DE741462C - Process for the preparation of o, o-dioxyazo or o-oxycarboxy dyes - Google Patents

Description

There are many processes in the literature for the granulation of sulfonic acid groups Mordant dyes have become known, all either in the application of chromium salts or consist of chromium hydroxide or chromites.

NaOH all these known processes go sulfonsäuregruppenfreie o-Oxycarboxyfafbstoffe on the type of Eriochromazurols B (2, o-Dichlordimethyloxyfuchsondicarbonsäure. See Schultz, dye tables, 7th edition, no. 838) or the Eriochrornflavins A (obtained by coupling diazotized i-aminobenzene -4-chloro-3-carboxylic acid with salicylic acid and heating the product with sodium hydroxide solution and copper powder, see Schultz, No. 258) into completely insoluble chromium compounds.

It is also known that sulfonic acid groups

ao pen-free o, o'-dioxyazof dyes by treatment with chromium salts in aqueous-alcoholic solution or by the action of chromium-releasing agents in alkaline agents in the presence of salts of aliphatic o-oxycarboxylic acids in alcohol-soluble chromium compounds can be transferred, but which are not water-soluble.

It has now been found that sulfonic acid groups are free Mordant dyes of the type mentioned above in water-soluble salts of Chromium compounds can be converted if they are in aqueous solution or Suspension at elevated temperature open or under pressure with water-soluble salts the complex chromium compounds of aromatic o-oxycarboxylic acids treated and at least one atom of chromium for each chromable group of the stain dye applies.

Water-soluble salts of complex chromium compounds of aromatic o-oxycarboxylic acids is obtained according to Barbieri (Renddconti dell'Accademia dei Lincci [5] 24 I. 608) by treating their alkali salt solutions with chromium salts. Suitable aromatic o-oxycarboxylic acids are, for example Salicylic acid, its homologues and substitution compounds, such as sulfosalicylic acid, sulfokres'otinic acids, and also o-oxynaphthioic acids and their substitution compounds,

like sulfo - /? - oxynaphthotic acid. Also diamine compounds complex chromium compounds of aromatic o-oxycarboxylic acids, such as diamine chromosalicylic acid, or their alkali salts, for example, from chromium salicylic acid alkali salts when standing with excess amines, such as ammonia, alkylamines, Ethylenediamine or pyridine, obtained as red-violet crystallized compounds, are suitable for use in accordance with the present method.

The formation of water-soluble salts of the chromium compounds of sulfonic acid group-free Mordant dyes could not be foreseen, and the very smooth course of the giromization is surprising, especially since complex chromium compounds of aliphatic o-oxycarboxylic acids, as experiments have shown, not very useful as a chromium-releasing agent for the chromating of mordant dyes are.

The new water-soluble salts of the chromium-chromium compounds of sulfonic acid groups " free o-oxycarboxy dyes expand the field of application of many well-known ones Dyes. For example, you can use them to dye cellulose fibers such as cotton or paper, for dyeing silk from weakly acidic baths or leather Find. Compared to the completely water-insoluble analog chromium compounds obtainable by known chromating processes represent the new water-soluble salts of the chromium compounds an essential Enrichment of technology.

The new water-soluble salts of chromium compounds of sulfonic acid group-free o. o'-dioxyazo dyes pull evenly on animal fibers from weakly acidic baths and partly also on cotton. They are also suitable for dyeing leather.

It is known, sulfonic acid group-free azo dyes, the metal complex-forming Contain groups by treatment with chromium salts of benzene or naphthalenesulfonic acids to be converted into chromium complex compounds which are soluble in water. However, it uses chromium salts obtained, which are converted into the alkali salts before use for dyeing have to. In contrast, the present method has the advantage that immediately the ready-to-use alkali salts are obtained. In addition, it also has the further advantage that the chromium complex compounds in a much shorter time than was previously possible.

example 1

9.6 parts of eriochromazurol B (sodium salt) are dissolved in 100 parts of water.

The solution is mixed with 100 parts of a solution of chromium salicylic acid ammonium, the ι gram atom of chromium in 2500 g of solution contains about 20 minutes at 90 to 100 ° € 5 touched. The yellow-red color of the solution goes under transient within 5 minutes Violet color turns into a pure blue. By salting out the cold Solution can be the new chromium compound as a violet-blue powder in the form of the ammonium salt split off. It is easily soluble in water with a pure blue color. It colors animal animals from organic acid baths and vegetable fibers pure blue. Very pure, blue tones are obtained on leather.

The apple-green solution of chromium salicylic acid ammonium is obtained, for example by stirring together the solutions of ι mol of chromium acetate in 2000 parts of water and 2 moles of ammonium salicylate in 400 parts of water at 90 to 100 ° and neutralize with ammonia to a permanent litmus-neutral reaction.

Similar complex dye chromium compounds are obtained with analogous chromium compounds homologous salicylic acids, salicylic acid mono- or disulfonic acid, o-oxynaphthoic acids and their sulfonic acids. . Example 2

9.7 parts of the dye eriochromflavin A are dissolved in 100 parts of water. the Solution is made with a solution of sodium chromium salicylic acid, corresponding to 4.5 parts Chromium oxide, boiled on a reflux condenser. The brown olive solution is created in a short time the water-soluble chromium compound of the dye. The new chromium-containing dye can be turned olive-yellow by salting out Powder can be obtained in the form of the sodium salt. From a weakly acidic bath on animal fibers, it produces light yellow Dyeings with good fastness properties.

Sodium chromsalicylic acid can be obtained, for example, by boiling a Chromium acetate solution containing 1 gram atom of chromium in 1.5 liters, with 2 gram molecules Sodium salicylate while neutralizing the acetic acid released with soda up to permanent lackmueneutral reaction.

Chromium compounds of eriochrome flavin A with similar properties are obtained with analogous complex chromium salt solutions from homologous salicylic acids, salicylic acid mono- or disulfonic acid, sulfocresotinic acids, o-oxynaphthoic acids and their sulfonic acids.

Example 3

19.6 parts of the 'sulfonic acid group-free Dye obtained from diazotized! 1-amino-2-oxy-5-nitrobenzene and i-phenyl-

3-methyl-S-pyrazolone, are dissolved _^0/0 sodium hydroxide solution domestic hot water 800 parts 100 parts 34 and boiled with 130 parts of a solution of sodium chromsulfosalicylsaurem (corresponding to 5 parts of chromium oxide) under reflux. The orange-colored solution separates about 5 parts of brown crystals of a water-insoluble, alcohol-soluble chromium complex compound, which are filtered off while hot after 2 hours. The new water-soluble chromium compound is obtained from the filtrate as the sodium salt by salting out. From a weakly acidic bath on animal fibers, it provides good lightfast, uniform yellow-orange colorations. Similar chromium-containing dyes are obtained with ammonium chromium sulfosalicylic acid and ammonium chromium sulfosalicylic acid. Ammonium.

The chromating agents mentioned are obtained by dissolving 1 gram atom of chromium hydroxide in a solution of 2 gram atoms of sulfosalicylic acid in 1 liter of water and neutralizing with soda or ammonia until the reaction remains litmus-neutral. The diamindhromsulfosalicylic acid ammonium is obtained from chromium sulfosalicylic acid ammonium as peach blossom-red crystals when the solution is saturated _{with NH 8.} With amines such as ethylenediamine, alkylamines, pyridine or piperidine, analogous compounds are obtained.

By treating the above-mentioned dye with sodium chromium salicylic acid a water-soluble chromium compound is obtained as the sodium salt, which is good for Dyeing leather is suitable.

ao dye chromed with:
a = chrome salicylic colour S, Coloring on C: blue yellow ι. Eriochromazurol B. acidic Na / NH ₄ the chrome
link Wool (W) 25th 2. Naphthochromium green G (phenooxy- b = chromium sulfo
salicylic acid
Na / NH ₄ blue Silk (S)
Leather (L)
Cellulose (C) yellow-orange dinaphthofuchsondicarboxylic acid, a S, L, C: green Schultz, a. a. 0. No. 851) orange 3 ·. 2- (4'-diethylamino-2'-oxy) -benzoyl- green 3o benzoic acid, condensed with ß-Re- a * S, L, C: red orange sorcylic acid and oxidized .-- 4. methylenedi-o-cresotinic acid hydrol, Red Red condensed with phenylmetnyl a S, L, C: brown 35 pyrazolone and oxidized Bordo red 5. 4-Dimethylamino-2-chlorobenzalde- Brown hyd, condensed with o-cresotinic acid a S, L, C: purple Bordo red and oxidized S, C: eelb 6. Eriochrome Flavin A violet W. yellow red-brown a yellow L, 4 ° 7. i-aminobenzene-2-carboxylic acid a yellow W, L, L. - > - I-phenyl-3-methyl-5-pyrazolone b 8. i-aminobenzene-2-carboxylic acid yellow W, L. -3 »2,4-dioxyquinoline b 45 9. i-Amino-2-oxy-5-nitrobenzene jelborange W, L. -> - i-phenyl-s-methyl-s-pyrazolone b 10. i-Amino ^ -oxy-s-methyl-s-nitro-
benzene - > ■ i-phenyl-3-methyl- orange W, L. 5-pyrazolone b So 11. i-Amino-2-oxy-5-nitrobenzene orange W, L. -> - 2,4-Dioxyquinoline b 12. i-aminobenzene-2-carboxylic acid Red W, L: - > - i-Oxy-4-methylbenzene ....... b 55 13. i-Amino ^ -oxy-S-chlorobenzene Dordo red W, L: -> ■ 2, 4-Dioxychinolin b 14. i-Amino-2-oxy-5-nitrobenzene jordo red W, L: -3- i-Oxy-4-methylbenzene b fin red-brown JU b

Claims (1)

Claim : Process for the preparation of chromium compounds free from silfonic acid groups o, o'-Dioxvazo- or o-Oxycarboxyfai'bstoffe, characterized in that the dyes in aqueous solution or Suspension at elevated temperature open or under pressure with salts of the complex Treated chromium compounds of aromatic o-oxycarboxylic acids and applying at least one atom of chromium to each chromable group of the stain dye.