Patent GB-805562-A (GB)
Title: New phthalocyanine compounds
Inventor: CLARK PETER FREDERICK
IPC: C09B62/10
Filed: 1956-03-14
Abstract: The invention comprises phthalocyanines of the formula <FORM:0805562/IV (c)/1> wherein (Pc) is a phthalocyanine radical, Y is a direct link or a divalent bridging radical, the system (Pc)-Y contains at least one solubilizing group, R is hydrogen, alkyl, aralkyl, or cycloalkyl, X is halogen, A is halogen or -O-B-, where B is a hydrocarbon or substituted hydrocarbon radical, and n is a whole number.  They are made by interacting an aminophthalocyanine of the formula (Pc)-(Y-NHR)n with a triazine of the formula <FORM:0805562/IV (c)/2> or, when Y is -SO2- or -CO-, by interacting a phthalocyanine sulphonic or carboxylic acid chloride of the formula (Pc)1-(Y11-Cl)n with an amino-triazine of the formula <FORM:0805562/IV (c)/3> where (Pc)1 is a phthalocyanine radical, Y11 is -SO2- or -CO-, and the system (Pc)1-Y11-contains a solubilizing group.  The aminophthalocyanine compounds used as starting materials, wherein Y is phenylene, -CO-phenylene, -SO2- phenylene, -NH- phenylene, -S- phenylene, -O- phenylene, -CH2S- phenylene, -CH2O- phenylene, -CH2- phenylene, -SCH2- phenylene, and SO2CH2- phenylene are obtained by sulphonation of the corresponding products of Specifications 569,200 and 589,118, [both in Group IV], and these aminophthalocyanines as well as those wherein Y is -NRCO- phenylene, -SO2NR- phenylene, -NRSO2- phenylene, and -SO2O- phenylene may be obtained from sulphonated phthalic acid and appropriately substituted phthalic acids as mentioned in the said Specifications by the usual phthalocyanine-forming reactions.  Those aminophthalocyanines where Y is CH2 may be obtained by sulphonating the amines of Specifications 717,137 and 724,212; those where Y is -CH2NR- phenylene by reacting a primary or secondary nitroaniline with a chlormethyl phthalocyanine containing SO3H or COOH, and reduction, or by reacting a chlormethyl phthalocyanine with a diaminobenzene sulphonic or carboxylic acid, those which contain the -SO2NR- alkylene linkage by reacting a chlorsulphonyl phthalocyanine with a monoacetyl alkylene diamine, followed by hydrolysis; those which contain the -SO2NR- phenylene -CH2- group by condensing a chlorsulphonyl phthalocyanine with an amino-N-benzylacetamide followed by hydrolysis; those containing a -CH2-NR- alkylene link by reacting a chlormethyl phthalocyanine containing a sulpho or carboxy group with a monoacetyl alkylene diamine and hydrolysing; those wherein amino is directly attached to the phthalocyanine nucleus by sulphonation of the aminophthalocyanines of Specification 529,847, [Group IV]; those containing the -CONR-or -SO2NR- phenylene link by reacting a phthalocyanine carboxylic or sulphonic acid chloride with a diaminobenzene sulphonic or carboxylic acid or with an aminobenzene sulphonic acid or aminobenzoic acid which contains a nitro group and reducing; those containing the -CONR- phenylene -CH2-link by reacting a phthalocyanine carboxylic chloride with an N-(aminobenzyl)-acetamide and hydrolysing.  The process of the invention is preferably carried out in aqueous medium in presence of an acid binding agent at a temperature below 30 DEG  C. to avoid hydrolysis of the halogen atoms attached to the triazine rings.  The dyestuffs are preferably isolated at a pH of 6-8, and the pastes are dried at, e.g., 20-40 DEG  C. in presence of buffering agents.  The products are blue to green dyes for, e.g., wool, silk, cotton, linen, regenerated cellulose, nylon, superpolyurethanes.  In examples, cyanuric chloride, as a suspension in a water-acetone mixture, is condensed with: (1) copper phthalocyanine-N-(41-amino-31-sulphophenyl) -sulphonamide sulphonic acid, prepared from copper phthalocyanine tetrasulphochloride and 2,5-diaminobenzene sulphonic acid; (2) copper phthalocyanine - N - (4 - b  - hydroxyethylamino - 3 - sulphophenyl) - sulphonamide - sulphonic acid, prepared similarly; (3) copper phthalocyanine - 4 - N - (31 - amino - 41 - sulphophenyl)-sulphonamide sulphonic acid; (4) copper - (4 - amino) - phthalocyanine sulphonic acid; (5) copper - 4 - p - aminobenzoyl - phthalocyanine-3-sulphonic acid; (6) copper 4-p-aminobenzene sulphonylphthalocyanine; (7) 4-p-aminophenylmercaptophthalocyanine sulphonic acid; (8) nickel phthalocyanine-N-(31\h-amino-41 - sulphophenyl) - sulphonamide - sulphonic acid; (9) copper phthalocyanine - N - [b  - [41 - amino - 21 - sulphophenylamino) - ethyl] - sulphonamide-sulphonic acid; (10) copper phthalocyanine - N - b  - aminoethylsulphonamide - sulphonic acid; (11) copper phthalocyanine - N - sulphonpiperazide - sulphonic acid.  Also in examples, copper phthalocyanine - 4 - N - (31 - amino - 41 - sulphophenyl) - sulphonamide - 4 - sulphonic acid is condensed with cyanuric bromide, 2,4 - dichloro - 6 - methoxy - s - triazine, and 2,4-dichloro-6-phenoxy-8-triazine.  Specification 515,637, [Group IV], also is referred to.