p-methoxyphenyl) -amino-5-naphthol-7-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 2-phenylamino-8-naphthol-6-sulfonic acid, 1-acetylamino-8-naphthol-3,6-disulfonic acid, 2-naphthol-6-sulfonic acid, f-naphthol, 2-oxy-3-naphthoic acid, 1- (p-sulfophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone, 5-sulfo-2-phenolazoresorcinol, Copper complex compound of 5-sulfo-2-phenolazoresorcinol and 8-oxyquinoline-5-sulfonic acid.

By treating these starting dyes with metallizing agents Metallkomplexfar materials are easily obtained in a known manner. So z. B. by heating the starting dyes together with copper ammonium or copper salt solutions obtained copper complex dyes under ammoniacal or acetic acid conditions.

In the present invention, these metal complex dyes are treated by treatment freed from the complex-bound metal with demetallizing agents. As a demetallizing agent can e.g. B. with particular advantage mineral acids, such as sulfuric acid or hydrochloric acid, be used. But it can also alkali compounds such as sodium sulfide or Sodium cyanide can be used. Organic acids such as oxalic acid can also be used for this be used.

These demetallizing agents all work depending on their type more or less in such a way that of the metal complex compounds of the starting dyes the complex-bound metal is split off, this into a water-soluble or difficult one soluble metal compound is transferred and removed as such.

If a metal complex salt of the dye is now according to the invention given general formula a demetallizing agent, e.g. B. a mineral acid, such as sulfuric or hydrochloric acid, added slowly and in the case of acids with a higher concentration close to room temperature or, in the case of acids of lower concentration, at increased Temperatures stirred for several hours, then the complex-bound The metal is easily split off from the dye. The reaction mixture is optionally diluted with water to separate out the dye, whereupon the precipitate is filtered off and is separated from the metal compound in solution. He will then dissolved in an aqueous alkali solution and salted out and the resulting precipitate filtered off and dried to obtain the desired dye.

The dyes obtained have a higher solubility in water and thus also a better dyeing power and a better leveling capacity for the fibers than the complex salts of the starting dyes. This is probably due to the fact that these are metal-free o, o'-dihydroxyazo dyes which, according to the invention, have been produced from the metal complex salts of the starting dyes by demetallizing treatment. The following describes the reaction mechanism when using a starting dye obtained by coupling tetrazotized 4,4'-diamino-3,3'-dimethoxydiphenyl with 1-amino-8-naphthol-2,4-disulfonic acid and β-naphthol in equimolar proportions is explained using formulas: This dye corresponds to a dye obtainable by coupling tetrazotized 4,4'-diamino-3,3'-dioxydiphenyl with the two coupling components mentioned. Compared to this known method, the method according to the invention seems to be a detour. In fact, however, the latter is much more advantageous, because the tetrazotized 4,4'-diamino-3,3'-dioxyphenyl is much less capable of coupling than the tetrazotized 4,4'-diamino-3,3'-dialkoxydiphenyl, so that it is extremely difficult is to couple the tetrazotized 4,4'-diamino-3,3'-dioxydiphenyl with the azo components. In particular, coupling with two different components does not go smoothly. In addition, to prepare 4,4'-diamino-3,3'-dioxydiphenyl it is generally necessary to saponify 4,4'-diamino-3,3'-dialkoxydiphenyl with aluminum chloride and to further purify the compound obtained.

In contrast, the starting dyes for the process according to the invention by coupling the more strongly couplable, tetrazotized 4,4'-diamino-3,3'-dialkoxydiphenyl or dichlorodiphenyl with two different azo components of the type mentioned can be easily obtained. Those also available from these starting dyes Metal complex salts are made by a very simple and economical measure converted into the desired final dyes. Thus, the method of the invention is very advantageous for the industrial production of these dyes.

By dyeing fibers, especially cellulose fibers, with the substantive dyes obtained according to the invention can very easily be uniform Colorations are generated after treatment with commercially available metal-containing Fixatives have excellent light and wash fastness properties.

Compared to the one known from German patent specification 926 385 Copper complex compound of an azo dye draws cotton dye available the cotton dyeing of the same azo dye, which has been re-coppered according to the invention through better wash fastness.

In the following, the invention is illustrated by means of exemplary embodiments explained in more detail. Parts in the examples are to be understood as meaning parts by weight.

Example 1 13.93 parts of a tetrazotized by alkaline coupling 4,4'-diamino-3,3'-dimethoxydiphenyl with 1-naphthol-4-sulfonic acid sodium and 2-amino-8-naphthol-6-sulfonic acid Disazo dye obtained in equimolar amounts are dissolved in water and this Solution '100 parts of copper ammonium solution with a copper content of 2.6% were added and stirred with heating for 20 hours. The reaction solution is then salted out and the precipitate filtered off and dried, yielding about 18.7 parts of a sodium chloride containing copper complex dye can be obtained.

15 parts of the copper complex salt thus obtained are slowly added at temperatures below 20 ° C. 270 parts of 95% strength sulfuric acid and stirred at this temperature for 6 hours, whereupon the reaction mixture is poured into 1000 parts of cold water for dilution and the precipitate is filtered off. This precipitate is again added to 500 parts of water and the suspension obtained is made slightly alkaline with sodium hydroxide solution and then salted out. By filtering off the resulting precipitate and drying, about 13.5 parts of the dye of the following formula are obtained This dye dissolves in water in a violet color and turns cellulose fibers black-gray. When treated with a copper-containing fixing agent, the color changes into a dark blue shade and shows considerably improved light and wash fastness. Example 2 13.93 parts of an alkaline coupling of tetrazotized 4,4'-diamino-3,3'-dimethoxydiphenyl with 1-amino-8-naphthol-2,4-disulfonic acid and β-naphthol in equimolar amounts. Amounts of the disazo dye obtained are heated with copper ammonium solution in the same manner as in Example 1, whereby about 37.5 parts of a copper complex dye containing sodium chloride are obtained.

15 parts of this copper complex dye become 178 parts at 20 ° C 37% hydrochloric acid was slowly added and the mixture was stirred for 8 hours, whereupon the reaction mixture Poured into 300 parts of cold water for dilution and the precipitate is filtered off will. This precipitate is again added to 450 parts of water and the resulting precipitate Made the suspension slightly alkaline with sodium hydroxide solution and then salted out. By Filtering off and drying the precipitate which has separated out is about 7.5 parts Dye received.

This dye dissolves in water in a violet-blue color and stains Cellulose fibers green-blue. The coloring goes through the treatment with a copper-containing one Fixing agent in a dark green-blue shade of very good lightfastness and washfastness above.

Example 3 The starting dyes listed in the table below are treated with copper ammonium solution as in Examples 1 and 2 and the copper complex salts thus obtained are further treated with concentrated sulfuric or hydrochloric acid as in Examples 1 and 2, respectively. Cellulose fibers are dyed with the dyes obtained in this way and treated with a copper-containing fixing agent, whereby very real dyes with the following shades can be achieved: Example 4 A disazo dye obtained in equimolar amounts by the alkaline coupling of tetrazotized 4,4'-diamino-3,3'-dimethoxydiphenyl with sodium 1-naphthol-4-sulfonic acid and 2-amino-5-naphthol-7-sulfonic acid is produced as in Example 1 treated with copper ammonium solution. 15 parts of the copper complex dye thus obtained are added to 400 parts of 18% hydrochloric acid, the mixture is boiled with stirring until dissolved and the treatment is continued for 1.5 hours. After cooling: the reaction mixture is diluted by adding 200 parts of water, then neutralized with sodium carbonate and then salted out. After filtering off the precipitate and drying, about 8.7 parts of dye are obtained.

This dye dyes cellulose fibers bluish purple: will this one Coloring as in Example 1 treated with the copper-containing fixative, so goes them in a very real, navy blue tone. Example 5 A by alkaline Coupling of tetrazotized 4,4'-diamino-3,3'-dimethoxydiphenyl with the copper complex compound of 5-sulfo-2-phenolazoresorcinol and 1-amino-8-naphthol-2,4-disulfonic acid in equimolar amounts Amounts of trisazo dye obtained are as in Example 1 with copper ammonium solution treated. 10 parts of the copper complex dye thus obtained become 300 parts Water added and after further addition of 27 parts of aqueous sodium sulfide solution, containing 7.2 parts of Na2S 9 1120, stirred at 45 to 50 ° C for 1 hour. The reaction mixture is filtered off, the filtrate neutralized with hydrochloric acid and then salted out and the precipitate filtered off and dried. The dye thus obtained dyes cellulose fibers bluish gray. If this coloring is done with the same copper-containing fixative as in Example 1 treated, it turns into a very real reddish-gray tone. Example 6 In Example 5, instead of the sodium sulfide solution, 26 parts of an aqueous solution Sodium cyanide solution containing 6 parts of sodium cyanide, used and at 60 to 65'C stirred for 1 hour, after which work is continued in the same way to the same To obtain dye.

Claims (2)

PATENT CLAIMS: 1. Process for the production of substantive dyes, characterized in that substantive dyes of the general formula: in which X is an alkoxy group or a chlorine atom, R and R 'are mutually different radicals of azo components, both of which have coordinative atomic groups in the o-position to the azo group and which contain at least one water-solubilizing group such as sulfonic and / or carboxylic acid group, in themselves treated in a known manner with a metallizing agent and the metal complex dyes obtained in this way are freed from the metal by treatment with a demetallizing agent with elimination of the complex-bound metal. 2. The method according to claim 1, characterized in that that a mineral acid, alkali sulfide, alkali metal cyanide or as demetallizing agent an organic acid can be used. German publications considered Patent Specification No. 926 385. At the notice of the application is a staining table has been interpreted with explanation.