Patent GB-408492-A (GB)
Title: Manufacture of metalliferous dyestuffs
IPC: C09B45/01
Filed: 1933-07-19
Abstract: Metalliferous dyestuffs by treating a non-sulphonated dye containing groups capable of forming metal-complexes, in an alkaline medium with agents yielding metals capable of forming complex metal compounds by combination with the said groups, wherein the action of the agent yielding metal is caused to proceed in presence of a salt of an aliphatic oxycarboxylic acid. The treatment with agents yielding copper of dyestuffs containing in o-position to an azo group a halogen atom which during such treatment is exchanged for a hydroxyl group, is excluded. Non-sulphonated mono- and polyazo dyes which contain in o-position to an azo linkage at least one substituted or unsubstituted hydroxy group or at least one carboxy group or at least one o-hydroxy-carboxy group, oxyanthraquinones, and triarylmethane, azine and oxazine dyes containing lake-forming groups may be treated; metal compounds include those of chromium, copper, iron, cobalt, nickel, manganese, zinc, vanadium, or titanium; suitable acid salt are the sodium, potassium and ammonium salts of lactic, tartaric, glycollic, tartronic, malic, dioxytartaric, citric, saccharic, gluconic and heptonic acids.  The process is carried out in the open or under pressure and other substances such as salt, sodium acetate or Glauber's salt may be present.  The products are suitable for colouring varnishes and plastic masses which consist of a basis of cellulose or a natural or artificial resin, for example, cellulose lacquers, condensation products of aldehyde with aromatic amines or acid amides, dicyandiamide-aldehyde condensation products, phenol-aldehyde condensation products, polybasic acids--polyhydric alcohols condensation products, vinyl resins, styrene resins.  In examples: (1) the azo dye 5-nitro-2-aminophenol --> b -naphthol is heated in alkaline solution with chromic sulphate and tartaric acid; a solution of the product in cellulose lacquer gives blue-grey coatings; using chromium and cobalt, or iron and cobalt, or aluminium and copper instead, violet dyes are obtained; the p  azo-dye 4-chloro-2-amino-phenol --> b -naphthol on being chromed or treated with chromium and iron in a similar manner, yields blue-violet or brown-violet coatings on solution in a cellulose lacquer; the azo-dye 4-chloro-2-aminophenol --> 2.3-oxynaphthoic acid anilide on chroming as above yields blue-violet coatings on solution in a nitrocellulose or acetylcellulose lacquer; grey-blue coatings are derived from the azo-dye 5-nitro-2-aminophenol --> 2.3-oxynaphthoic acid anilide on chroming as above; (2) the azo-dye 4-nitro-2-aminophenol --> 4-benzoyl-1-oxynaphthalene is heated in alkaline solution with chromic sulphate and tartaric acid to give a product colouring nitro- or acetyl-cellulose lacquers bluish tints; (3) the azo-dye 4-chloro-2-aminophenol --> 1 - phenyl - 3 - methyl - 5 - pyrazolone is treated as in (2) to give a scarlet red colour for nitrocellulose varnish; using a nickel salt a yellow orange dye is obtained; (4) the azo-dye 4-nitro-2-aminophenol --> 1-phenyl - 3 - methyl - 5 - pyrazolone is heated in alkaline solution with chromium fluoride and tartaric acid to give a yellow-orange product; (5) the azo-dye 5-nitro-2-aminophenol --> 1-phenyl-3-methyl-5-pyrazolone is treated as in (2) to give a bluish-red colour for nitro- or acetyl-cellulose lacquers; (6) the azo-dye 4-chloro-2-aminophenol --> 2-4-dioxyquinoline is heated in alkaline solution with chromium hydroxide and tartaric acid; (7) the azo-dye 5-nitro-2-aminophenol --> b -naphthylamine is heated in alkaline solution with cobalt sulphate and tartaric acid to give a greenish-blue colour for nitro- or acetyl-cellulose lacquers; the azo-dye 4-nitro-2-aminophenol --> b -naphthylamine may be similarly treated; (8) the azo-dye 4-chloro-2-aminophenol --> b -naphthol is heated in alkaline solution with chromium and cobalt sulphates and tartaric acid to give a violet colour for cellulose lacquers; the cobaltiferous dye from 4-chloro-2-aminophenol --> b -naphthylamine dyes violet; (9) the azo-dye 4-chloro-2-aminophenol --> 2.4-dioxyquinoline is heated in alkaline solution with chromic sulphate and potassium saccharate to give a brown-red colour; (10) the azo-dye 5-nitro-2-aminophenol --> resorcinol is heated in alkaline solution with ferric chloride and lactic acid to give a blackish-brown colour; (11) the azo-dye 4-nitro-2-aminophenol --> 1-phenyl-3-methyl-5-pyrazolone is heated in alkaline solution with manganese sulphate and citric acid to give a yellow-orange colour. A further example illustrates the colouring of a cellulose varnish.  Specifications 301,772, [Class 2 (iii)], 343,014, and 360,356 also are referred to.