Patent GB-706586-A (GB)
Title: A process for producing insoluble brown azo-dyestuffs on the fibre
IPC: D06P5/12
Filed: 1951-12-06
Abstract: 1 - Acylamino - 6 - naphthols and 2 - acyl - amino- 7 -naphthols are prepared by condensing the corresponding aminonaphthols with acid chlorides in the presence of an acid binding agent and an organic solvent.  Specified products are terephthalyl - N : N1 - bis - 1 : 6-amino - naphthol, N - phenyl - N1 - (711- hydroxy - naphthyl - 211)-urea and hexamethylene di - N1 - (711 - hydroxy - naphthyl - 211) - urea.  The acyl residues may be benzoic, substituted benzoic (e.g. m - nitro or p - chloro - benzoic), phenylacetic, phenoxyacetic, phthalic, terephthalic, naphthoic, naphthalene dicarboxylic, (e.g. 2 : 3, 1 : 8) naphthalene - 1 : 4 : 5 : 8-tetracarboxylic, phenylcarbamic, phenylenedicarbamic, carbonic, oxalic, adipic, hexamethylene dicarbamic, diphenyl - 4 : 41 - dicarboxylic or diphenylurea - 4 : 41 - dicarboxylic acid.  The amino-naphthols may be N - monosubstituted, e.g. by methyl, phenyl or benzyl.ALSO:Insoluble brown azo dyestuffs are produced on the fibre by known methods from diazotized p-aminodiphenylamine (or a substitution product thereof) and a 1-acylamino-6-naphthol or a 2-acylamino-7-naphthol.  White resists may be obtained by impregnating the fabric with an alkaline solution of the acylaminonaphthol, printing with a nonvolatile acidic compound, drying and developing with the diazo component.  Suitable acidic compounds are glycollic, tartaric, citric and oxalic acids, aluminium, zinc and ammonium sulphates, sodium bisulphate and monosodium phosphate.  Coloured resists are produced by adding to the printing paste a diazo compound which will couple in an acid medium or by printing with a leuco-ester salt of a vat dyestuff and (1) an ammonium salt of a nonvolatile acid, sodium chlorate and ammonium vanadate or (2) lead chromate, ammonium thiocyanate and potassium sulphite; in case (2) a separate acid development is necessary.  In the examples: (1) cotton is impregnated with an alkaline solution of terephthalyl-N : N\sv-bis-(1-amino-6-naphthol containing Turkey Red Oil and printed with a starch tragacanth paste containing (a) aluminium sulphate, (white resist), (b) aluminium sulphate and the zinc chloride double salt of 3 : 5-bis-trifluoromethylbenzene diazonium chloride (yellow resist), (c) aluminium sulphate and the zinc chloride double salt of 2-methoxy-4-nitrobenzene diazonium chloride (red resist), (d) aluminium sulphate and the zinc chloride double salt of 2 : 6-dichloro-2\sv : 5\sv-dimethoxyazobenzene-4\sv-diazonium chloride (blue resist), (e) sulphuric ester of leuco dimethoxydibenzanthrone, diglycol, potassium sulphite, ammonium thiocyanate, lead chromate and ammonia (green resist), (f) sulphuric ester of leucodibenzpyrenequinone, diglycol, ammonia, ammonium oxalate, sodium chlorate and ammonium vanadate (yellow resist); finally the fabric is impregnated with 4 - methoxydiphenylamine - 4\sv - diazonium chloride and chromium acetate and developed with sulphuric acid; (2) as in (1) the grounding solution being N - phenyl - N\sv-(7"-hydroxynaphthyl-2")-urea and the resists aluminium sulphate (a) above (white), (b) with the zinc chloride double salt of 2 - chloro - 5 - trifluoromethylbenzene diazonium chloride (orange) (c) with the zinc chloride double salt of 2 : 5-dimethoxy-4-cyanobenzene diazonium chloride (red); the final diazo component is diphenylamine-4-diazonium chloride; (3) cotton is impregnated with an alkaline solution of hexamethylene-di-N\sv - (7" - hydroxy - naphthyl - 2")-urea containing Turkey Red Oil and printed with a paste containing the sulphuric ester of leuco dimethoxydibenzanthrone, diglycol, potassium sulphite, ammonium thiocyanate, lead chromate and ammonia (green resist); it is then impregnated with 4 - methoxydiphenylamine - 4\sv - diazonium chloride and developed with sulphuric acid.  Other suitable acylamino-naphthols and diazo components are mentioned. Specification 20889/90, [Class (ii)] is referred to.  Condensation products are obtained by reacting 1-amino-6-naphthol and 2-amino-7-naphthol with acyl halides in the presence of an acid binding agent and an organic solvent.  The amino groups may be monosubstituted with alkyl, aralkyl, aryl or cycloalkyl groups.  Among the acyl groups that can be so introduced (see Group IV(b)) are those of stilbene-4 : 4\sv-dicarboxylic acid and azobenzene-4:4\sv-dicarboxylic acid.