Patent GB-779489-A (GB)
Title: New water-soluble mordant azophthalo-cyanine dyestuffs and process for making them
IPC: C09B43/12
Filed: 1954-01-13
Abstract: The invention comprises water-soluble mordant azo - phthalocyanine dyestuffs, which consist of a substituted or unsubstituted metalliferous phthalocyanine residue to which are bound in the four positions each corresponding to the 3 - or 4 - position of the phthalimide from which the phthalocyanine is derived at least one and not more than three identical or different groups of formula:- <FORM:0779489/IV(b)/1> and at least one and not more than three identical or different groups of the formula <FORM:0779489/IV(b)/2> and any of the said four positions not so substituted is substituted by a group of the formula - (SO3M), in which m is H, halogen CH3, OH, or SO3M, x is H, halogen CH3, OH, NO2, or SO3M, y is halogen, alkyl, alkoxy, NO2, SO3M, or COOM, z is H, halogen, alkyl, or alkoxy, M is H, an alkali metal, or NH4, and in which dyestuff the -SO2NH-group occupies a metaor para - position relatively to the azo linkage. They are made by reacting one mol of a phthalocyanine sulphochloride of the formula:- <FORM:0779489/IV(b)/3> in which A represents a substituted or unsubstituted metalliferous phthalocyanine residue to which the SO2Cl and - SO3M groups are bound in 3 - or - 4 - position of the phthalimide from which the phthalocyanine is derived, and n is a number from 2 to 4, in an aqueous medium and in presence of an acid-binding agent with 1, 2, or 3 mols. of one or more aminoazo dyes of the general formula:- <FORM:0779489/IV(b)/4> in which the NH2 group is meta - or parato the azo linkage, and with 1, 2, or 3 mols. of one or more dihydroxybenzene carboxylic acids of the formula:- <FORM:0779489/IV(b)/5> the aforesaid reactions being carried out simultaneously or in either order of succession and under such conditions that any unreacted sulphochloride group is hydrolysed. The products may be fixed on the fibre as a chromium lake, e.g. in chrome printing of cotton, or aftertreated with agents yielding metal, e.g. copper, e.g. on nylon, viscose or wool.  In examples (1) various copper phthalocyanine tetrasulphochlorides obtained by the reaction of copper phthalocyanine with chlorsulphonic acid or by sulphonation of copper phthalocyanine with oleum followed by conversion with chlorsulphonic acid and thionyl chloride, or by the action of chlorosulphonic acid on copper phthalocyanine - 4, 41, 411, 4111 - tetrasulphonic acid are reacted with varying proportions of 3 - amino - 41 - hydroxy - 1, 11 - azobenzene - 51 - carboxylic acid and 1, 3 - dihydroxybenzene - 4 - carboxylic acid; (2) instead of the azobenzene derivative used under (1), there may be used (a) 4 - amino - 31 - methyl - 41 - hydroxy -1, 11 - azobenzene - 51 - carboxylic acid, (b) 4 - amino - 41 - hydroxy - 1, 11 - azobenzene - 51 - carboxy - 6 - sulphonic acid, (c) 4 - amino - 2 - methyl - 5 - methoxy - 41 - hydroxy - 1:1 - azobenzene - 51 - carboxy - 31 - sulphonic acid, (d) 3 - amino-41 - hydroxy - 1, 1 - azobenzene - 51 - carboxy - 6 - sulphonic acid, (e) 4 - amino - 2 - methyl - 41 - hydroxy - 1:11 - azobenzene - 51 - carboxylic acid, (f) 4 - amino - 21, 41 - dihydroxy - 1, 11 - azobenzene - 51 - carboxylic acid (g) 4 - amino - 2 - methyl - 5 - methoxy - 51 - nitro - 21 - hydroxy - 1, 1 - azobenzene - 31 - carboxylic acid.  Also in examples, (3) copper phthalocyanine disulphochloride disulphonic acid is reacted as under (1); (4) copper phthalocyanine tetrasulphochloride is reacted with 1, 4 - dihydroxybenzene - 5 - carboxylic acid and (a) 4 - amino - 21, 41 - dihydroxy - 1, 11 - azobenzene - 51 - carboxylic acid or (b) 3 - amino - 4 - hydroxy - 1, 11 - azobenzene - 51 - carboxy - 6 - sulphonic acid, or (c) 3 - amino - 4 - hydroxy - 1, 11 - azobenzene - 51 - carboxylic acid; (5) copper phthalocyanine tetrasulphochloride is reacted with 6 - bromo - 1, 3 - dihydroxy - benzene - 4 - carboxylic acid and (a) 4 - amino - 2 - methyl - 41 - hydroxy - 1, 1 - azobenzene - 51 - carboxylic acid or (b) 3 - amino - 41 - hydroxy - 1, 1 - azobenzene - 51 - carboxylic acid or (c) 4 - amino - 31 - methyl - 41 - hydroxy - 1 11 - azobenzene - 51 - carboxylic acid. Other examples describe similar combinations of reactants and also the reaction of tetrasulphochlorides of cobalt, nickel, chromium, iron, and aluminium.  Specifications 763,343 and 768,444 are referred to.