Patent GB-464511-A (GB)
Title: Improvements in the dyeing of cellulose esters and ethers
Filed: 1935-08-14
Abstract: Cellulose esters or ethers, dyeing; azo dyes, forming on the material.--In the production of azo dyestuffs upon cellulose ester or ether material with the use of triazene (diazoamino) compound, such compound is applied to the material from a neutral or slightly alkaline bath.  The coupling component may be applied simultaneously with the triazene or in a subsequent developing bath.  The triazenes used are those obtainable by reacting diazo compounds with secondary aliphatic or cycloaliphatic amines (cf. Specifications 306,844, [Class 2 (iii)] 429,618, and 435,171), or with cyanamide or cyanamidecarboxylic acid (cf. Specification 443,222).  The diazo compounds used are those of the aromatic series, free from water-solubilizing groups, customarily employed in the production of ice colours and numerous such compounds are specified.  The specified coupling components are arylides of acetoacetic, 2 : 3-oxynaphthoic, 2 : 3-oxycarbazolecarboxylic and 2 : 3-oxyanthracenecarboxylic acids, m-phenylenediamine, the amides of 4-oxydiphenyl-3-carboxylic, 3-oxydiphenylamine-4 or 5-carboxylic, 3 - oxydiphenylether - 5 - carboxylic, 6-chloro-2 : 3-oxynaphthoic and 6-ethoxy-2 : 3-oxynaphthoic acids, the anilides of 3 : 6-dioxynaphthalene-2 : 7-dicarboxylic (cf. Specification 395,365), oxyphenanthrene-o-carboxylic and oxychrysene-o-carboxylic acids, 1 - phenyl-3-methyl-5-pyrazolone, a - and b -naphthols, aminonaphthols, 3-oxycarbazole, 3-oxyfluorene and its 2-carboxylic acid-o-toluidide, 3-oxydiphenyleneoxide and its 2-carboxylic acid-p-chloranilide, 1-oxyethylamino-5-naphthol, oxyanthracenes, oxyphenanthrenes and sulphatoethyl-m-toluidine.  The following examples are specified: (1) acetate rayon is entered into an aqueous bath at room temperature containing soda ash and a dispersion, with the sodium salt of the condensation product from naphthalenesulphonic acid and formaldehyde, of the triazene from diazotized 4-(4<1>-amino)phenylazo-1-naphthylamine and secondary hexaethenoxyamine, the bath is heated slowly to 50 DEG  C. and so maintained for \ba3/4\be hour, whereupon the dyeing is developed in a second bath at 85 DEG  C. containing 2 : 3-oxynaphthoic acid and acetic acid to a black shade; (2) acetate rayon is similarly dyed violet to purple with the use of the triazene from diazotized aminoazotoluene and secondary hexaethenoxyamine; (3) acetate rayon is similarly dyed a brilliant scarlet with the use of a dispersion with turkey red oil of the triazene from diazotized aniline and piperidine; (4) acetate rayon is entered into an aqueous bath containing trisodium phosphate, common salt and a re-dispersion with turkey red oil of the triazene, pasted with the sodium salt of (1), from diazotized 5-chloro-2-toluidine and diethanolamine, the bath is heated to 80 DEG  C. and so maintained for \ba3/4\be hour, whereupon the colour is developed to a bright scarlet in a second bath at 80 DEG  C. containing the anilide of 2 : 3-oxynaphthoic acid, acetic acid, sodium N-oleyl-4-aminoanisol-2-sulphonate and glue; (5) acetate rayon is entered into an aqueous bath containing soda ash and a dispersion with the sodium salt of (1) of the triazene from diazotized 4 - aminophenyl - azo - cresidine and diethanolamine, worked for 1 hour in this bath at 80--85 DEG  C., rinsed and developed to a bright blue in a second bath containing 2 : 3-oxynaphthoic acid and acetic acid; (6) acetate rayon is treated for 10 minutes in an aqueous bath at 80 DEG  C. containing equimolecular amounts of (a) the diazoimino compound from diazotized 5-chloro-2-toluidine and secondary hexaethenoxyamine and (b) the sodium salt of the anilide of 2 : 3-oxynaphthoic acid and is then rinsed and developed to a brilliant red by immersion for \ba1/2\be hour in a solution at 80 DEG  C. of dilute acetic acid; (7) acetate rayon is similarly dyed a deep reddish brown with the use of the diazoimino compound from 4-(4-amino)phenyl-azo-1-naphthylamine and secondary hexaethenoxyamine and, as coupling component, the sodium salt of sulphatoethyl-m-toluidine; (8) acetate rayon yarn is entered into an aqueous bath at 40 DEG  C. containing trisodium phosphate, sodium chloride, a re-dispersion with turkey red oil of the triazene, pasted with the sodium salt of (1), from diazotized 5-chloro-2-toluidine and diethanolamine and, as coupling component, the 5<1>-chloro-2<1>-toluidide of 2 : 3-oxynaphthoic acid pasted with the sodium salt of the acid sulphuric ester of the alcohols obtained by saponification of sperm oil, the bath is heated during \ba1/4\be hour to 80 DEG  C. and so maintained for \ba3/4\be hour, whereupon, after rinsing, the dyeing is developed to a bright bluish red, fast to washing, by treatment for \ba1/2\be hour in dilute acetic acid at 80 DEG  C.; with delustred goods the temperature may be 95--98 DEG C.; (9) acetate rayon yarn is similarly dyed a bright greenish blue with the use of a re-dispersion with turkey red oil of the triazene, pasted with the sodium salt of (1) and sodium N - oleyl - 4 - aminoanisol - 2 - sulphonate, from diazotized 4-benzoylamino-2 : 5-diethoxyaniline and diethanolamine and, as coupling component, the anilide of 2 : 3-oxynaphthoic acid; (10) acetate rayon yarn is similarly dyed orange with the use of a turkey red oil dispersion of the triazene compound from diazotized 2 : 5-dichloraniline and cyanamidecarboxylic acid and, as coupling component, the 5<1>-chloro-2<1>-toluidide of 2 : 3-oxynaphthoic acid.  A table is also given showing the shades obtainable with other combinations of diazo triazene-forming and coupling components, additional diazo components being 4- and 6-chloro-2-toluidines, 3-chloraniline, 4-nitro-2-aminoanisol, dianisidine, 1-naphthylamine, 3-benzoylamino-4-methoxyaniline, 1-aminoanthraquinone, 2-benzoylamino-4-chloro-5-aminoanisol, 2 : 5-dichloraniline, o-anisidine and 4-chloro-2-nitraniline, additional triazene-forming components being ethyl-(b <1>-oxyethyl-b  - oxy)ethyl - amine, morpholine, secondary tetraethenoxyamine, N - carbethoxypiperazine and cyanamide, and additional coupling components being di(acetoacetyl) tolidine, the 4<1>-chloranilide of 2 : p 3-oxycarbazolecarboxylic acid, the 2<1>-toluidide of 2 : 3-oxyanthracene carboxylic acid, 2-naphthol and the 3<1>-nitroanilide 2<1>-anisidide, 5<1>-methoxy-2<1>-toluidide, and 4<1>-bromo-2<1>-anisidide of 2 : 3-oxynaphthoic acid. Specifications 211,720, 237,739, [both in Class 15 (ii)], 436,371, and 454,869 also are referred to.  Secondary tetra- and hexa-ethenoxyamines are obtained by condensing ethylene oxide (4 and 6 mols. respectively) with 4-toluenesulphonamide (1 mol.) and hydrolyzing the product with sulphuric acid.  Ethyl - (b <1> - oxyethyl - b  - oxy)ethyl - amine is obtained by hydrolyzing with caustic soda the 4-nitroso compound of the reaction product from N-ethylaniline or N-ethyl-1-naphthylamine (1 mol.) with ethylene oxide (2 mols.).