Patent GB-470356-A (GB)
Title: Manufacture of dyestuffs containing metal in complex union
IPC: C09B45/01
Filed: 1936-03-05
Abstract: Complex metal compounds of dyestuffs are made by treating in the presence of an aliphatic aminocarboxylic acid or a salt thereof a dyestuff containing a group capable of binding metal in complex union with an agent yielding a metal of atomatic weight between 58 and 64, i.e. copper, nickel and cobalt.  The dyestuff may also be treated with a copper, nickel or cobalt salt of an aliphatic aminocarboxylic acid or a dyestuff containing copper, nickel or chromium in complex combination may be treated with an aliphatic aminocarboxylic acid or a salt thereof.  Water soluble products are obtained useful for dyeing wool, silk and leather. The dyeing of an oxide film on aluminium is also mentioned.  In examples: (1) the dyestuff 4 : 4<1>-diaminodiphenylurea \sQ salicylic acid is treated with ammoniacal copper oxide and the insoluble product mixed with sodium glycocoll; (2) the dyestuff (salicylic acid-azo-hydroquinone dimethylether-azo)2-dinaphthyl J acid is treated with copper glycocoll or with a copper salt of ethyl- or diethylaminoacetic acid, aminosuccinic acid, a -aminopropionic acid or a -amino-butyric acid; (3) the dyestuff (salicylic acid-azo-p-cresol methyl ether-azo)2-dinaphthyl J acid is treated with copper sulphate and the insoluble product treated with glycocoll and sodium carbonate; ethyl glycocoll and a -amino-propionic or butyric acid may be used; (4) the starting dyestuff of (2) is converted into an insoluble copper compound by means of copper sulphate or ammoniacal copper oxide and ground with sodium glycocoll; (5) the dyestuffs salicylic acid-azo-p-cresol methyletherazo - dinaphthyl J acid - azo - hydroquinone-dimethylether-azo-salicylic acid, [5-nitrophenol-2-azo-dinaphthyl J acid-azo]2-p : p<1>-dihydroxy-diphenylsulphone, salicyclic acid - azo - naphthalene - 6 - sulphonic acid - azo - naphthalene-6-sulphonic acid-azo-J acid and the dyestuffs obtained by condensing monoacetyl-p-phenylenediamine --> salicylic acid or 4-amino-1-phenol-2-carboxylic acid --> m-phenylenediamine with 4 : 4<1>-dinitrostilbene-2 : 2<1>disulphonic acid (cf. Specification 348,283) are treated with copper glycocoll; (6) the mixed urea from 4-chloraniline-3-sulphonic acid --> cresidine and p-aminosalicylic acid --> aniline, the mixed urea from metanilic acid --> o-anisidine and p-aminosalicylic acid --> aniline and the dyestuff o-cresotinic acid \sM benzidine --> 1-(m-sulphophenyl)-3-methyl-5-pyrazolone are treated with copper glycocoll; (7) the dyestuff 6-nitro-2-aminophenol-4-sulphonic acid --> b -naphthol is treated with copper glycocoll and the product precipitated on a substratum of aluminium sulphate and heavy spar; the dyestuffs 5-nitro-2-aminophenol --> 2-naphthylamine-6-sulphonic acid, 4-nitro-2-aminophenol-6-sulphonic acid --> 1-phenyl-3-methyl-5-pyrazolone, 4-chlor-2-aminophenol --> 2-naphthol - 6 - sulphonic acid, 4-nitro-2-aminophenol --> resorcinol or 1-phenyl-3-methyl-5-pyrazolone, and 1-amino-2-naphthol-4-sulphonic acid --> a - or b -naphthol may be similarly treated; (8) the dyestuff 1-amino-2-naphthol-4-sulphonic acid --> a -naphthol is similarly treated; (9) the dyestuff 2-amino-1-naphthol-4-sulphonic acid --> b -naphthol is treated with cobalt glycocoll; (10) 1 : 2-dihydroxyanthraquinone - 3 - sulphonic acid (Alizarine Red S) is treated with copper glycocoll; (11) 1 : 2 : 4 : 5 : 6 : 8-hydroxy-anthraquinone-3 : 7-disulphonic acid (Anthracene Blue SWX) is treated with copper glycocoll; the product may be used for dyeing oxide films on aluminium; (12) highly oxidized log-wood extract is treated with copper glycocoll; (13) the dyestuffs Naphthochrome Green G and Naphthochrome Azurine B are treated with copper glycocoll; (14) the copper or nickel compound of the dyestuff from 6-nitro-1-diazo-2-naphthol-4-sulphonic acid and b -naphthol is treated with sodium glycocoll; the copper and nickel compounds of the dyestuff 1-amino-2-naphthol-4-sulphonic acid --> a - or b -naphthol may be similarly treated; (15) the starting dyestuff of (3) is treated with copper or nickel sulphate and the insoluble compound stirred with sodium carbonate and glycocoll; (16) the dyestuff from 6-nitro-1-diazo-2-naphthol-4-sulphonic acid and b -naphthol is treated with sodium glycocoll and copper sulphate or other copper sulphate or a nickel or cobalt salt; (17) the starting dyestuff of (2) is treated with sodium glycocoll, sodium carbonate and copper sulphate or other salt.  Samples have been furnished under Sect. 2 (5) of the dyestuffs obtained by treating (1) Brilliant Alizarine Blue SD with copper glycocoll; (2) Gallocyanine DH with copper diethanolamino acetate (from copper chloracetate and diethanolamine); and (3) Gallein with copper diethylamino acetate.  Specifications 446,746 and 458,501 also are referred to.