Patent GB-489645-A (GB)
Title: Process for pigmenting or dyeing fibrous or film-like materials produced from highly polymeric organic bodies
IPC: D06P1/44
Filed: 1936-10-24
Abstract: White or coloured pigmenting of artificial fibrous or film-like materials made from hydrophobic, organophilic highly polymerized products, containing salt-forming groups bound to polymeric components of high molecular weight, is effected by producing on or in the material a white or coloured insoluble precipitate of a metal or a purely inorganic metal compound or a compound of a metal with an organic substance other than a dyestuff.  Specified polymeric components of high molecular weight are (a) polymerizates from unsaturated carboxylic acids and interpolymerizates therefrom with vinyl and like unsaturated compounds, (b) the mono-esters, soluble in organic solvents, of di- and poly-carboxylic acids with polyhydroxy compounds such as methyl-, ethyl- or acetyl-cellulose still containing hydroxyl groups or partially acetalated vinyl alcohol (cf. Specification 459,711), (c) polyvinyl resins containing basic groups, e.g. polyacrylic acid-o -diethylaminoethylamide, (d) basic derivatives of polyglycide, (e) basic cellulose derivatives, e.g. diethylaminoethylcellulose or its esters or ethers (cf. Specifications 455,602 and 472,630).  The acid and/or basic salt-forming groups may be produced in the materials, e.g. by hydrolysis, alkylation, amination or oxidation.  The pigmenting reaction may be, for example, (a) the reaction of a heavy metal such as mercury, silver, lead, copper, cadmium, iron, cobalt, nickel or uranium, combined with an acid group in the material, with hydrogen or ammonium sulphide, sodium or magnesium hydrosulphide or a substance readily yielding sulphur, e.g. thiourea or sodium hyposulphite, (b) the reaction of a heavy metal, such as zinc, copper or iron, combined in the material, with a ferro- or ferri-cyanide, (c) the formation of lead or barium chromate in the material, (d) the reaction of a heavy metal, combined with an acid group in the material, with an organic compound, not a dyestuff, such as inter alia a b -dicarbonyl compound, an oximinoketone, an a -dioxime, an amidooxime, a hydroxyamidooxime, a polyhydric phenol, a hydroxyquinoline, a nitrosoarylhydroxylamine or an arylide of thioglycollic acid, specified compounds, additional to those referred to in the examples below, being anisoylbenzoylmethane, oxymethylenecamphor, the diimine from ethylenediamine (1 mol.) and acetylacetone (2 mols.), isonitrosoacetoacetic acid anisidide, the isonitroso compound of acetoneoxalic acid ester anil, isonitrosoacetophenone, a -benzildioxime, benzamidoxime, oxalic acid diamidooxime, phenylglyoxalbenzoin, pyrocatechol, 8-oxyquinoline, tannin, m-dimethylamino nitrosophenylhydroxylamine, a  - picolinic acid, quinaldic acid, quinoxaline-2 : 3-dicarboxylic acid and dicyandiamidine, (e) precipitation of a metal, e.g. silver, by reduction of a metal compound in or on the material.  The absorption of the components may be assisted by a swelling agent, e.g. acetone, alcohol, acetic acid, phenol, a thiocyanate, urea, thiourea or pyridine and leaching out of the components may be prevented by the addition of a substance diminishing the solubility, e.g. in the case of components with acid groups, calcium or zinc salts, high molecular amines or ammonium salts, such as dodecylamine hydrochloride, dodecyltrimethylammonium chloride or octodecylamine acetate, or, in the case of components with basic groups, alkylnaphthalenesulphonic, sulphosalicylic and trichloracetic acids and their salts.  The components may be applied in the spinning machine or in the precipitating bath or to the finished fibres, films, &c. and various applications of the invention in direct, discharge and resist printing are described.  In examples, (1) to (7) an acetate artificial silk fabric in which strips of the warp contain the interpolymerizate from vinyl methyl ether (1 mol.) and maleic anhydride (1 mol.) is treated with a solution of copper acetate, rinsed and immersed in a solution of (1) ammonium sulphide to obtain a brown to greenish black; (2) dimethylglyoxime to obtain an apple green; (3) potassium ferrocyanide to obtain a brown-red; (4) anthranilic acid to obtain a green; (5) salicylic acid to obtain a blue-green; (6) nitrosophenylhydroxylamine to obtain a stone green; (7) 4-nitrobenzhydroxamic acid to obtain a grass green on the said warp strips; (8) a similar fabric is treated successively with a solution of ferrous ammonium sulphate in presence of oleylpolyglycol and a solution of potassium ferricyanide to obtain a brilliant greenish blue or successively with a solution of ferric nitrate and a solution of potassium ferrocyanide to obtain a dull blue-green on the warp strips; (9) an acetate artificial silk fabric containing the interpolymerizate from vinyl ethyl ether (1 mol.) and maleic anhydride (1 mol.) is treated successively with solutions of ferric chloride and 4-nitrobenzhydroxamic acid to obtain a rust brown; (10) a similar fabric which has been treated with a solution of ferrous ammonium sulphate in presence of oleylpolyglycol and developed with a -nitroso-b -naphthol is treated successively with solutions of copper acetate and ammonium sulphide to obtain a field grey; (11) an acetate artificial silk fabric having warp strips as in (1) and other warp strips containing polyvinyl chloracetate is treated successively with solutions of cadmium acetate and ammonium sulphide to obtain a yellow on the first warp strips, then treated with pyridine vapour (cf. Specification 455,849) and dyed with Indigosol green IB to obtain a green on the second warp strips; (12) a mixed fabric of acetate artificial silk and the same containing the interpolymerizate from vinyl formate (1 mol.) and maleic anhydride (1 mol.) is dyed with Celliton yellow 5G and thereafter treated successively with copper acetate and ammonium sulphide to obtain a yellow and black effect; (13) a fabric as in (1) is dyed with Cellitazol R, treated with a solution containing copper and sodium acetates and developed with ammonium sulphide to a black on the warp strips and the dyeing is then diazotized and developed with phenol to a reddish yellow ground; (14) an acetate artificial silk skein containing the interpolymerizate of (12) is treated successively with cobalt acetate and ammonium sulphide and after-treated with a solution containing dodecylamine acetate and octodecyltrimethylammonium chloride to obtain a deep black; (15) an acetate artificial silk skein containing the interpolymerizate of (1) and treated successively with tetra-(g -chloro-b -hydroxypropyl)ammonium acetate and ethylene imine is treated with copper acetate and developed with ammonium sulphide to a black and, if desired, dyed or printed deep shades with acid dyes; (16) an acetate artificial silk fabric containing the interpolymerizate of (1) is treated successively with cobalt acetate and diphenylthiocarbazone to obtain a brownish violet; (17) an acetate artificial silk fabric containing warp strips mordanted with cobalt acetate and containing the interpolymerizate of (1) and other similar, but unmordanted, strips is treated with ammonium sulphide to develop a black on the first warp strips, then mordanted with nickel acetate and treated with dimethylglyoxime to obtain a red on the second warp strips and after-treated with a solution of quaternary ammonium bromides derived from trimethylamine and the product of the action of hydrogen bromide on the reduction products of palm nut oil fatty acids; (18) an acetate artificial silk fabric containing the interpolymerizate of (1) is grounded with silver acetate, preferably in presence of a desensitizer such as Tartrazine O, and treated with sodium phosphate to develop a violet brown or with hydrogen sulphide to a brown or exposed to light, under a negative or otherwise, to obtain a brownish silver which can be toned reddish with sodium selenosulphate, a sensitizer such as Rhodamine B being advantageously used; (19) to (23) a mixed fabric having a woven pattern in part of acetate artificial silk and in part of the same containing the interpolymerizate of (12) is treated successively with solutions of (19) zinc acetate and potassium ferrocyanide to obtain a matt effect on the part containing the interpolymerizate, whereupon the whole may be top-dyed with a basic dyestuff; (20) barium acetate and sodium bisulphite to obtain, on oxidation in the air, a barium sulphate matt effect; (21) barium acetate and sodium bichromate to obtain a yellow; (22) lead acetate and potassium bichromate to obtain a yellow; (23) lead acetate and potassium iodide to obtain a reddish gold-yellow; (24) an acetate artificial silk fabric containing polyvinyl chloracetate and the interpolymerizate of (1) is aminated with pyridine, dyed with Indigosol green IB, developed with chromic acid, and treated simultaneously or subsequently with lead acetate to obtain a yellow-green; (25) an acetate artificial silk warp containing the interpolymerizate of (1) is impregnated with a size containing gelatine, urea, oleic acid diethanolamide and an ammoniacal copper solution and, after working up, is desized in a soap bath containing ammonium sulphide to obtain a greenish black; (26) an acetate artificial silk fabric containing polyvinyl chloracetate and the interpolymerizate of (12) is treated successively with pyridine, barium thiocyanate, urea and hydrogen peroxide to produce barium sulphate in the fibre; (27) fabric as in (16) is treated successively with zinc acetate or zinc and cadmium acetates and with sodium hyposulphite to obtain a pigmented matt effect; (28) an acetate artificial silk fabric as in (1) is treated successively with manganese acetate and potassium permanganate to obtain a lustrous brown on the warp strips; (29) an acetate artificial silk fabric containing polyvinyl chloracetate is aminated with pyridine and treated successively with sodium sulphate and potassium permanganate to obtain a brown dischargeable to white with