Patent GB-670522-A (GB)
Title: Process for dyeing with complex metal compounds
IPC: D06P3/64
Filed: 1949-06-28
Abstract: Sparingly-soluble metal complexes of dyestuffs containing once or twice the grouping <FORM:0670522/IV (c)/1> (where X is hydroxyl or carboxyl, A is an aromatic residue and B is an aromatic or heterocyclic residue), but having no hydroxyl oto a carboxyl group, are treated in aqueous suspension with ammonia or a water-soluble organic base so that the latter enters into the complex; the metals concerned are copper, nickel and cobalt.  The products are used in neutral or alkaline dyebaths for such fibres as linen, cotton, artificial silk and staple fibres of regenerated cellulose, the ammonia or organic base being split off again and the sparingly-soluble starting material being fixed on the fibre.  In the above formula, A may be a benzene or naphthalene residue and B a benzene, naphthalene or pyrazolone residue.  When X is carboxyl, a suitable starting material is the copper complex of the disazo dyestuff from tetrazotized benzidine-3 : 31-dicarboxylic acid and 1 - (61 - sulpho - 21 - naphthyl) - 3 - methyl - 5-pyrazolone. Preferred are copper derivatives of bis-o : o1-dioxyazo compounds of the type <FORM:0670522/IV (c)/2> where X is a direct linkage or a bridge member between two aromatic nuclei.  Thus the -R-X-R- residue may be a 1 : 3-bis-(sulphonaphthylamino) - 5 - phenylamino - triazine, diphenyl - 4 : 41 - bis - pyrazolone, stilbene-4 : 41-bis-pyrazolone or a simple diphenyl residue.  Suitable dyestuffs of these types are listed.  They may be prepared by treating the parent dioxy-azo compounds or mono-alkyl ethers thereof with metallizing agents by the usual methods, e.g. using a cuprammine complex or an aliphatic hydroxyamine as in Specification 644,883.  The water-soluble base used in the process of the invention may be ammonia, ethylamine, n-propylamine, n-butylamine, n-amylamine, n-hexylamine, monoethanolamine, ethylene diamine, N : N-diethyl-ethylene diamine, cyclohexylamine, diethylamine, diethanolamine, taurine or n-butyl-ethanolamine.  The base is preferably used in excess. The complexes formed thereby give submicroscopic dispersions or true solutions in water; they may be isolated in the solid state but are normally kept as stock solutions for making up dye baths. The examples show dyeing with the complexes obtained from copper derivatives of the following dyestuffs: 3 : 31-dioxybenzidine \sQ 1 - naphthol - 3 - sulphonic acid, 3 : 31 - dioxybenzidine \sQ 1 mol. of 1-(21-sulphophenyl)-azo-J-acid and 1 mol. of J-acid, 3 : 31-dioxybenzidine \sQ 2-oxyethylamino-8-naphthol - 6 - sulphonic acid, 3 : 31 - dioxybenzidine \sQ 1 - (81 - sulpho - 21 - naphthyl) - 3 - methyl - 5-pyrazolone, 3 : 31-dioxybenzidine \sQ J-acid, dianisidine \sQ N-oxyethyl-J-acid and 3 : 31-dioxybenzidine \sQ 1-(61-sulpho-21-naphthyl)-3-methyl-5-pyrazolone.  The cobalt and nickel derivatives of dianisidine \sQ N-oxyethyl-J-acid are also mentioned.  Details are given for the preparation of the sparingly-soluble copper derivatives of the disazo dyestuff 3 : 31-dioxybenzidine \sQ J-acid and the trisazo dyestuff 3 : 31 - dioxybenzidine \sQ 1 mol. of 1 - (21-sulphophenyl)-azo-J-acid and 1 mol. of J-acid. Specification 458,501 also is referred to.  According to the Specification as open to inspection under Sect. 91 the process is applicable to dyestuff complexes with any metal of atomic number 24-30, and in addition B in the first formula above may be any cyclic residue.  This subject-matter does not appear in the Specification as accepted.