Process for modifying the affinity of artificial fibrous and film-like materials

摘要

The affinity for acid or basic substances, especially dyestuffs, of artificial fibres, threads, films and the like consisting of or containing highly polymerized organic substances, free from protein but containing basic groups forming a part of such substances or of other components not removable by rinsing with water, is modified by treating the undyed material, in the absence of other alkylating agents or of dyestuffs, with a compound containing an alkylene oxide, sulphide or imine heterocyclic ring and reacting with splitting of the ring. Specified materials treated are (a) cellulose derivatives carrying basic residues in an ester or ether group, e.g. the reaction products of cellulose with halogen alkylamines, halogen oyxalkylamines, ethyleneimine or its derivatives or substituted aminopropenoxides, (b) polymerizates carrying basic groups, e.g. reaction products of a polyvinyl alcoholate with a halogen alkylamine or of polyacrylic acid methyl ester with an aliphatic polyamine such as b -diethylaminoethylamine, (c) basic aldehyde resins, e.g. those from halogenmethylarylsulphamides and formaldehyde (cf. Specification 455,602), (d) basic phenol-formaldehyde resins, (e) basic alkyd resins. Specified reagents containing an alkylene oxide, sulphide or imine heterocyclic ring are, in addition to those used in the examples below, 1 : 2-propylene oxide, 1 : 2-butylene oxide, 1 : 2-cyclohexylene oxide, phenoxypropenoxide, 3-dichloro-1 : 2-propylene oxide, ethylene imine, N-butylethylene imine, N - diethylethyleneiminium chloride, N-pentamethyleneethyleneiminium chloride and the biquaternary spirocyclic compound from di-g -chloro - b - hydroxypropylpiperazine (addition product from 1 mol. piperazine and 2 mols. epichlorhydrin). The reaction may be accelerated by catalytically acting substances, e.g. sodium or calcium chloride, tetramethylammonium chloride, dodecyltrimethylammonium chloride, bases, substances containing acid groups or acid-reacting salts. Such catalysts may be applied locally to the materials to obtain pattern effects in subsequent dyeing. In examples, (1) acetate artificial silk containing the basic resin from polyacrylic acid ethyl ester (1 mol.) and b -diethylaminoethylamine (1 mol.) (cf. Specification 450,692) is rinsed with dilute acetic acid, dried and treated for 15 hours with a moist atmosphere at 80 DEG C. containing epichlorhydrin vapour; (2) a viscose fabric, treated as described in Specification 465,105 with piperidopropenoxide and then washed successively with dilute hydrochloric acid and water, is treated for 14 hours with 1 : 2-propylene sulphide or butadiene dioxide at 70 DEG C.; (3) acetate artificial silk containing the basic resin obtainable by heating dimethylaminomethanol in alcohol with a novolak from phenol (10 mols.) and formaldehyde (7 mols.) is treated for 12 hours with a moist atmosphere at 80 DEG C. containing epichlorhydrin and ethylene oxide; (4) threads of acetylated diethylaminoethylcellulose are washed successively with dilute hydrochloric or thiocyanic acid and water and treated for 15 hours with epichlorhydrin or 1-chloro-2 : 3-propylene sulphide at 80 DEG C.; (5) copper artificial silk, pre-treated with ethylene imine (cf. Specification 460,590), is impregnated with a solution of 3 - cyclohexyliminodipropenoxide - 1 : 2 or of its methyl iodide or dimethyl sulphate addition product or of 2 : 3 : 5 : 6-tetramethylpiperazinodipropenoxide and heated at 90 DEG C.; simultaneously or finally the material may be caused to react with an alkylene oxide free from nitrogen; (6) viscose artificial silk, pre-treated with ethylene imine, is immersed in dilute hydrochloric acid, washed with water and treated for 16 hours with a moist atmosphere at 80 DEG C., containing epichlorhydrin; (7) a viscose fabric, pre-treated with 3-diethylamino - 1 : 2 - propenoxide, is treated for 16 hours in presence of formaldehyde or glyoxal, and preferably of urea or a like resinformer, with a moist atmosphere at 90 DEG C. containing epichlorhydrin. Specifications 463,043, 467,173, 469,457, 472,630, and 472,899 also are referred to. 3 - Cyclohexyliminodipropenoxide - 1 : 2 is obtained by reaction of cyclohexylamine (1 mol.) with epichlorhydrin (2 mols.). 2 : 3 : 5 : 6 - Tetramethylpiperazinodipropenoxide is obtained by reaction of 2 : 3 : 5 : 6-tetramethylpiperazino (1 mol.) with epichlorhydrin (2 mols.). 1 - Chloro - 2 : 3 - propylene sulphide is obtained by reaction of potassium thiocyanate or thiourea on epichlorhydrin.