Patent GB-455274-A (GB)
Title: Production of fast tints on cellulosic fibres
IPC: D06P3/64
Filed: 1935-04-10
Abstract: In the dyeing of cellulosic fibres, e.g. of cotton or regenerated cellulose, by application of a direct cotton azo dyestuff of which the complex metal compounds are sparingly soluble or insoluble in water and after-treatment with an agent yielding a metal of atomic weight above 52 adapted to form such complex compounds, the dyeing and the after-treatment are performed in one and the same bath. Specified metals are cobalt, nickel, manganese, zinc and copper.  The dyebath advantageously contains a dispersing, wetting or emulsifying agent, such as ammonia, an amine, e.g. pyridine, alkylamines, ethanolamine, cyclohexylethanolamine or butylethanolamine, a benzene- or naphthalene-sulphonic acid, which may be alkylated, an alcohol, e.g. glycerine, an alcohol sulphuric ester salt, a soluble condensation product of a higher fatty acid or ethylene oxide with an amine, oxyoleic acids, sulphoricinates, glue, sulphite cellulose lye, dextrin, albuminous degradation products, e.g. protalbinic or lysalbinic acid, aldehyde polymerization products or soluble degradation products of cellulose.  When dyestuffs not fully exhausted in the bath are used, the agents yielding metal are advantageously such as are stable to weak alkali, e.g. products of reaction of ammonia or amines with agents yielding copper, copper glycocollate, alkaline solutions of the product of reaction of an agent yielding the metal on an aliphatic oxycarboxylic acid, e.g. lactic, tartaric, glycollic, tartronic, malic, dioxytartaric, citric, saccharic, gluconic or heptonic acid.  The following examples are specified: (1) cotton is entered into an aqueous bath at 40 DEG  C. containing sodium carbonate, Cotton yellow G and the dyestuff, salicylic acid-azo-aminohydroquinone dimethyl ether (2 mols.) \sQ 5 : 5<1>-dioxy-2 : 2<1>-dinaphthylamine-7 : 7<1>-disulphonic acid (1 mol.), the temperature is raised to 90--95 DEG  C., Glauber's salt is added, the bath is boiled gently for 1 hour, a feebly alkaline copper sulphate-sodium tartrate solution is then added, dyeing is continued at 95--100 DEG  C. for \ba1/2\be hour and the goods are soaped to obtain a green dyeing, fast to washing; (2) cotton is similarly dyed with the use, as dyestuff, of (a) salicylic acid-azo-aniline --> 5 : 5<1>-dioxy-2 : 2<1>-dinaphthylamine-7 : 7<1>-disulphonic acid \sM 5-nitro-2-aminophenol, (b) 4 : 4<1>-diaminodiphenyl-3 : 3<1>-dicarboxylic acid \sQ 1 : 8 : 4-aminonaphtholsulphonic acid or 1-phenyl-5-pyrazolone-3-carboxylic acid (1 mol.) and the 2-chloranilide of acetoacetic acid (1 mol.) or (c) 4 : 4<1>-diaminodiphenyl-3 : 3<1>-dicarboxylic acid \sQ N-phenyl-2-naphthylamine (1 mol.) and 5 : 5<1>-dioxy-2 : 2<1>-dinaphthylamine-7 : 7<1>-disulphonic acid, 1-naphthol-5-sulphonic acid or resorcinol (1 mol.); (3) cotton is similarly dyed with the use, as dyestuff, of (a) the second dyestuff in (1) above, (b) salicyclic acid-azo-1-naphthylamine --> 1 - naphthylamine - 6 - sulphonic acid --> 2-phenylamino-5-naphthol-7-sulphonic acid or (c) salicylic acid-azo-1-naphthylamine - 6 - sulphonic acid --> 1 - naphthylamine --> 2 - phenylamino - 5 - naphthol - 7 - sulphonic acid; (4) cotton is entered into an aqueous bath at 40 DEG  C. containing sodium carbonate, Glauber's salt and (a) the dyestuff of the first paragraph of example 5 of Specification 348,283, (b) the products of reaction of p-aminosalicylic acid, 4-aminophenyl-azo-o-cresotinic acid or p-aminosalicylic acid --> 1-naphthylamine on 4 : 4<1>-dinitrostilbene-2 : 2<1>-disulphonic acid in presence of alkali at raised temperature or (c) salicylic acid-azo-1-naphthylamine-6-sulphonic acid --> 1-naphthylamine --> 2 : 5 : 7-aminonaphtholsulphonic acid and dyed for \ba3/4\be hour at 90--100 DEG  C., copper glycocollate, ethylglycocollate or diethylglycocollate is then added, dyeing is continued for 15--30 minutes at 80--100 DEG  C. and the goods are rinsed and dried to obtain a dyeing fast to washing; (5) cotton is similarly dyed with the use, as dyestuff, of salicyclic acid-azo-cresidine (2 mols.) \sQ 5 : 5<1>-dioxy-2 : 2<1>-dinaphthylamine-7 : 7<1>-disulphonic acid (1 mol.), and, as agent yielding metal, of a neutralized copper sulphatetartaric acid solution; (6) cotton is similarly dyed, with the use, as dyestuff, of Cotton yellow G and, as agent yielding metal, of triethanolamino-cupri-sulphate; (7) cotton is dyed similarly to (1) above with the use, as dyestuff, of the product of reaction of p-phenylenediamine --> salicylic acid on 4 : 4<1>-dinitrostilbene-2 : 2<1>-disulphonic acid in presence of alkali and, as agent yielding metal, copper sulphate, the bath being neutralized with acetic acid before adding the copper sulphate; (8) cotton is similarly dyed with the use, as dyestuff, of 4 : 4<1>-diaminodiphenyl-3 : 3<1>-dicarboxylic acid \sQ N-phenyl-2-naphthylamine (1 mol.) p  and 5 : 5<1>-dioxy-2 : 2<1>-dinaphthylamine-7 : 7<1>-disulphonic acid (1 mol.); (9) cotton is entered into an aqueous bath containing the dyestuff of the fourth paragraph of example 5 of Specification 348,283, and Glauber's salt, the temperature is raised to the boil and dyeing continued for \ba3/4\be hour, the bath is then allowed to cool to 80 DEG  C., triethanolamino-cupri-sulphate is added, dyeing is continued for 20--30 minutes at 80 DEG  C. and the goods are rinsed, soaped, rinsed and dried to obtain a brown-red dyeing, fast to light and washing; (10) cotton is entered into an aqueous bath at 30--40 DEG  C. containing the dyestuff, 4 : 4<1>-diaminodiphenyl-3 : 3<1>-dicarboxylic acid \sQ N-phenyl-2-naphthylamine (1 mol.) and resorcinol (1 mol.), sodium carbonate and the cyclohexyl ester of sulphophthalic acid, the temperature is raised to the boil, Glauber's salt is added and dyeing is continued for \ba3/4\be hour at 90--100 DEG  C., a neutral or weakly alkaline copper-sulphate-saccharic acid or trioxyglutaric acid solution is then added, dyeing is continued for \ba1/2\be hour at 90--100 DEG  C. and the goods are rinsed, washed, soaped, rinsed and dried to obtain a violet-brown dyeing, fast to washing; (11) cotton is dyed similarly to (1) with the use, as dyestuff, of 4 : 4<1>-diaminodiphenyl-3 : 3<1>-dicarboxylic acid \sQ 1 : 8 : 4-aminonaphtholsulphonic acid (1 mol.) and the 2-chloranilide of acetoacetic acid (1 mol.) and, as agent yielding metal, of a neutral or weakly alkaline copper sulphateglycollic acid solution; (12) cotton is similarly dyed with the use, as dyestuff, of 4-aminodiphenyl - 3 : 3<1> - dicarboxylic acid - 4<1> - azo - N-phenyl-2-naphthylamine (2 mols.) \sQ 5 : 5<1>-dioxy-2 : 2<1>-dinaphthylamine-7 : 7<1>-disulphonic acid (1 mol.) and, as agent yielding metal, of a neutral or weakly alkaline copper-sulphatetartaric acid solution; (13) cotton is dyed similarly to (4) above with the use, as dyestuff, of the product of condensation, in presence of alkali, of dinitrostilbenedisulphonic acid (1 mol.) with 2 : 4-diamino-4<1>-oxy-3<1>-carboxyazobenzene (2 mols.) (cf. Specification 348,283) and, as agent yielding metal, of ammoniacal cobalt oxide; (14) cotton is dyed similarly to (1) above with the use, as dyestuff, of 4 : 4<1>-diaminodiphenyl-3 : 3<1>-dicarboxylic acid \sQ N-phenyl-2-naphthylamine (1 mol.) and 1 : 5-naphtholsulphonic acid (1 mol.) and, as agent yielding metal, of a weakly alkaline copper sulphate-gluconic acid or malic acid solution; (15) cotton is dyed similarly to (4) above with the use, as dyestuff, of the condensation product from dinitrostilbenedisulphonic acid (1 mol.) and 4-aminophenol-2-carboxylic acid (2 mols.) (cf. Specification 348,283) and, as agent yielding metal, of alkaline nickel tartrate.