Patent GB-830920-A (GB)
Title: Water-soluble azophthalocyanine dyestuffs
IPC: C09B47/26
Filed: 1957-09-04
Abstract: The invention comprises water-soluble azophthalocyanines of the formula <FORM:0830920/IV(c)/1> where Pc is a radical of a phthalocyanine containing, if desired, ionic and/or non-ionic substituents, R is -SO2-or-CO-, R1 is an amino-group containing radical of the naphthalene, pyrazolone or acylacetic acid arylamide series linked via the amino group to the radical R and containing a coupling position in the molecule to which is connected the azo group, R2 is the radical of a diazo component containing at least one water-solubilizing group, and n is a number from 1 to 4.  The compounds of the above formula are made by coupling diazo compounds containing at least one watersolubilizing group with phthalocyanine sulphonamides or carbonamides capable of coupling and of the formula <FORM:0830920/IV(c)/2> Diazo compounds mentioned include those derived from aminobenzene mono- and disulphonic and carboxylic acids which may contain halogen, nitro, hydroxyl, alkyl, alkoxy and acylamino p  substituents, aminonaphthalenes, aminodiphenylene, aminostilbene and heterocyclic compounds and may be substituted by one or more azo groups.  The coupling is conducted in conventional manner. The phthalocyanine sulphon- or carbonamides of the above formula are made by reacting phthalocyanines having 1-4 sulphonyl or carboxylic acid chloride groups with primary or secondary amines of the naphthalene, pyrazolone or acylacetic acid arylamide series capable of coupling with diazo compounds.  The phthalocyanine may be metal-free or metal-containing such as copper, cobalt, nickel, iron, chromium or zinc phthalocyanines containing the acid chloride groups in the 3- and/or 4-positions or in annellated rings such as naphthalene rings or in aryl radicals linked directly or via -CO-, -CO2- or -NH-groups.  In forming the amide unreacted acid chloride groups may be saponified to free acid groups or reacted with ammonia or amines.  The phthalocyanine may also contain halogen, alkyl, alkoxy or acylamino substituents.  The dyes may be converted in substance or on the fibre into lakes with alkali metal salts or into complexes with salts of chromium, cobalt, copper or nickel.  In examples, copper phthalocyanine-3-trisulphochloride is reacted with (1) 1-(41-aminophenyl) - 3 - methyl - pyrazolone - 5 and the sulphonamide coupled with diazotized 1-aminobenzene - 2 - sulphoni acid, 2 - aminobenzoic acid, 1 - aminobenzene - 2 : 5 - disulphonic acid, 1 - amino - 4 : 5 - dichlorobenzene - 2 - sulphonic acid, 4 - nitro - 41 - aminostilbene-2 : 21 - disulphonic acid, 4 - nitro - 2 - aminobenzoic acid, 2 - (41 - amino - 31 - sulphophenyl) - 6 - methyl - 7 - sulphobenzothiazole, 2 - (41 - aminophenyl) - 6 - methyl - 7 - sulphobenzothiazol or 2 - aminonaphthalene - 5 - sulphonic acid, or the same trisulphochloride is reacted with 1-(31-aminophenyl) - 3 - methylpyrazolone-5 and coupled with diazotized 1-amino - 2:5:6 - trichlorobenzene - 3 - sulphonic acid, (3) 31-aminobenzoylacetic acidphenyl-amide and the sulphonamide coupled with diazotized 1-amino-4 : 5-dichlorobenzene-2-sulphonic acid, (4) acetoacetic acid-41-aminoanilide and coupled with diazotized 1-aminobenzene-2-sulphonic acid, and (6) 2-hydroxynaphthalene - 3 - carboxylic acid - (31 - aminophenyl)-amide and coupled with diazotized 2-aminobenzoic acid; in other examples nickel phthalocyanine - 3 - trisulphochloride is reacted with (4) aceto-acetic acid-(21-methoxy-41 - amino - 51 - chlorophenyl) - amide and coupled with diazotized 2-aminobenzoic acid, and (7) 1 - amino - 7 - hydroxy - naphthalene and coupled with diazotized 1-aminobenzene-2 : 5-disulphonic acid; in further examples, (2), nickel phthalocyanine-3-tetrasulphochloride is reacted with 1-(41-aminophenyl0-3-methylpyrazolone-5 and the sulphonamide coupled with diazotized 1-amino-3-carboxy-4-hydroxybenzene-5-sulphonic acid, or a smaller quantity of the pyrazolone is used and the unreacted sulphonyl chloride groups are saponified before the coupling is effected, (5) copper phthalocyanine - 4 - tetrasulphochloride is reacted with 1 - (41 - aminophenyl) - 3 - methyl - pryazolone-5 and coupled with diazotized 1-aminobenzene-2-sulphonic acid, and (8) copper phthalocyanine tetracarboxylic acid chloride obtained by reacting the sodium salt of copper phthalocyanine - 4 - tetracarboxylic acid with PCl2 is reacted with 1-(41-aminophenyl)-3-methyl-pyrazolone-5 and coupled with diazotized 1-aminobenzene - 2 : 5 - disulphonic acid, or a smaller amount of the pyrazolone is used and the unreacted carboxylic acid chloride groups are saponified before the coupling is effected.