Patent GB-377207-A (GB)
Title: Manufacture of insoluble azo-dyestuffs on the fibre
IPC: C09B39/00
Filed: 1931-03-19
Abstract: Azo dyes forming on the material.--Insoluble azo-dyestuffs are made on the fibre by applying a mixture containing an alkali salt of a 4-diazo- or 4 : 4<1>-tetrazo-sulphonic acid of the diarylamine series and an alkali salt of a hydroxylated coupling component (including b -ketonic acid derivatives) and steaming. There may be substituted for the alkali salt of the coupling component the corresponding free coupling component, together with sufficient alkali to form the alkali salt.  The aromatic nuclei of the diazo-sulphonates may contain substituents, e.g. alkyl, alkoxy, aryloxy, alkylmercapto, aroylamino, halogen, nitro, arylsulphonyl and arylaminocarboyl groups.  Coupling components specified are b -naphthol and its derivatives, e.g. aroylaminonaphthols, arylides of 2 : 3-oxynaphthoic acid (c.f. Specification 23732/13, [Class 2 (iii), Dyes &c.]), and its 6-halogen- or arylamino derivatives (c.f. Specification 330,349, [Class 2 (iii), Dyes &c.]) and arylides of 2-oxycarbazole-3-carboxylic acid; derivatives of 1-naphthol-4-carboxylic acid (c.f. Specification 211,223, [Class 2 (iii), Dyes &c.]), e.g. 1-naphthol-4-phenylketone; pyrazo lones and acetoaceticarylides (c.f. Specifications 211,772 and 211,814, [both in Class 2 (iii), Dyes &c.]); dioxyquinolines (c.f. Specification 332,940, [Class 2 (iii), Dyes &c.]), arylides of 6- or 7-hydroxy-2 : 1- and 1 : 2-naphthocarbazolecarboxylic acids (c.f. Specification 330,643, [Class 2 (iii), Dyes &c.]), and arylides of 2-hydroxyanthracene-3-carboxylic acid (c.f. Specification 367,907). The mixtures of diazosulphonate and coupling component are advantageously mixed with dyeing assistants having wetting, emulsifying or solvent properties and also with the additional agents used in nitrosamine-printing colours, e.g. chromate.  Sulphur may also be added.  In examples, (1) a paste containing the sodium salt of diphenylamine-4 : 4<1>-bis-diazosulphonic acid (from tetrazotized 4 : 4<1>-diaminodiphenylamine, sodium sulphite and sodium carbonate), 2 : 3-oxynaphthoic acid anilide, caustic soda, thiodiglycol, water and starch tragacanth is printed on a textile material, dried and steamed; a blueish-black print is obtained, (2) the diazo sulphonates of 4-amino-diphenylamine and its 4<1>-methoxy derivative are used as above, (3) the diazo sulphonate of 4-amino-3-methoxydiphenylamine (see Specification 338,240, [Class 2 (iii), Dyes &c.]), and the m-nitranilide of 2 : 3-oxynaphthoic acid are used as in (1) with the addition of alcohol and a neutral chromate solution to the printing paste, (4) the o-toluidide of 2 : 3-hydroxy-carbazolecarboxylic acid or diacetoacetyl-tolidine and diphenylamine-4 : 4<1>-bisdiazosulphonate are used as in (1), (5) a black print is obtained by applying a paste which contains the sodium salt of diphenylamine-4 : 4<1>-bis-diazosulphonic acid, the o-anisidide of 2 : 3-oxynaphthoic acid, caustic soda, sulphur, thiodiglycol and starch tragacanth and steaming, (6) a navy-blue is obtained by using the 4<1>-methoxydiphenylamine - 4 - diazosulphonate and the anilide of 2 : 3-oxynaphthoic acid as in (5) with the addition of sodium chromate and alcohol instead of thiodiglycol, (7) a bleached calico fabric is impregnated with a solution containing the sodium salt of 4<1>-methoxydiphenylamine-4-diazo-sulphonic acid, and the anilide of 2 : 3-oxynaphthoic acid, caustic potash, alcohol, thiodiglycol, sodium chromate and mucilage of tragacanth, dried and steamed; a blue self-coloured dyeing is obtained, (8) a mixture of the sodium salt of 4<1>-methoxy-diphenylamine - 4 - diazosulphonic acid, the anilide of 2 : 3-oxynaphthoic acid, sulphur and sodium hydroxide is ground together and made up into a printing paste, (9) a mixture of the sodium salt of 3-methoxydiphenylamine-4-diazosulphonic acid, the m-nitranilide of 2 : 3-oxynaphthoic acid and caustic soda is made up into a printing paste, (10) a mixture of the disodium salt of diphenylamine-4 : 4<1>-bis-diazosulphonic acid and the disodium salt of the m-nitranilide of 2 : 3-oxynaphthoic acid and sulphur is made into a printing paste, advantageously with the addition of caustic soda and used as above.  A table showing the shades obtained using various diazosulphonates and coupling components is given in the Specification.  Diarylamine derivatives.--4-Amino-3<1>-methoxydiphenylamine is made by condensing 1-amino-3-methoxybenzene with 1-chlor-4-nitro-benzene-2-sulphonic acid, splitting off the sulpho group and reducing.  Similarly 4-amino-4<1>-methylmercapto-diphenylamine may be obtained from 1-amino-4-methylmercaptobenzene, 4 - amino - 2<1> : 4<1>-dimethoxydiphenylamine from 1-amino-2 : 4-dimethoxybenzene and 4 - amino - 3<1> : 4<1> - dimethoxydiphenylamine from 1 - amino - 3 : 4 - dimethoxybenzene. 4-Amino-3<1>-chloro-6<1>-nitrodiphenylamine is made by condensing p-phenylenediamine with 1-chloro-3 : 4-dinitrobenzene. 4-Amino-2 : 5-dimethyl-3<1>-chloro-6<1>-nitrodiphenylamine is made similarly from 1 : 4-diamino-2 : 5-dimethylbenzene.  4 - Amino - 3 - methyl - 2<1> : 4<1> - dinitrodiphenylamine is made from 1 : 4-diamino-3-methylbenzene and 1 - chloro - 2 : 4 - dinitrobenzene; similarly 4-amino-3-methoxy-2<1> : 4<1>-dinitrodiphenylamine is made from 1 : 4-diamino - 3 - methoxybenzene, 4 - amino - 3 - chloro-2<1> : 4<1>-dinitrodiphenylamine from 1 : 4-diamino-3-chlorobenzene and 4-amino-2 : 5-dimethoxy-2<1> : 4<1>-dinitrodiphenylamine from 1 : 4-diamino-2 : 5 - dimethoxybenzene.  4 - Amino - 3 - (4<1> - methylbenzene - sulphonyl) - diphenylamine is made by oxidizing 4-aminodiphenylamine with 4-methylbenzene-1-sulphinic acid. 4-Amino-3<1>-(phenylamino-carboyl)-diphenylamine is made by condensing 1-chloro-4-nitrobenzene-2-sulphonic acid with metanilic acid, splitting off the sulpho group, condensing with aniline and reducing.  4 - Amino - 2 - methyl - 4<1> - methoxydiphenylamine is made by condensing p-anisidine with 1-methyl-2-chloro-5-nitrobenzene-3-sulphonic acid (obtained by sulphonating 1-methyl-2-chloro-5-nitrobenzene), splitting off the sulpho group and reducing. 4-Amino-3-methyl-5-chloro-4<1>-methoxydiphenylamine is made by the semidine rearrangement of 4<1>-methoxy-2-methyl-6-chloroazobenzene obtained by methylating the azo dyestuff 1 - amino - 2 - methyl-6-chlorobenzene --> phenol.