Patent GB-492743-A (GB)
Title: Process for increasing the affinity for dyestuffs of articles of cellulose, cellulose derivatives or polymers soluble in organic solvents
IPC: D06M11/13
Filed: 1937-01-21
Abstract: The affinity for dyestuffs of articles such as threads, yarns, fabrics or films, made from cellulose, cellulose derivatives, or polymers, (e.g. polystyrol or polyvinyl chloride) soluble in organic solvents is increased by incorporating in substance therein a reaction product of a sulphonic acid ester of a carbohydrate or carbohydrate derivative with ammonia, an amine or urea, thiourea or a substitution product thereof, which reaction product still contains sulphonic acid ester groups. Such products may be incorporated by admixture into the solutions or plastic masses from which the articles are made or by treatment of the finished articles. In the latter case the product may be applied in a solvent or emulsifying agent having a swelling action on the material treated. Specified sulphonic acid ester components are the benzene, toluene, ethane and other sulphonic acid esters of sugars, mannite, starch, cellulose and alkyl-and hydroxyalkyl-celluloses. Specified amines are isopropylamine, isobutylamine, hexylamine, isohexylamine, cyclohexylamine, diethanolamine, ethylenediamine, benzylamine, pyridine, piperidine and morpholine.  For admixture into solutions or plastic masses of cellulose the reaction products may, in the case of viscose be dissolved in a solvent such as isobutylamine or benzylamine with or without an emulsifying agent and, in the case of cuprammonium cellulose, be emulsified in aqueous ammonia. Specified solvents for use in treatment of the finished articles, especially of cellulose derivatives, are glacial acetic acid, glycol monoacetate, butylamine, benzylamine and pyridine.  The fixation of the reaction products on the articles may be improved by an after-treatment with a solution of an electrolyte such as sodium chloride and/or by adding salts of amines, thiocyanates, thiosulphates, or mordants to the impregnating and/or the after-treatment baths.  In examples: (1) a solution of p-toluenesulphonic acid chloride in ethylene dichloride is added to a solution of glucose triacetate in acetic acid, ethylene dichloride and pyridine and after 5-6 hours at 30-40 DEG  C. the ethylene dichloride is distilled off and the mass poured into water, washed with water and methyl alcohol, dried and heated with benzyl amine for 1 hour at 80 DEG  C.; the product is precipitated with water, washed and mixed with a solution of cellulose triacetate in glacial acetic acid; articles precipitated from this solution are intensively dyed by acid wool dyestuffs such as Acid anthracene red 3BL or Alizarin cyanin green 5G; (2) benzenesulphonic acid chloride, emulsified in water with a condensation product from oleyl alcohol and ethylene oxide, is mixed into a solution of soluble starch in dilute caustic soda and after 8-12 hours at 30-40 DEG  C. with addition of caustic soda solution at intervals, the product is filtered off, washed, dried and heated with pyridine for 2 hours at 80-90 DEG  C.; after distilling off the excess of pyridine the product is precipitated with water, dried and dissolved in acetic acid with an addition of chromium acetate; acetate artificial silk yarns or fabrics are impregnated for 20-30 minutes with this solution at 40-50 DEG  C. and are then passed through a solution at 80-90 DEG C. of sodium chloride or acetate, rinsed and dried; the products may be dyed, fast to alkaline fulling, with Alizarin cyanin green 5G, Acid anthracene brown W or Chromoxan pure blue B; (3) cellulose triacetate yarn is impregnated for 20-30 minutes with a solution in aqueous pyridine or glycol monoacetate at 70-80 DEG  C. of the product of (2) from the benzenesulphonic acid ester of starch and pyridine, and further treated as in (3); (4) cellulose triacetate yarn is impregnated as in (2) with a solution of a product obtained by reacting the benzene-sulphonic acid ester of starch with benzylamine for 1 hour at 70-80 DEG  C.; the treated yarn may be dyed with acid dyes as in (2) and its affinity is increased for direct dyes such as Benzo fast red L, cellulose acetate dyestuffs and grounding components used in ice-colour dyeings; thus it may be dyed with Cellit fast blue A or may be grounded with Fast blue BB base in an aqueous soap solution at 70-80 DEG  C., diazotized and developed with Naphthol ASD; the treated yarn may be bleached with chlorine or hydrogen peroxide or carbonized with hydrochloric acid solution at 100 DEG  C. prior to dyeing; (5) acetate artificial silk is impregnated as in (2) with a solution of a product obtained by reacting the benzene sulphonic acid ester of starch for 2 hours on the water bath with a mixture of diethanolamine and pyridine, benzylamine and pyridine, isobutylamine and pyridine, benzylamine and diethanolamine or pyridine and urea etc.; (6) cuprammonium artificial silk is impregnated and further treated as in (3) to impart affinity for acid dyes and increased affinity for direct dyes; (7) a cotton fabric is printed with a paste containing a solution in glacial acetic acid of the reaction product of (2) from the benzenesulphonic acid ester of starch and pyridine, dried, washed and dyed with an acid wool dyestuff having no affinity for cotton to obtain a pattern effect; (8) cellulose artificial silk yarn, impregnated as in (2), is dyed with Acid anthracene brown KE and after-treated with potassium bichromate solution; (9) an emulsion or a solution in pyridine or ethylenediamine of a reaction product from a benzenesulphonic acid ester of methylcellulose and pyridine is added to a cuprammonium cellulose solution from which is then formed a film having affinity for acid wool dyestuffs: (10) an emulsion or solution in aqueous benzylamine of a reaction product from a benzenesulphonic acid ester of starch as in (2) and a mixture of pyridine bases and benzylamine is added to a viscose solution which is then formed into threads or films having an affinity for acid wool dyestuffs.