Patent GB-455602-A (GB)
Title: Improved manufacture of artificial fibres, threads, fabrics, films and the like
IPC: D01F2/28
Filed: 1935-01-18
Abstract: To impart to artificial fibres, threads, films, &c. made from solutions in organic solvents of cellulose derivatives and artificial resins, an affinity for acid dyestuffs &c., there is dissolved in the solutions artificial resins containing basic groups and selected according to their capacity to fix acid dyestuffs, or alternatively artificial resins capable of being converted into resins containing basic groups by hydrolysis, reduction or alkylation applied to the artificial fibres &c. during or subsequent to their formation. Suitable resins are: (1) condensation products of aromatic amines and formaldehyde which are soluble in acids, for example, the polymeric methyleneaminobenzyl aniline obtained by treating methylene-orthotoluidine with glacial acetic acid and subsequent reaction in acid solution with formaldehyde; (2) basic ethers of condensation products from carbonyl compounds particularly such as contain in addition ester, acyl amido, sulphamido and alkoxy groups, for example, the reaction products of b -chlorethyldiethylamine with artificial resins made by condensing phenols with less than the molecular proportion of formaldehyde under acid conditions, a particularly valuable product being obtained by boiling the condensation product from salicylic acid-dimethylamide and formaldehyde with b -chlorethyldiethylamine in the presence of sodium alcoholate and absolute alcohol; (3) products of reaction of chlorinated methylene-alkylaryl resins with amines or substitution products thereof, such as dimethylamine, piperidine, morpholine, ethanolamine and glycine ester; (4) products of the reaction of amines with halogen acyl compounds of artificial polymeric polyhydroxyl compounds such as polyvinyl chloracetate, mixed polymerization products containing vinyl chloracetate as starting component, polyglycide chloracetate, mixed polymerisates with vinyl chloracetate and vinyl alkyl ethers, acrylic acid alkyl esters, chloracetates of the product of the oxyalkylation of resins of the type (2) above; (5) products of the reaction of ammonia or amines with ethers of resins containing active halogen in the ether groups, particularly compounds having 1 : 2-halogenoxy groups, for instance, products of the reaction of epichlorhydrin on oxyethyl ethers of phenol-formaldehyde resins of the type (2) above, partially saponified polyvinyl esters, and the glycides obtained by the treatment of chlorhydrins with alkali, the reaction being conducted under pressure, at a temperature between 130 and 170 DEG C., and in the presence of boric acid, dimethyl sulphate, toluene sulphonic acid or other catalyst; (6) polymerization products of vinyl compounds which contain basic nitrogen or are capable of conversion by saponification or reduction into products having basic nitrogen, for instance, the polymerization product from g -oxyquinoline vinyl ether, and polymerizates of para-acetaminostyrene and para-nitrostyrene as may be prepared by the process described in Specification 407,997; (7) basic amides of polymeric carboxylic acids, for example, the product of condensation of polyacrylic acid amide or partial amidated polyacrylic acid methyl ester with dimethylaminomethanol etc.; (8) products of reaction of amines and resins from halogen methylarylsulphamides and formaldehyde &c., for example, p-chloromethylbenzene sulphamide is condensed with formaldehyde at 100--130 DEG C., and the resulting resin caused to react with a tertiary amine at a lower temperature; (9) soluble products of the reaction of ammonia or amines with sulpho-esters of polyhydroxyl compounds, for example, toluene sulphopolyglycide. In the case of materials made from cellulose esters or polyvinyl esters, the dyeing effects obtainable can be still further improved by subjecting the materials to partial saponification during or subsequent to formation; such saponification may be effected in the presence of an accelerator such as an alkali salt or a quaternary ammonium salt, for example, one which contains as kation a carbon chain of more than eight carbon atoms, and may be superficial, or uniform throughout the entire fibre as by the employment of ammonia or an organic amine. The saponification may be combined with a dyeing with direct dyestuffs, for example, with sulphurized or vat dyestuffs; this may be followed with top dyeing with acid dyestuffs. The saponification and the conversion of the added resin to a basic product can be locally effected either by printing, stencilling, &c., or by the application of a reserve. When the added resin contains a nitro or nitroso group the saponification may be effected by sodium sulphide or by an additional reducing agent such as hydrosulphite or stannite; for reduction apart from saponification, stannous chloride, titanous salt or other acid reducing agent may be employed. In examples, a film is cast from a solution in acetic acid or ethylene chlorhydrin of a solution of cellulose acetate containing an artificial resin from orthotoluidine and formaldehyde; an artificial silk is dry spun from an acetone solution of cellulose acetate containing the artificial resin made by treating an acid condensation product from phenol and formaldehyde with dimethylaniline and formaldehyde; to an acetone solution of cellulose acetate there is added an acetone solution obtained by adding piperidine to a solution of polyvinyl chloracetate, and from the resulting solution artificial silk is dry spun; artificial silk is dry spun from an acetone solution of cellulose acetate containing the basic resin from polyglycide chloracetate and morpholine; a film is made from a solution of ethyl cellulose in methylene chloride-ethanol containing the basic resin obtained by the action of morpholine on the chlorinated condensation product from xylene and formaldehyde; to an acetic acid solution of cellulose acetate there is added the artificial resin obtained from orthotoluidine and formaldehyde, and the resulting solution used for the casting of a film which may be partly saponified by immersion in ammonia solution; an artificial silk made by dry spinning cellulose acetate together with the artificial resin from phenol, formaldehyde and dimethylamine is partly saponified by a caustic soda solution containing sodium acetate; to a solution of ethyl cellulose in benzene-alcohol there is added the chlorinated condensation product from xylene and formaldehyde with sodium mercaptide, and the material made therefrom treated with methyl iodide; a solution of cellulose acetate in acetone-alcohol containing the condensation product treated with nitrous acid and prepared by condensation of b -chlorethylmethylamine with an acid phenol-formaldehyde resin, is spun into an aqueous precipitating bath containing dioxane, sodium salicylate and acid zinc formaldehydesulphoxylate, and the resulting threads cut into staples and treated with stannous chloride and salicylic acid in order to split off the nitroso groups and to give a product intensely dyed by acid wool dyes; a solution of cellulose ester containing a resin obtained by heating para-(methylthiomethyl)-benzene sulphamide with formaldehyde in the presence of formic acid, is spun into a neutral precipitating bath containing emulsified toluene sulphonic acid methyl ester, and the resulting material is heated with prepared chalk; a film is made from a solution in benzene-alcohol of ethylated cellulose acetate containing the product obtained by after-treating a para-butylphenolformaldehyde resin with b -bromethylamine and then adding chloral, the resulting film being finally treated with dilute formic acid containing salicylic acid.  Specifications 340,541, 369,017, 395,694, and 406,686 also are referred to.