Patent GB-516240-A (GB)
Abstract: 516,240. Dye preparations; printing textiles. SOC. OF CHEMICAL INDUSTRY IN BASLE. June 22, 1938, Nos. 18554 and 18555. Convention dates, June 22, 1937, and May 24, 1938. [Classes 2 (iii) and 15 (ii)] Dyestuff mixtures giving valuable grey to black shades in printing textiles, especially of cotton or regenerated cellulose, comprise a dyestuff of 'the benzanthrone series dyeing blue to violet, an indigoid dyestuff of the general formula wherein R is an o-naphthylene radicle (substituted or not) connected to the S atom in - 1-position and R1 is an o-phenylene radicle (substituted or not) and, if desired, one or more orange, brown or yellow shading vat dyestuffs for standardizing the tone of the black. The benzanthrone dvestuffs mav be of the' dibenzanthrone, isodibenzanthrone or benzanthronepyrazoleanthrone series. The indigoid dyestuffs are obtainable by condensing 1:2-naphthioindoxyl or its 21-carboxylic acid with a reactive 21-derivative of isatin. The. shading dyestuffs may be of the anthraquinonoid series, e.g., flavanthrone, dibenzpyrenequinone, pyranthrone or anthanthrones, or of the indigoid series, e.g., there may be used the condensation product from 1:4:5:8-naphthalenetetracarboxylic acid (1 mol.) and o-phenylenediamine (2 mols.), 2:1:2<1>:1<1>-naphththioindigo or the condensation product of 8-chloro-1:2-naphththioindoxyl with the 2-(p-dimethylaminoanil) of 2:1- naphththioindoxyl. The mixtures may be made by mixing the dyestuff powders and converting the mixture into a paste or by mixing-pastes of the dyestuffs or by adding the individual dyestuffs to the printing paste and the dyestuffs may be present in non-reduced or reduced condition, e.g., as leuco-esters. The powders or pastes may also contain a phenol, e.g., crude cresol, a water-soluble alcohol, e.g., glycerol, glycol or thiodiglycol, a hydrotropic agent, e.g., p-toluenesulphonic acid, cymenesulphonic acid, urea, sulphite cellulose liquor, benzylanilinesulphonic acid, aliphatic or hydroaromatic acids of high molecular weight or salts thereof containing at least 8 carbon atoms with organic bases, wetting or emulsifying agents, reduction catalysts, e.g., alkali-2:6'-anthraquinone-disulphonates, anthraquinone, hydroxyanthraquinones or salts thereof, heavy metal salts, e.g., ferrous sulphate, fillers, e.g., dextrin, starch or sugar, reducing agents, e.g., sodium hydrosulphite, and alkalies, e.g., caustic potash or soda, potassium or sodium carbonate, ammonium or magnesium hydroxide. In examples, (1) a mixture is prepared as an aqueous paste containing, in defined proportions, dibenzanthrone, the dyestuff from 8-chloro-1:2-naphththioindoxyl, and 5-bromisatin-alpha-chloride, 2:1:2<1>:1<1>- naphththioindigo and flavanthrone, and this is stirred with an aqueous thickening comprising wheat starch, tragacanth, British gum, potassium carbonate and glycerol, and additions of hydrosulphite R and sodium benzylsulphanilate; cotton goods are printed with this paste, steamed, washed, soaped and dried to obtain a fast black print ; (2) a mixture in the form 'of an aqueous paste containing in defined proportions dibenzanthrone paste, the dyestuff from 8-chloro-1:2-naphththioindoxyl and 5- bromizatin-alpha-chloride, flavanthrone, 2:1:2<1>:1<1>- naphththioindigo, glycerol, sodium, benzenesulphonate and sulphite cellulose liquor is ground to a homogeneous paste which is concentrated on the water bath, ground and sifted ; the product is used in printing as in (1) ; (3) a mixture in the form of an aqueous paste containing, in different defined proportions, the dyestuffs of (2), dextrin and sodium cymenesulphonate is dried .and ground and used in printing as in (1) ; (4) a mixture in the form of an aqueous paste containing in defined proportions dibenzanthrone, the dyestuffs from 1:2-naphththioindoxyl and isatin-alpha-chloride, flavanthrone, 2:1:2<1>:1<1>-naphththioindigo, glycerol, sodium cymenesulphonate, sodium benzylsulphanilate and sulphite cellulose liquor is concentrated and used in printing as in (1) ; (5) a mixture in the form of an aqueous paste is prepared as in (1) with the use, as second dyestuff, of that from 8-bromo-1:2-naphththioindoxyl and 5-bromisatin-alpha-chloride and containing urea in place of sodium benzylsulphanilate is similarly used in printing ; (6) a mixture in the form of an aqueous paste containing dibenzanthrone, the dyestuff from 8-chloro-1:2- naphththioindoxyl and 5-bromisatin-alpha-chloride, bromdibenzpyrenequinone (cf. Specification 345,650), 2:1:2<1>:1<1>-naphththioindigo, thickening as in (1), hydrosulphite R and urea is similarly used in printing ; (7) and (8) similar mixtures containing pyranthrone and dichloranthanthrone in place of bromdibenzpyrenequinone are similarly used in printing. Specification 260,998, [Class 2 (iii)], also is referred to.