DE1151621B - Process for the production of metal-containing, water-insoluble azo dyes - Google Patents

Description

Process for the preparation of metal-containing, water-insoluble azo dyes where A and B are radicals of the benzene or naphthalene series, coupled with arylamides of aromatic or heterocyclic o-oxycarboxylic acids or of acyl acetic acids in bulk, on the fiber or on another substrate, the diazo and azo components being free of water-solubilizing groups, such as sulfonic acid - Or carboxylic acid groups, and the dyes thus obtained are treated with metal donating agents.

This process gives valuable azo dyes that are In addition to good general fastness properties, they are characterized in particular by very good light fastness properties.

In pursuing this inventive concept, it has now been found that valuable, metal-containing, water-insoluble azo dyes are also obtained if the diazonium compounds of amines of the general formula are used where A and B are radicals of the benzene or naphthalene series, here with azo components that couple in the neighboring position to form an oxy group, with the exception of the arylamides of aromatic or heterocyclic o-oxycarboxylic acids or acyl acetic acids, combined in substance, on the fiber or on another substrate , wherein the diazo and azo components do not contain any water-solubilizing groups, such as sulfonic acid or carboxylic acid groups, and the dyes thus obtained are treated with metal donating agents.

As amino compounds which correspond to the formula given above and which can be used advantageously in the present process, the amines mentioned in the main patent come into consideration, i.e. compounds in which the benzene or naphthalene radicals A and B are replaced by groups that do not make water soluble, for example halogen atoms, Alkyl, alkoxy, aryloxy, acylamino, tri $ uormethyl, sulfonic acid amide or carboxamide groups can be substituted. These amino compounds can be prepared using the method described in German Auslegeschrift 1088 060.

As azo components that do not have any water-solubilizing groups, such as Containing sulfonic acid or carboxylic acid groups come in the case of the invention Method Compounds into consideration which couple in an adjacent position to form an oxy group, d. H. aromatic or heterocyclic oxy compounds and compounds that have a contain enolizable or enolized ketomethylene group, which is in a heterocyclic Ring is located. Such compounds are, for example, those substituted in the 4-position Derivatives of phenol, such as p-cresol, p-chlorophenol, 4-oxy-1,2-xylene, 4-oxyacetophenone and hydroquinone monomethyl ether, the derivatives of α-naphthol substituted in the 4-position, such as 4-chloro-1-naphthol, 4-methoxy-1-naphthol and 4-benzoyl-1-naphthol, β-naphthol and its derivatives such as 6-bromo-2-naphthol, 7-oxy-2-methoxynaphthalene, 1-benzoylamino-7-naphthol and 4-benzolazo-1-amino-7-naphthol and 6-oxyquinone, 2-oxycarbazole, 3-oxydiphenylene oxide and 1-aryl-3-methyl-5-pyrazolones. In addition to these monooxy compounds, there are also azo components also aromatic polyoxy compounds which couple in the o-position to the oxy groups or heterocychic series into consideration, for example resorcinol, benzoylresorcinol, Terephthaloyl bisresorcinol, 2,6-dioxynaphthalene and 3; 6-dioxydiphenylene oxide.

The production of the new dyes takes place in different ways Way. For example, vegetable fibers, including those made from regenerated Cellulose, with the alkaline solutions of the azo components, which are mostly not or are only a few nouns, impregnated and from the excess by squeezing or spinning off to be freed.

After any intermediate drying of the impregnated The dyestuff is dyed in the usual way in one of the diazonium compounds one of the amine-containing developing baths used according to the invention is carried out.

The azo dyes can be metallized in the developing bath be made by giving it metal-donating before or during the coupling Agent adds and the metallization is completed by increasing the temperature.

However, the metallization can also follow the dye formation in a special bath that is neutral, weakly acidic or weakly alkaline is held and, in addition to the metal-donating compounds, optionally dispersing or Detergents, for example fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers. Alkyl naphthol polyglycol ethers, fatty acid polyglycol esters or fatty acid amide polyglycol ethers, may contain.

With a suitable working method, the new dyes can also be used on animals Fibers, such as wool or silk, as well as synthetic fibers, such as polyamide or Polyvinyl alcohol fibers.

The dyes can also be produced in substance and through Treatment with the metal donating agents in aqueous solution or in organic Solvents such as acetone or dimethylformamide into the metal complex compounds convict. The dyes obtainable in this way are suitable for dyeing synthetic ones Fibers as well as high molecular weight organic plastic masses.

The metal-releasing agents used in the method according to the invention predominantly copper, cobalt and nickel releasing compounds are considered, which in Form of their inorganic or organic salts, for example as chlorides, bromides, Sulphates, nitrates, formates or acetates, or as complex compounds, in particular with oxyalkylamines, for example diethanolamine, triethanolamine or N-methylethanolamine, or with aminocarboxylic acids, e.g. B. aminoacetic acid or nitrilotriacetic acid, or with aliphatic oxycarboxylic acids, e.g. B. citric acid, tartaric acid, or gluconic acid Glycolic acid, or with alkali phosphates, e.g. B. alkali pyrophosphates or alkali polyphosphates, can be used. When using a cobalt-releasing agent affects an addition of compounds of hexavalent chromium or of others Oxidizing agents, for example alkali borates, alkali permersulfates or alkali percarboates, favorably on the metallization.

On vegetable fibers, the present method is obtained Invention of dyes which, in addition to good general fastness properties, have very good light fastness properties distinguish. Those using copper compounds are particularly valuable available shades of brown. Example A cotton fabric is made on the foulard with the following Solution padded and dried: 14.4 g of β-naphthol are mixed with 30 g of a wetting agent of the type of oil sulfonate and 10 ccm sodium hydroxide solution of 38 ° B6 made into a paste and with boiling Water containing 3 g of tragacanth thickening per liter, dissolved and adjusted to one liter.

The dried fabric is 15 to 20 minutes at 20 ° C and then after slow heating to 95'C for 20 to 30 minutes at 90 to 95'C in the following Developed development bath described in a long liquor. Then 3 ccm Hydrochloric acid of 20 ° Be in liter of water and rinsed -15 minutes at 60 ° C with 2 g of soap Soaped, rinsed and dried in a liter of water.

Development bath 1.75 g of 2- (2'-amino-4 ', 5'-diethoxyphenyl) -6-chlorobenzotriazole-1-oxide in the form of a diazonium compound prepared in the usual way are in 1 1 of water dissolved, the 2 g of an action product of about 20 moles of ethylene oxide to 1 mole of octadecyl alcohol, 1 cc of acetic acid (50ol), 7 g of sodium acetate and 1.25 g contains copper sulphate.

A brownish black color is obtained. The table below also contains a number of further components which can be used according to the invention and the color shades of the metal-containing azo dyes obtainable therefrom on the fiber, which likewise have good fastness properties. hue Diazo component azo component copper cobalt nickel complex complex complex 2- (2'-Amino-4 ', 5'-diethoxyphenyl) - ß-naphthol brownish yellowish brown 6-chlorobenzotriazole-l-oxide black brown Likewise. 2-chloro-1-naphthol black and dark yellowish tinge brown brown dark Brown Likewise 4-chloro-1-naphthol black-red-tinged red-tinged brown dark dark brown brown (Continuation) hue Diazo component azo component copper cobalt nickel complex complex complex 2- (2'-Amino-4 ', 5'-diethoxyphenyl) - Resorcinol Gray-brown, yellow-tinged gray-brown 6-chlorobenzotriazole-1-oxide gray brown same. 3-oxydiphenylene oxide black yellow brown yellow brown the same. Terephthaloyl- yellow streaked red streaky red-brown bisresorcin dark dark brown brown p-cresol brownish brownish brownish Gray gray-yellow gray-yellow the same. 2,6-Dioxynaphthalene reddish yellowish yellowish Gray brown gray brown gray brown Likewise 3-oxydiphenylamine dark brown red brown gray brown likewise. 2-oxycarbazole brownish dark brown yellowish Black dark brown the same. 2,4-Dioxybenzo- yellowish dark brown red brown phenon dark Brown Likewise 3-oxycarbazole black bluish greenish tinge brown red brown gray brown p-chlorophenol gray-brown yellow-brown greenish Yellow-brown 2- (2'-Amino-4'-methoxy-5'-acetylamino-β-naphthol Brown Brown Brown phenyl) benzotriazole-1-oxide resorcinol brown - brown also 3-oxydiphenylene oxide brown brown - the same. 3-oxydiphenylamine greenish - - Brown likewise. 2-oxycarbazole brown brown brown likewise 2,4-dioxybenzo brown brown brown phenone also p-chlorophenol brown - - likewise. 3-oxycarbazole brown brown brown 2- (2'-Amino-4'-methoxy-5'-methyl-β-naphthol Brown Brown Brown phenyl) benzotriazole-1-oxide resorcinol brown brown brown 4-chloro-1-naphthol brown brown brown 3-Oxydiphenylene Oxide Brown Brown Brown also p-cresol brown - - likewise. 3-oxydiphenylamine greenish brown brown Brown likewise. 2-oxycarbazole brown brown brown likewise 2,4-dioxybenzo brown brown brown phenone p-chlorophenol brown brown brown likewise. 3-oxycarbazole brown brown brown 2- (2'-Amino-4 ', 5'-diethoxyphenyl) - ß-Naphthol Brown Brown Brown 6-methoxybenzotriazole-1-oxide resorcinol brown brown brown 4-chloro-1-naphthol brown brown brown 3-Oxydiphenylene Oxide Brown Brown Brown also p-cresol brown brown - likewise. 3-oxydiphenylamine brown brown brown likewise. 2-oxycarbazole brown brown brown (Continuation) hue Diazo component azo component copper cobalt nickel complex complex complex 2- (2'-Amino-4 ', 5'-diethoxyphenyl) - 2,4-Dioxybenzo- Brown Brown Brown _ 6'-methoxybenzotriazole-1-oxide phenone p-chlorophenol brown brown brown likewise. 3-oxycarbazole brown brown brown 2- (2'-Amino-4'-methoxy-5'-acetylamino-β-naphthol Brown Brown Brown phenyl) -6-methylbenzotriazole-1-oxide resorcinol brown brown brown same. 3-oxycarbazole brown - - 2- (2'-aminonaphthyl-1 ') = 6-methoxy-4-chloro-1-naphthol brown brown brown benzotriazole-l-oxide also p-chlorophenol - brown - - 2- (2'-aminonaphthyl-1 ') - 6-methyl-4-chloro-1-naphthol brown brown brown benzotriazole-l-oxide also p-cresol brown - - 2- (2'-Amino-4'-acetylamino-5'-methyl-β-naphthol Brown Brown Brown phenyl) benzotriazole-1-oxide also resorcinol brown - - 4-chloro-1-naphthol brown brown brown same. 3-oxydiphenylene oxide browning - - same. 3-oxycarbazole brown - - 2- (2'-Amino-4 ', 5'-dimethoxyphenyl) - ß-Naphthol Brown Brown Brown 6-methylbenzotriazole-1-oxide resorcinol brown brown brown 3-Oxydiphenylene Oxide Brown Brown Brown likewise. 3-oxydiphenylamine brown brown brown likewise. 2-oxycarbazole brown brown brown likewise 2,4-dioxybenzo brown brown brown phenone same. 3-oxycarbazole brown brown - 2- (2'-Amino-4 ', 5'-dimethylphenyl) - ß-Naphthol Brown Brown Brown benzotriazole-l-oxide the same. Resorein brown brown brown also: 4-chloro-l-naphthol brown brown brown 3-Oxydiphenylene Oxide Brown Brown Brown likewise. 3-oxydiphenylamine brown brown brown likewise. 2-oxycarbazole brown brown brown likewise 2,4-dioxybenzo-brown brown red-brown phenone p-chlorophenol brown brown brown likewise. 3-oxycarbazole brown brown brown

Claims (1)

PATENT CLAIMS: 1. Modification of the process for the preparation of metal-containing, water-insoluble azo dyes according to Patent 1,126,545, characterized in that the diazonium compounds of amines of the general formula where A and B are radicals of the benzene or naphthalene series, here with azo components that couple in the neighboring position to form an oxy group, with the exception of the arylamides of aromatic or heterocyclic o-oxycarboxylic acids or acyl acetic acids, combined in substance, on the fiber or on another substrate wherein the diazo and azo components do not contain any water-solubilizing groups, such as sulfonic acid or carboxylic acid groups, and the dyes thus obtained are treated with metal donating agents. 2. The method according to claim 1, characterized in that the treatment with the metal-releasing agents is carried out during the coupling. 3. The method according to claim 1, characterized in that the treatment with the metal donating agents is carried out after coupling in a neutral, weakly acidic or weakly alkaline medium. 4. The method according to claim 1 and 3, characterized in that the treatment with the metal donating agents is carried out in the presence of dispersants or detergents. 5. The method according to claim 1 to 4, characterized in that complex compounds of copper, cobalt or nickel with oxyalkylamines, amino acids or polyphosphates are used as metal donating agents. When the application was announced, a coloring table with an explanation was displayed.