Patent GB-422488-A (GB)
Title: Process of printing textile materials
IPC: D06P3/68
Filed: 1933-07-14
Abstract: Printing.--Pattern effects are produced upon textile materials by printing thereon a paste containing a mixture of a substantive azo component free from sulphonic or carboxylic acid groups, sufficient alkali to dissolve this component, a water-soluble diazoamino compound, a resist to ester salts of leuco vat dyestuffs such as an oxide, hydroxide or carbonate of zinc, an alkaline earth metal or magnesium, and, if desired, a small quantity of a mild reducing agent, thereupon over-printing in a different pattern with a paste containing an ester salt of a leuco vat dyestuff, an oxidizing agent, e.g. sodium chlorate, an oxidation accelerator, e.g. ammonium vanadate, and an agent yielding a non-volatile acid, e.g. diethyl tartrate or an ammonium salt or an easily dissociating metal salt of such an acid, e.g. ammonium thiocyanate, glycollate, oxalate, lactate, citrate or tartrate or a sulphate of magnesium, zinc or aluminium, and thereafter steaming, washing and soaping the materials. Alternatively, an aniline black or like preparation and a resist therefor, such as an oxide, hydroxide or carbonate of zinc or manganese, may be substituted for the ester salt of a leuco vat dyestuff and its resist, respectively, with the substitution, if desired, for the agent yielding a non-volatile acid in the over-printing paste, of a free non-volatile organic acid or a feeble non-volatile inorganic acid, e.g. phosphoric acid.  Further effects are obtainable by printing, in a separate pattern or in admixture with the diazoamino compound preparations, either mixtures of alkali metal salts of aromatic nitrosamines with substantive azo components or preparations containing vat dyes to be developed by the formaldehyde sulphoxylate process.  Specified substantive azo components are naphthols, pyrazolones, arylides of 2 : 3-oxynaphthoic acid or of b -ketocarboxylic acids such as acetoacetic, benzoylacetic or terephthaloyldiacetic acids, e.g. diacetoacetylbenzidine or diacetoacetyltolidine, and arylides of 2 : 3-oxyanthracenecarboxylic acid, o-oxycarbazolecarboxylic acids or o-oxybenzocarbazolecarboxylic acids.  The water-soluble diazoamino compounds may be those of Specifications 320,324 and 329,353, [both in Class 15 (ii)].  The following examples are specified.  (1) White cotton goods are printed with an aqueous paste containing alcohol, caustic soda, starch tragacanth thickening, zinc white, sodium thiosulphate and a dyestuff preparation (cf. Specification 334,529, [Class 15 (ii)]) consisting of a mixture of the sodium salt of the o-toluidide of 2 : 3-oxynaphthoic acid with the diazoamino compound from 5-chloro-2-methyl-1-aminobenzene and 4-sulpho-2-aminobenzoic acid, the goods are dried and over-printed with an aqueous paste containing ethylenethiodiglycol, starch tragacanth thickening, ammonia, glycollic acid, ammonium thiocyanate, sodium chlorate, ammonium vanadate and the sodium salt of the sulphuric acid ester of leuco-5 : 7 : 5<1> : 7<1>-tetrabromindigo and the over-printed goods are dried, steamed for 5 minutes, rinsed and soaped at the boil; the over-printed parts of the first printed pattern are red and the remaining over-printed parts are blue. (2) The goods are printed with aqueous pastes side by side, containing (a) alcohol, caustic soda, starch tragacanth thickening, zinc white, sodium thiocyanate and a mixture (cf. Specification 334,529) of the sodium salt of the 2<1>-toluidide of 2 : 3-oxynaphthoic acid with the diazoamino compound from 3-chloraniline and 4-sulpho-2-aminobenzoic acid; (b) alcohol, caustic soda, starch tragacanth thickening, zinc white, magnesia, sodium thiosulphate and a mixture of the sodium salt of the anilide of 2 : 3-oxynaphthoic acid with the diazoamino compound from 1-amino-2-methoxy-4-benzoylamino - 5 - methylbenzene and sarcosine, the printed goods are dried and over-printed with an aqueous paste similar to the over-printing paste in (1) containing as the dyestuff the sodium salt of the sulphuric acid ester of leucodimethoxydibenzanthrone, and the over-printed goods are steamed for 5 minutes, rinsed and soaped at the boil; the over-printed parts of patterns (a) and (b) are vivid orange and violet respectively and the remaining over-printed parts are green.  (3) The goods are printed with aqueous pastes side by side containing alcohol, caustic soda, starch tragacanth thickening, zinc white, sodium thiosulphate and (a) a mixture (cf. Specification 334,529) of the sodium salt of the 2<1>-phenetidide of 2 : 3-oxynaphthoic acid with the diazoamino compound from 5-chloro-2-methyl-1-aminobenzene and 4-sulpho-2-aminobenzoic acid; (b) a mixture (cf. Specification 328,383, [Class 15 (ii)]) of the potassium salt of the nitrosamine from 5-chloro-2-methoxy-1-aminobenzene, diacetoacetyltolidine, sodium acetate and sodium bicarbonate, the goods are dried and over-printed with an aqueous paste similar to the over-printing paste in (1) containing as the dyestuff the ester salt of leuco-5 : 6 : 7-trichlorothionaphthene-5<1> : 7<1>-dichloroindol-2-indigo and the over-printed goods are steamed for 5 minutes, rinsed and soaped at the boil; the over-printed parts of pattern (a) are red, pattern (b) is yellow throughout, and the remaining over-printed parts are violet.  (4) The goods are printed with aqueous pastes side by side containing (a) alcohol, caustic soda, starch tragacanth thickening, zinc white, sodium thiosulphate and a mixture (cf. Specification 334,529) of the sodium salt of the 2<1>-phenetidide of 2 : 3-oxynaphthoic acid with the diazoamino compound from 5-chloro-2-methyl-1-aminobenzene and 4-sulpho-2-aminobenzoic acid; (b) ethylenethiodiglycol, starch tragacanth thickening, ammonium thiocyanate, sodium thiosulphate and the sodium salt of the sulphuric ester of leuco-dimethoxydibenzanthrone, the goods are dried and over-printed with a mixture containing aniline salt, aniline oil, starch tragacanth thickening, potassium ferrocyanide, sodium chlorate, glycollic acid and water, and the over-printed goods are dried, steamed, treated with a potassium bichromate-sodium carbonate solution, rinsed and soaped at the boil; the over-printed parts of patterns (a) and (b) are scarlet and green respectively and aniline-black is developed on the remaining over-printed parts.  (5) The goods are printed with an aqueous paste containing alcohol, caustic soda, starch tragacanth thickening, zinc white, sodium thiosulphate, a mixture of the sodium salt of the 4<1>-methoxy-2<1>-methylanilide of 2 : 3-oxynaphthoic acid with the sodium salt of the nitrosamine from 4-chloro-2-methyl-1-aminobenzene and a mixture of the sodium salt of the same arylide of 2 : 3-oxynaphthoic acid with the diazoamino compound from 4-chloro-2-methyl-1-aminobenzene and 4-sulpho-2-aminobenzoic acid, the printed goods are dried, over-printed as in (1), steamed, rinsed and soaped at the boil; the over-printed parts of the first pattern are dark red, the whole of the first pattern shows a pink shade due to development of the nitrosamine colour, and the remaining over-printed parts are blue.  The Specification as open to inspection under Sect. 91 comprises also the over-printing of an aniline-black mixture upon a pattern printed with a preparation containing an ester salt of a leuco vat dyestuff, ammonium thiocyanate and, if required, a small quantity of a reducing agent.  On steaming, the vat dyestuff is developed in the over-printed parts of the pattern.  This subject-matter does not appear in the Specification as accepted.