Patent GB-499868-A (GB)
Title: Process of colouring nitrogenous materials
IPC: D06P3/00
Filed: 1937-06-25
Abstract: Fibrous or plastic material containing amino groups is coloured by causing it to react, at a temperature above 50 DEG  C. and in presence of an acid-binding agent, with an organic compound containing one or more chromophoric groups and one or more residues capable of splitting off acid by reaction with the hydrogen atoms of the amino groups.  The colorations are specially fast to water, washing and chemical action.  Specified fibrous or plastic materials coloured are wool, hair, silk, gelatine, casein, glue and other albuminous materials, albumens hardened, e.g. with formaldehyde, urea-formaldehyde and other nitrogenous plastic materials soluble or insoluble in water, animalized staple fibre and cellulose or cellulose derivatives in which basic compounds containing amino groups have been incorporated.  Specified chromophoric groups are those of the anthraquinone and triphenylmethane radicles and the azo group and specified acid residues are halogen atoms and nitro groups. Specified acid-binding agents are carbonates and bicarbonates of alkali and alkaline earth metals and of organic bases, alkali acetates, free organic bases, e.g. triethanolamine or pyridine, and ammoniacal steam.  Their action may be assisted catalytically by the presence of a metal, e.g. copper or nickel, a metal salt or a metal complex, e.g. a pyridinium compound.  The colouring compound, if water-soluble, may be applied in aqueous solution, and, if water-insoluble, may be applied in conjunction with a diluent such as a mono- or poly-hydric alcohol and a dispersing agent such as a soap, a sulphonated fatty alcohol, a condensation product of a fatty acid with an amino- or hydroxy-alkylsulphonic acid or an aminoalkylcarboxylic acid, a condensation product of an organic compound with ethylene oxide or a quaternary ammonium compound of high molecular weight; a protective colloid such as methylcellulose, sulphite cellulose liquor or starch may also be added.  In examples, (1) a deep bluish red coloration, fast to washing and fulling, is obtained on wool by treatment for 1 1/2 hours in an aqueous solution at 80 DEG  C. containing 1-amino-4-bromoanthraquinone-2-sulphonic acid and sodium bicarbonate; (2) wool, dyed in an acetic acid bath with 1-amino-4-bromoanthraquinone-2-sulphonic acid, is treated for 1 hour in an aqueous solution at 80 DEG  C. of sodium bicarbonate; (3) wool, similarly dyed, is exposed for 1/2 hour to an ammoniacal atmosphere at above 50 DEG  C.; (4) wool is coloured as in (1) with the addition of a trace of a copper salt to the solution. A table is also given showing the colorations obtainable on wool with the following anthraquinone derivatives, viz. the 1-amino-4-bromo-2-methanesulphonic acid (cf. Specification 440,208), 1-anilino-4-bromo-2-sulphonic acid, 1-hydroxy-4-bromo-2-sulphonic acid, 1 : 5-dibromo-4 : 8-dihydroxy-3 : 7-disulphonic acid, 1-amino-4-iodo-6-sulphonic and 2 : 6-disulphonic acids, 1-chloro-8-sulphonic acid 1-amino-4-bromo-2-carboxylic acid, 1-amino-2 : 4-dibromo-5- and 6-sulphonic acids, 1 : 8-dihydroxy-4 : 5-dinitro-disulphonic acid, 1-amino-4-bromo-5-acetylamino-2-sulphonic acid (cf. Specification 432,647) and 1 : 4-dichloro-6-sulphonic acid (cf. Specification 386,997), and with the following dyestuffs, viz. Toluylene red RT, Rhodamine 5G and Eosin G. 1-Anilino-4-bromoanthraquinone - 2 - sulphonic acid is obtained by diazotizing 1-amino-4-bromoanthraquinone-2-sulphonic acid, converting the product into the 1-iodo compound by the Sandmeyer reaction and reacting the 1-iodo compound with aniline in presence of cuprous chloride and sodium carbonate.  1 - Hydroxy - 4 - bromoanthraquinone - 2 - sulphonic acid is obtained by diazotizing the corresponding 1-amino compound and boiling the solution.  1 - Amino - 4 - iodoanthraquinone - 6 - sulphonic acid is obtained by diazotizing 1 : 4-diaminoanthraquinone-2 : 6-disulphonic acid (cf. Specification 264,879, [Class 2 (iii)], converting the product into the 4-iodo compound by the Sandmeyer reaction and splitting off the 2-sulphonic acid group by acid or alkaline treatment.  1 : 8-Dihydroxy-4 : 5-dinitroanthraquinone-disulphonic acid is obtained by nitrating the product obtained by sulphonating chrysazine.ALSO:Gelatine, glue and like albuminous materials containing amino groups are coloured by causing them to react, at a temperature above 50 DEG  C. and in presence of an acid-binding agent, with an organic compound containing one or more chromophoric groups and one or more residues capable of splitting off acid by reaction with the hydrogen atoms of the amino groups.  The colorations are specially fast to water, washing and chemical action.  Specified chromophoric groups are those of the anthraquinone and triphenylmethane radicles and the azo group and specified acid residues are halogen atoms and nitro groups. Specified acid-binding agents are carbonates and bicarbonates of alkali and alkaline earth metals and of organic bases, alkali acetates, free organic bases, e.g. triethanolamine or pyridine, and ammoniacal steam.  Their action may be assisted catalytically by the presence of a metal, e.g. copper or nickel, a metal salt or a metal complex, e.g. a pyridinium compound.  The colouring compound, if water-soluble, may be applied in aqueous solution and, if water-insoluble, may be applied in conjunction with a diluent, such as a mono- or poly-hydric alcohol, a dispersing agent and, if desired, a protective colloid.  Specified colouring compounds used are the following anthraquinone derivatives, viz. the 4-bromo-2-sulphonic acid derivatives of 1-amino-, 1-anilino-, 1-hydroxy- and 1-amino-5-acetylamino-anthraquinones, the 1-amino-4-bromo-2-methane sulphonic acid, the 1 : 5-dibromo-4 : 8-dihydroxy-3 : 7-disulphonic acid, the 1-amino-5-iodo-6-sulphonic and 2 : 6-disulphonic acids, the 1-chloro-8-sulphonic acid, the 1-amino-4-bromo-2-carboxylic acid, the 1-amino-2 : 4-dibromo-5- and 6-sulphonic acids, the 1 : 8-dihydroxy-4 : 5-dinitrodisulphonic acid and the 1 : 4-dichloro-6-sulphonic acid, and the following dyestuffs, viz.  Toluylene red RT, Rhodamine 5G and Eosin G.