Patent GB-520679-A (GB)
Title: The production of resist effects illuminated with vat dyestuffs
IPC: D06P5/12
Filed: 1938-07-29
Abstract: 520,679. Dyeing textiles. MILBURN, D. P., and IMPERIAL CHEMICAL INDUSTRIES, Ltd. July 29, 1938, No. 22689. Addition to 489,235. [Classes 2 (iii) and 15 (ii)] Printing.-Resist effects coloured with vat dyes are obtained upon fabrics made of or containing cellulosic fibres by applying thereto a printing paste containing the vat dyestuff and an isocyanate of the general formula R-X-N =C =O, wherein R is a saturated or unsaturated aliphatic hydrocarbon residue containing at least 12 carbon atoms and X is a substituted or unsubstituted aromatic or hydroaromatic residue or is a substituted or unsubstituted aliphatic, aromatic or hydroaromatic residue linked to R through -O-, -S-, -CO.O-. -O.CO-, -NR<SP>1</SP>-, -NR<SP>1</SP>-CO-, -CO.NR<SP>1</SP>-, -SO 2 -, -NR<SP>1</SP>.SO 2 - or -SO 2 .NR<SP>1</SP>- (R' being a hydrocarbon residue), steaming and applying a dyestuff, e.g. a vat dye (applied, if desired, in the form of a soluble ester of its leuco compound), an azoic dye or a mordant dye, to provide the ground colour. Specified isocyanates are the 4-dodecyl-, 4-cetyl-, 4-dodecyl- 2-methyl- and 4-dodecyl-2- or -3- nitroderivatives of phenyl isocyanate, 4-cetylcyclohexyl isocyanate, the dodecyl and cetyl ethers of 4-hydroxyphenyl isocyanate, the tetradecyl ether of 2-hydroxyphenyl isocyanate, the 4- dodecyl- and 4-cetyl-thio ethers of phenyl isocyanate, #-stearyloxyethyl isocyanate, the dodecyl, cetyl and octodecyl esters of phenyl isocyanate-4-carboxylic acid, 4-stearyloxyphenyl isocyanate, cetyloxyethyl isocyanate, the N- dodecyl- and N-tetradecyl-derivatives of methyl aminoethyl isocyanate, 4-stearomethylamidophenyl isocyanate, 2-octodecylsulphonophenyl isocyanate, 4-cetylsulphonomethylamidophenyl isocyanate and the heptadecylmethylamides of phenyl isocyanate-4-carboxylic and -4-sulphonic acids. The examples correspond to those of the parent Specification with the substitution for the heptadecyl isocyanate used therein of 4-cetylphenyl isocyanate. Isocyanates of the above general formula are obtainable by the action of sodium azide on the corresponding acid chlorides or by treating the appropriate amines, some of which are obtainable as described below, with phosgene (cf. Specifications 462,182 and 483,308). 4-Cetylcyclohexylamine is obtained by hydrogenation under pressure of 4-cetylaniline (cf. Specification 468,226) in presence of a nickel catalyst. 4-Dodecyloxy- and 2-tetradecyloxy-anilines are obtained by reducing the nitro groups in the products of reaction of dodecyl bromide with sodium 4-nitrophenolate and of tetradecyl bromide with sodium 2-nitrophenolate respectively. Cetyl-4-aminophenyl sulphide is obtained by reducing the nitro group in the product of reaction of cetyl bromide with the sodium salt of 4-nitrophenylmercaptan. #-Stearyloxyethylamine, as hydrochloride, is obtained by reaction of stearyl chloride with ethanolamine hydrochloride. 4-Carbocetyloxy- and 4-carbooctodecyloxyanilines are obtained by reducing the nitro groups in the products of reaction of cetyl and octodecyl alcohols respectively with 4-nitrobenzoyl chloride. Cetyloxyethylamine is obtained by heating with ammonia under pressure the sodium salt of the sulphuric ester of cetyloxyethanol, obtained by reaction of the sodium'salt of the sulphuric ester of cetyl alcohol with the monosodium salt of ethylene glycol. N-dodecyl-N-methyl- and N-tetradecyl-N- methyl-ethylenediamines are obtained by reducing the nitriles obtained by the action of formaldehyde and hydrogen cyanide on N- dodecyl - and N - tetradecyl-methylamines respectively. 4-Stearomethylamidoaniline is obtained by reducing the nitroso group in the product of reaction of stearoyl chloride with 4-nitroso-N- methylaniline. 2-Octodecylsulphonoaniline is obtained by reducing the nitro group in the product obtainable by oxidation with hydrogen peroxide in acetic acid solution of the product of reaction of octodecyl bromide with the sodium salt of 2- nitrophenylmercaptan. 4-Cetylsulphonomethylamidoaniline is obtained by reducing the nitroso group in the product of reaction of hexadecanesulphonic acid chloride with 4-nitroso-N-methylaniline. 4 - Amino -  N - methyl - N - heptadecylbenzamide and 4-amino - N - methyl - N - heptadecylbenzene - sulphonamide are obtained by reducing the nitro groups in the products of reaction of methylheptadecylamine with 4-nitrobenzoyl chloride and 4-nitrobenzenesulphonyl chloride respectively.