Patent GB-468362-A (GB)
Title: Production of fast tints on vegetable fibres
IPC: D06P3/64
Filed: 1935-12-30
Abstract: Dyeings fast to washing and to light are produced upon vegetable fibres by dyeing them with direct cotton dis- or poly-azo dyestuffs containing lake-forming groups and treating the dyeings with agents yielding metal, at least one phase of the process being performed in a caustic alkaline medium at a raised temperature.  Alternatively, the fibres are dyed with a complex metal compound of a direct cotton dyestuff in a caustic alkaline medium at a raised temperature. Specified metals are copper, chromium, cobalt, nickel, aluminium, manganese, zinc, vanadium and titanium.  When the complex metal compounds are sparingly soluble or insoluble in water the parent dyestuff or the metal complex therefrom is preferably pre-treated with, or used in conjunction with, a dispersing, wetting, or emulsifying agent, of which many types are specified.  The lake-forming character of the dyestuffs may be derived from the use of diazo components containing a hydroxyl, carboxyl or alkoxyl group in o-position to the diazo group or in o- or peri-position to a cyclic tertiary nitrogen atom or from the use of diazo or coupling components containing the salicylic acid grouping.  The substantive character of the dyestuffs may be derived from the use, as components, of benzidine, stilbene, diarylazoxy, carbazole or acetoacetic acid derivatives, ureas or thioureas from arylenediamines, pyrazolones or aminonaphthols or their derivatives. When the treatment with the agent yielding metal is effected in a caustic alkaline medium at a raised temperature, the agents are preferably such as are stable to dilute caustic alkali, e.g. those obtainable by treating a compound of the metal with an aliphatic oxycarboxylic acid such as lactic, tartaric, glycollic, tartronic, malic, dioxytartaric, citric, saccharic, gluconic or heptonic acid or an aminocarboxylic acid such as glycocoll, and with an alkali or amino compound.  The following examples are specified: (1) cotton is entered into an aqueous bath at 30--40 DEG  C. containing Glauber's salt, caustic soda and the dyestuff, 4 : 4<1>-diaminostilbene-3 : 3<1>-dicarboxylic acid \sQ 2-phenylaminonaphthalene (1 mol.) and 5 : 5<1>-dioxy2 : 2<1>-dinaphthylamine-7 : 7<1>-disulphonic acid (1 mol., coupled alkaline), the temperature is raised to boiling and so maintained for \ba3/4\be hour, an alkaline solution of copper sulphate, tartaric or saccharic acid and caustic soda is then added and the goods are further treated for \ba1/2\be hour at 90--100 DEG C. or, if desired, at a much lower temperature to obtain a strong, level, pure blue dyeing; (2) cotton is similarly dyed with the use, as the parent dyestuff, of benzidine \sQ o-cresotinic acid (2 mols.); the alkaline solution of copper sulphate may, alternatively, be added to the bath initially; (3) cotton is entered into an aqueous bath at 30--40 DEG  C. containing Glauber's salt and the copper compound of the dyestuff, benzidine-3 : 3<1>-dicarboxylic acid \sQ 2-phenylaminonaphthalene (1 mol.) and 1 : 8 : 4-aminonaphtholsulphonic acid (1 mol., coupled alkaline), such compound having been first pasted with tartaric acid or glycollic acid amide and an excess of caustic soda and the temperature is raised to boiling and so maintained for 1 hour to obtain a reddish blue dyeing, fast to washing; (4) cotton is similarly dyed with the use of the same copper compound pasted with tartaric acid or malonic acid monoamide, copper sulphate and an excess of caustic soda; (5) cotton is entered into an aqueous bath at 30--40 DEG  C. containing Glauber's salt, glycerol, caustic soda and, as dyestuff, the product of condensation of 4 : 4<1> - dinitrostilbene - 2 : 2<1>-disulphonic acid with the dyestuff, 4-amino-acetanilide --> salicylic acid (cf. Specification 348,283), the temperature is raised to 90--100 DEG  C. and so maintained for \ba1/4\be hour and an alkaline solution of copper sulphate, tartaric acid or ammonium citrate, and caustic soda is added and dyeing is continued at 90 DEG  C. for 15--20 minutes to obtain an orange dyeing fast to light and washing; (6) cotton is entered into an aqueous bath at 30--40 DEG  C. containing Glauber's salt, sugar or ethyl alcohol, caustic soda and the dyestuff, 2 mols. of (salicylic acidazo-aminohydroquinone-dimethyl ether) \sQ 5 : 5<1>-dioxy-2 : 2<1>-dinaphthylamine-7 : 7<1>-disul phonic acid (1 mol.), the temperature is raised to boiling and so maintained for \ba1/2\be hour, an alkaline solution of copper sulphate, tartaric or lactic acid and caustic soda is then added and dyeing is continued for 15--20 minutes to obtain a blue dyeing fast to light and washing; the first component of the dyestuff may be replaced by salicylic acid-azo-cresidine; (7) cotton is entered into an alkaline bath at 30--40 DEG  C. containing Glauber's salt, caustic soda, the dyestuff, 2 mols. of (salicylic acid-azocresidine) \sQ 5 : 5<1>-dioxy - 2 : 2<1>-dinaphthylamine-7 : 7<1>-disulphonic acid (1 mol.), copper sulphate and potassium sodium tartrate or aminotartaric acid and the temperature is raised to boiling and so maintained for \ba3/4\be--1 hour to obtain a strong level pure blue dyeing, fast to washing; (8) cotton is entered at 30--40 DEG  C. into an aqueous bath containing sodium carbonate and the dyestuff of (5), the temperature is raised to boiling and so maintained, after addition of Glauber's salt, for \ba3/4\be hour, an alkaline solution of chromium and nickel sulphates, tartaric or tartronic acid and caustic soda is then added and dyeing is continued at 90--100 DEG  C. for \ba1/2\be hour to obtain an orange dyeing fast to washing and light; (9) cotton is treated for \ba3/4\be hour in an aqueous bath at 90--100 DEG  C. containing Glauber's salt, sodium carbonate and the dyestuff of (7), an alkaline solution of cobalt hydroxide in ammonia or ethanolamine, chromium sulphate, tartaric or glycollic acid and caustic soda is then added and treatment continued for \ba1/2\be hour to obtain a blue dyeing fast to washing and light which may be improved by treatment in a sodium carbonate-soap bath at 50 DEG  C.; (10) cotton is dyed as in (8) with replacement of the dyestuff by Cotton yellow G and of the nickel sulphate by copper sulphate; (11) cotton is entered into an aqueous bath at 30 DEG  C. containing Glauber's salt, caustic soda and a dyestuff corresponding to that in (7) with replacement of the twice-coupling component by the 2-amino-4 : 6-di(5<1>-oxy-7<1>-sulpho-2<1>-naphthyl)-amino derivative of cyanuric acid, the temperature is raised to boiling and so maintained for \ba3/4\be--1 hour, a solution containing copper sulphate, potassium sodium tartrate or sodium gluconate and caustic soda is added and the treatment continued at 80--100 DEG  C. for \ba1/2\be hour to obtain a strong level pure blue dyeing, fast to washing; (12) cotton is entered into an aqueous bath at 30--40 DEG  C. containing Glauber's salt, sodium carbonate or caustic soda and the dyestuff, dianisidine \sQ 1 : 8 : 4-aminonaphtholsulphonic acid (2 mols., coupled alkaline), the temperature is raised to boiling and so maintained for \ba3/4\be hour, an alkaline solution of copper sulphate, tartaric or lactic acid and caustic soda is added and the treatment continued at 95--100 DEG  C. for \ba1/2\be hour to obtain a green-blue dyeing fast to light; (13) cotton is entered into an aqueous bath at 30--40 DEG C. containing Glauber's salt and the dyestuff of (1), the temperature is raised to boiling and so maintained for \ba3/4\be hour and the goods are rinsed and treated for \ba1/2\be hour in a fresh bath containing an alkaline solution at 60--70 DEG  C. of copper sulphate, tartaric acid and caustic soda to obtain a fast blue dyeing; (14) cotton is treated in a first bath as in (13), an alkaline solution of copper sulphate, tartaric acid caustic soda and ammonia is then added and treatment continued at 95--100 DEG  C. for \ba1/2\be hour to obtain a fast blue dyeing; (15) cotton is treated in a first bath as in (13), sodium benzylnaphthalenesulphonate or the sodium salt of sulphophthalic acid diamyl ester (as emulsifying agent) and an alkaline solution of copper sulphate, tartaric or glycollic acid and caustic soda are then added and treatment continued at 95--100 DEG C. for \ba1/2\be hour to obtain a fast blue dyeing; (16) cotton is dyed as in (14) with the use of the dyestuff of (3) and with omission of the ammonia to obtain a reddish blue dyeing, fast to alkali; the copper sulphate may be replaced by nickel sulphate; (17) cotton is similarly dyed with the use, as dyestuff, of benzidine-3 : 3<1>-dicarboxylic acid \sQ 1-(4<1>-oxy-3<1>-carboxy) phenyl-3-methyl-5-pyrazolone (2 mols.) to obtain a fast red-brown dyeing; (18) cotton is dyed as in (14) with the use of the dyestuff of (17) to obtain a fast red-brown dyeing; (19) cotton is dyed as in (15) with the use of the dyestuff of (17) and the use, as emulsifying agent, of a preparation from glue and soap to obtain a fast red-brown dyeing; (20) wetted cotton satin is entered into an aqueous bath at 50 DEG  C. containing the copper compound of the dyestuff, salicylic acid \sM benzidine --> resorcinol \sM 2-aminophenol-4-sulphonic acid, the temperature is raised to 95 DEG  C. and, after addition of Glauber's salt, so maintained for \ba1/2\be hour, a solution containing copper sulphate, potassium tartrate or glycollic acid amide and caustic soda is then added and treatment continued for \ba1/2\be hour at 90--95 DEG  C. to obtain a strong brown dyeing fast to light, washing and alkali; (21) wetted cotton satin is similarly dyed with the dyestuff, benzidine \sQ o-cresotinic acid (1 mol.) and 1-(4<1> sulpho) phenyl - 3 - methyl - 5 - pyrazolone (1 mol.), to obtain a similarly fast orange dyeing; (22) wetted cotton satin is similarly dyed with the disazo dyestuff obtainable by the action of phosgene on equimolecular proportions of 4<1> - aminobenzene - azo - 4 - oxybenzene - 3 - carbox