Patent GB-791359-A (GB)
Title: Manufacture of phthalocyanine pigments and their use
IPC: C09B43/00
Filed: 1956-01-30
Abstract: The invention comprises phthalocyanine pigment dyes of the formula <FORM:0791359/IV (b)/1> wherein A represents a phenylene, naphthylene, or 1,2,3-triazolophenylene radical which is bound at two neighbouring C atoms and which can be still further substituted except by sulpho groups and M is a co-ordinated heavy metal atom, e.g. copper.  They are made by (a) heating unsulphonated o-aminoazo dyes of the formula <FORM:0791359/IV (b)/2> wherein X1 or X2 and Y each represent a carboxyl group or a salt, anhydride, ester, amide, imide, or nitrile thereof, and the other X represents hydrogen, and wherein A represents a phenylene, naphthylene, or 1,2,3-triazolophenylene radical which is bound at two neighbouring carbon atoms to the N atoms and which may possibly be still further substituted, the heating being performed at a temperature of 120-220 DEG  C. in the presence of oxidizing agents effecting the triazole formation (e.g. aromatic nitro compounds) possibly in presence of ammonia and/or agents giving off heavy metal as well as of the additives which further the phthalocyanine formation, or (b) by heating an unsulphonated 2 - phenyl - 11,21 : 4,5 - benzo - 1,2,3-triazole compound of the formula <FORM:0791359/IV (b)/3> in presence of an amount of 10-100 per cent of the triazole compound of aliphatic sulphonic acids, aromatic carboxylic or sulphonic acids or the salts, amides, or imides thereof and/or sulphuric acid or its salts, and in presence of high-boiling organic solvents as well as possibly ammonia and/or agents giving off heavy metal and in presence of catalysts furthering the phthalocyanine formation.  The aminoazo dyes used as starting materials are made from diazotized 3- or 4-aminophthalic acids or their derivatives and azo components such as 1-amino-3-methoxy or ethoxy-4-methylbenzene, 1-amino-3 - methoxy - or ethoxy - 4 - chlorobenzene, 2-aminonaphthalene or its 1-sulphonic acid, 2-aminonaphthalene-6-sulphonic acid dimethyl-, diethyl-, or N-ethylphenyl amide, 1-amino-5,8-dichloronaphthalene, 2 - amino - 6 - methyl sulphonyl naphthalene, 5 - aminobenztriazole, 5-amino - 2 - phenyl - benztriazole, 5 - amino - 2 - naphthyl - (11) - benztriazole, 5 - amino - 6 - methyl, 6-methoxy, or 6-chloro-2-phenyl benztriazole.  Additives favouring phthalocyanine formation are ammonium molybdate, iron, aluminium, titanium, and zirconium chlorides and oxychlorides, arsenic oxides, ammonium vanadates, alkyl or aryl carboxylic or sulphonic acids and derivatives thereof, or sulphuric acid, and cobalt, nickel, zinc, or aluminium compounds may be used to provide metal.  In examples, the following materials are converted to phthalocyanines by heating with urea, cupric chloride, and customary additives: (1) 3,4-dicarboxybenzene - azo - 21 - aminonaphthalene, or 4 - [21 - (naphtho - 111,211 : 41 : 51) - 11 : 21 : 31-triazolyl] - benzene - 1,2 - dicarboxylic anhydride derived therefrom by oxidation, (2) 3,4-dicarboxybenzene - azo - 21 - amino - 41 - methoxy-51-methylbenzene, (3) 2,3 - dicarboxybenzene-azo-21 - aminonaphthalene, (4) 3,4 - dicarboxybenzene - azo - 51 - aminobenztriazole, (5) 4 - [51-aminobenztriazolyl - (21)] - benzene - 1,2 - dicar - boxylic acid.  Other starting materials are referred to. The products are used to colour lacquers, varnishes, synthetic materials and printing pastes for textiles.ALSO:Polyvinyl chloride and urea-alkyd resins are coloured with phthalocyanines of the formula: <FORM:0791359/IV (a)/1> where A is a phenylene, naphthylene, or 1,2,3-triazolophenylene radical bound at two neighbouring carbon atoms to the N atoms of the triazole ring and which is free from sulpho groups, and M is a co-ordinated heavy metal atom such as copper, cobalt, nickel or zinc.  In examples: (1) a modified urea-alkyd resin as a 60 per cent solution in xylene/butanol 1:1 is mixed with turpentine, xylene, titanium dioxide, and a pigment as above where A is 1.2-naphthylene and M is copper, and the mixture poured on to aluminium sheets and stoved; (2) polyvinyl chloride is mixed on hot rolls with dioctyl phthalate, dibutyl tin dilaurate, titanium dioxide, and a pigment as above where M is copper and A is 4-methoxy-5-methylphenylene.