Patent GB-455320-A (GB)
Title: Manufacture of coloured masses
IPC: C08K5/00
Filed: 1935-08-12
Abstract: Coloured masses from cellulose derivatives, e.g. nitro-, acetyl-, ethyl- or benzylcellulose or other cellulose esters or ethers, natural or artificial resins, e.g. copal, amber, shellac or colophony, condensation products of aldehydes with phenols, aromatic amines, e.g. aniline, or acid amides, e.g. urea, thiourea, or their derivatives, or arylsulphonamides, or of polyhydric alcohols with polybasic acids, e.g. glycerol and phthalic acid, or polymerization products, e.g. vinyl, styrene or acrylic acid resins, waxes, e.g. carnauba wax or ozokerite, natural polymerization products, e.g. caoutchouc, balata or guttapercha, or casein, or solutions thereof, e.g. in water, alcohols, glycols, ketones, e.g. acetone, hydrocarbons, e.g. benzene or toluene, ethers, ether alcohols, e.g. glycol alkyl ethers, esters, e.g. butyl acetate, drying or hardening oils, or mixtures of solvents, are manufactured by incorporating in the mass to be coloured a complex metal compound of an arylmethane dyestuff which is sparingly soluble or insoluble in lacquer solvents and has been prepared by the action of an agent yielding a metal of atomic weight between 48 and 66, in an acid or neutral medium, on an arylmethane dyestuff containing a group capable of binding such metal in complex union.  Suitable dyestuffs are those of the diphenyl-, dinaphthyl-, triphenyl- or trinaphthylmethane series containing one, two or more metal complex-forming groups, i.e. hydroxy groups in o-position to a carboxylic group, e.g. the products obtained by oxidation of the condensation product from 1 mol. of an aromatic aldehyde (which may contain as substituents nitro, alkyl, sulphonic or alkoxy groups or halogen, e.g. chlorine or bromine) with 2 mols. of an aromatic o-oxycarboxylic acid, e.g. 2-oxybenzene-1-carboxylic acid or its 3-methyl derivative, or by the action of formaldehyde and an oxidizing agent on o-oxybenzoic acids, or by condensing 1 mol. of a benzotrichloride with 2 mols. of an o-oxynaphthoic acid, or by the action of carbon tetrachloride on o-oxyarylcarboxylic acids in alkaline solution in the presence of copper.  The metal compounds are made by treating the dyestuffs, singly or in admixture, with an agent yielding metal, in acid or neutral medium, in an open vessel or under pressure, and in presence of absence of additions, e.g. salts of organic or inorganic acids or free acids, e.g. sodium formate, benzenesulphonic acid, naphthalenesulphonic acids, sodium acetate, common salt, Glauber's salt, formic, acetic or tartaric acid.  The metal compound of the dyestuff may be incorporated in the mass by, for example, mixing a solution of the mass with the metal compound, e.g. by grinding, or by treating the solid mass with the dyestuff by rollers or kneading devices. There may be added suitable substances such as higher fatty acids, fillers, e.g. barium sulphate, zinc oxide or titanium dioxide, softening agents or plasticizers, e.g. triphenyl or tricresyl phosphate, glycerol or castor oil.  In examples: (1) the nickel compound of Naphthochrome Azurine B is incorporated in an oil varnish containing copal; (2) the vanadium compound of Naphthochrome Azurine B (prepared by boiling the dye in water with ammonium vanadate) is incorporated in a spirit lacquer; (3) the copper compound of Naphthochrome Azurine B is incorporated in an acetylcellulose lacquer, together with a further quantity of acetylcellulose, titanium oxide and a diluent, yielding a plastic mass from which pressed objects may be made; (4) the copper compound of Eriochrome Azurol B (prepared by boiling the dye in water with copper sulphate) is added to a moulding powder containing a phenol-formaldehyde condensation product, together with titanium oxide; (5) the cobalt compound of Naphthochrome Azurine B is mixed with a moulding powder from a ureaformaldehyde condensation product and lithopone; (6) the copper compound of Naphthochrome Azurine B is rubbed with glycerol and mixed with a mass ready for casting consisting of phenol-formaldehyde and glycerol-phthalic acid condensation products, which is then hardened; (7) the dyestuff of (6) is mixed with a moulding powder from an aniline-formaldehyde condensation product.  The following additional dyestuffs are specified: the nickel, zinc, cobalt, copper and chromium compounds of the condensation product of 1 mol. of p-dimethylaminobenzaldehyde and 2 mols. of 3-methyl-2-oxybenzoic acid (prepared by boiling the dye in water with nickel sulphate or an agent yielding zinc, cobalt, copper or chromium), the zinc, nickel, cobalt and chromium compounds of Eriochrome Azurol B, the iron, manganese, zinc, chromium and tungsten compounds of Naphthochrome Azurine B, and the chromium, copper, cobalt and iron compounds of Naphthochrome Green G. Titanium compounds are also referred to.  The Specification as open to inspection under Sect. 91 comprises the use of metal complex compounds of arylmethane dyestuffs in general, including aluminium compounds and compounds prepared in alkaline medium.  In additional examples: (1) the aluminium compound of Naphthochrome Green G (prepared by boiling the dye in water with aluminium sulphate) or of Naphthochrome Azurine B is ground with tricresyl phosphate and butyl acetate and the mixture is incorporated in a nitrocellulose lacquer; (2) the aluminium compound of Eriochrome Azurol B is incorporated in a lacquer containing a phenol-formaldehyde condensation product; (3) the same dyestuff is incorporated in a moulding powder from a urea - formaldehyde condensation product.  Reference is made to the aluminium compound of the condensation product from p-dimethylaminobenzaldehyde and 3-methyl-2-oxybenzoic acid, the cobalt compound of Naphthochrome Azurine B prepared by heating the dye in water with cobalt sulphate with the addition of tartaric acid and caustic soda, and the nickel compound of Naphthochrome Green G prepared by boiling the dye with a solution, alkaline to phenolphthalein, of nickel sulphate, tartaric acid and caustic soda. This subject-matter does not appear in the Specification as accepted.ALSO:Coloured masses from natural polymerization products such as caoutchouc, balata or guttapercha, or solutions thereof, are manufactured by incorporating in the mass to be coloured a complex metal compound of an arylmethane dyestuff which is sparingly soluble or insoluble in lacquer solvents and has been prepared by the action of an agent yielding a metal of atomic weight between 48 and 66, in an acid or neutral medium, or an arylmethane dyestuff containing a group capable of binding such metal in complex union.  Chromium, iron, cobalt, nickel, manganese, zinc, copper, tungsten, vanadium and titanium compounds are specified.  The Specification as open to inspection under Sect. 91 comprises the use of metal complex compounds of arylmethane dyestuffs in general, including aluminium compounds and compounds prepared in alkaline medium.  This subject-matter does not appear in the Specification as accepted.