Patent GB-561054-A (GB)
Title: Metallized azo pigments
Filed: 1942-07-29
Abstract: Metallized azo dye pigments are obtained by the reaction, in an aqueous or aqueous-alcoholic medium, of a water-soluble salt of a divalent metal of atomic weight between 50 and 66 with an azo dye obtainable by coupling a diazotised arylamine, devoid of any hydroxy or ether group in o-position to the diazotised amino group and devoid of sulphonic and carboxylic acid groups, with a 4-hydroxy-2-pyridone compound as defined below, 1 atom of the metal entering into reaction per 2 mols. of the pyridone radicle. The metal salt may be present during the coupling or may be added thereafter.  The 4-hydroxy-2-pyridone compounds used are defined as 4-hydroxy-2-pyridone itself and its N-phenyl, N-cyclohexyl and N-alkyl (C1 to C8) derivatives, their substitution products carrying alkyl (C1 or C2), halogen or nitro groups in 5- or 6-positions or with 5- and 6-substituents together forming an isocyclic ring, which may be substituted by halogen, methyl, methoxy, ethoxy or nitro groups or which may be in the form of a benzo derivative.  Specified coupling components, in addition to 4-hydroxy-2-pyridone and its N-phenyl derivative as above, are 4 : 6-dihydroxypicoline, 4 - hydroxy - 2 - quinoline and its N-methyl, N-butyl, 7-chloro, 6-bromo, 7-nitro, 6-methyl, 7-methoxy, 7-ethoxy and 5 : 6- and 7 : 8-benzo derivatives. Specified diazo and tetrazo components are p-aminobenzonitrile, p - aminoacetophenone, p - aminobenzophenone, p-aminobenzanilide, sulphanilamide, a - and b  - naphthylamine, 4 - nitro - 1 - aminonaphthalene, aminoazobenzene, aminoazotoluene, benzidine, 2 : 21-dichlorobenzidine, 2 - nitrobenzidine, 3 - nitro - 4 - chloroaniline, 2 - chloro - 4 - aminophenetole, thioaniline, 4 : 41-diaminobenzophenone, benzidine sulphone, 4 : 41-diaminodiphenylamine, b -aminoanthraquinone, 2 - amino - 5 - methyl - thiazole, 2-aminobenzothiazole and its 6-ethoxy derivative, 5- and 6 - aminoquinolines, 1 - phenyl - 3 - methyl - 4 - amino - 5 - chloropyrazole, toluidines, xylidines, m- and p-anisidines and phenetidines and their chloro derivatives, chloroanilines, bromoanilines, 4 - chloro - 2 - aminotoluene, nitrotoluidines, e.g. 2-nitro-4-aminotoluene, nitro - m - and p - anisidines, e.g. 2 - nitro - 4 - aminoanisole, 4 - aminophenyl - methyl sulphone, 3 - aminophenyl - ethyl sulphone, p  4-aminodiphenyl sulphone, m- and p - aminoacetanilides, 2 -, 3 - and 4 - aminodiphenyls, 3- and 4-aminodiphenyl ethers, m- and p-aminophenylureas, o-, m- and p - aminophenyl - sulphondimethylamides, o-, m- and p-aminobenzamides, p-aminoacetanilide or p - anisidine --> m - toluidine, o-anisidine --> a -naphthylamine, aniline --> m - anisidine or m - aminoacetanilide, 3-amino-2 : 5-diphenylpyrrole, 2 - methyl - 3 - aminoindole, 4-amino-1 : 3 : 5-trimethylpyrazole, 3 - aminoindazole, Bz - 4 - aminoantipyrine, 5-amino-1 : 2 : 4-triazole, 1-phenyl-5-aminotriazole, 5 - aminotetrazole, 3 - aminopyridine, 2 - chloro - 5 - aminopyridine, 3 - amino - quinoline and its 2-methyl derivative.  Specified metals are chromium, manganese, iron, nickel, cobalt, copper and zinc. Examples relate to the production of (1) the nickel compound of aniline --> 2 : 4 - dihydroxyquinoline by (a) heating with an aqueous ammoniacal nickel acetate solution, (b) heating with nickel hexammine chloride in neutral solution, (c) heating with nickel chloride in sodium acetate solution, (d) effecting the coupling in presence of nickel chloride or nickel hexammine chloride; the products are suitable for use in lacquer emulsion and other printing preparations for textiles; (2) the nickel compound of m-nitroaniline --> 2 : 4-dihydroxyquinoline; (3), (4) and (5), the nickel, cobalt and copper compounds respectively of p-nitroaniline --> 2 : 4-dihydroxyquinoline; (6) the nickel and cobalt compounds of p-aminobenzonitrile --> 2 : 4-dihydroxyquinoline; (7) the nickel compound of p-nitroaniline --> 2 : 4-dihydroxy-5 : 6-benzoquinoline; (8) the nickel compound of p - nitroaniline --> 4 - hydroxy - N - methyl - or N-phenyl-2-quinolone; (9) and (10), the nickel compounds of p - chloroaniline --> (9) 2 : 4-dihydroxyquinoline, (10) 6 - bromo - 2 : 4-dihydroxyquinoline, (11) the copper compound of benzidene \sQ 2 : 4-dihydroxyquinoline (2 mols.) by heating with copper sulphate solution buffered with ammonia, mono-, di- or tri-ethanolamine, mono-, di-, or tri-ethylamine, pyridine, urea or sodium acetate.  A table is also given showing (Examples (12) to (34)) the shades of the lacquer emulsion prints obtainable on cotton with the pigments from various metal compounds of the products of coupling of 2 : 4-dihydroxyquinoline with various diazo components.  Example (35) relates to the production of the nickel compound of aniline --> 2 : 4-dihydroxyquinoline by heating with nickel chloride solution buffered with diethanolamine (5 mols.) and a table is given showing (Examples (36) to (56)) the properties of inks prepared from pigments comprising this nickel compound prepared with the use of various molecular proportions of various buffering agents, viz. mono-, di-and tri-ethanolamines, di- and tri-ethylamines, diethylaminoethanol, ethylenediamine, tri-ethylenetetramine, glycine, methylglucamine, aniline, dimethylaniline, N - phenylethanolamine, benzylamine, pyridine, quinoline, piperidine, morpholine, urea, disodium phosphate and tetramethylammonium hydroxide.  Further examples relate to the production of (57) the nickel compound of aniline --> 2 : 4-dihydroxyquinoline by heating in aqueous alcoholic solution with nickel chloride in presence of sodium acetate, ammonia or diethanolamine, (58) the nickel compound of p-nitroaniline --> 2 : 4-dihydroxyquinoline by heating in aqueous solution with nickel chloride in presence of pyridine.  Specification 465,167 is referred to.  The Specification as open to inspection under Sect. 91 (4) (a) comprises also (a) the use, as coupling components of 2 : 4-dihydroxypyridine-5-carboxylic acid amide, N-methyl-4-hydroxy-6-methyl-2-pyridone, the N-octyl, N-cyclohexyl and N-(41-methylcyclohexyl) derivatives of 4-hydroxy-2-quinolone, and 2 : 4-dihydroxy-5 : 6 : 7 : 8-tetrahydroquinoline, (b) the use as diazo and tetrazo components of dianisidine, p - aminoacetanilide --> cresidine or 2 : 5-dimethoxyaniline, p - anisidine --> 2 : 5-dimethoxyaniline, a -aminotetronic acid, 2-phenyl-4 : 5-diaminotriazole and 1-methyl-2-phenyl-3-aminoindole, (c) examples of the production of the copper compound of 5-nitro-2-aminoanisole --> 2 : 4-dihydroxyquinoline, the nickel compound of p - nitroaniline --> 2 : 4-dihydroxy-5 : 6-dihydropyrindene, (d) references to the nickel and cobalt compounds of 4-nitroaniline --> cresidine.  This subject-matter does not appear in the Specification as accepted.