Patent GB-484984-A (GB)
Title: Process for modifying the affinity of fibrous and film-like materials for dyestuffs
IPC: D06P3/40
Filed: 1936-08-11
Abstract: The affinity for dyestuffs of undyed fibrous and film-like materials containing no basic groups but comprising firmly fixed substances in which acidic salt-forming hydroxyl or acidic mercapto groups, other than thiocarbonic acid groups, are attached to carbon, is modified by treatment with an alkylene imine which reacts with opening of the imine ring or with a salt thereof.  The material treated may be organophilic, e.g. acetyl- or ethylcellulose or a vinyl polymerizate or hydrophilie, e.g. cotton or regenerated cellulose. The acid groups may be produced by a preliminary saponification or oxidation (cf. Specification 459,711).  Specified types of acid components are polymeric carboxylic acids, anhydrides and esters and interpolymerizates therefrom, ester acids of cellulose, pectin esters, alkyd resins of high acid number, anhydric condensation products from aromatic hydrocarbons with side chains and a  : b -unsaturated dicarboxylic acids (cf. Specification 441,016), phenol-aldehyde resins and their acyl derivatives, tannin, acetyltannin, sulphurized phenols and polyvalent mercapto compounds and their acyl derivatives.  The acid groups are advantageously saturated with organic bases carrying halogenalkyl groups prior to treatment with the alkylene imines.  Specified alkylene imines are ethylene imine and its C-methyl, N-methyl, N-butyl and N-cyclohexyl derivatives and the quaternary iminium salts from N : N1-dimethyl-di(b -chlorethyl) ethylenediamine or N : N1-di(g -chlorob -hydroxypropyl) piperazine.  In some cases they may have an aminating action and may be used with other aminating or similarly acting agents, e.g. pyridine, trimethylamine, isoquinoline or triethylphosphine.  The fastness of the dyeings and their uniformity when admixtures with animal fibres are to be dyed may be improved by treatment before, during or after the dyeing with an alkylating agent such as dimethyl sulphate, p-toluenesulphonic acid methyl ester, epichlorhydrin, 3-chloro-1 : 2-propylene sulphide, chloracetic acid diethylamide, benzyl chloride, xylylene bromides, 1 : 4-dichlorobutene-2 : 3, chloracetone, 1 : 3-dichloracetone, a  : a -dichlorodimethyl ether or diethylethyleneiminium chloride (cf. Specifications 467,173 and 469,457).  In examples, acetate artificial silk is adapted to be dyed with acid and in some cases with substantive dyes by (1) incorporating an interpolymerizate from vinyl methyl ether (1 mol.) and maleic anhydride (1 mol.) and treating for 14 hours in a closed vessel at 60 DEG  C. with N-butylethyleneimine under rhythmic variation of pressure (cf. Specification 464,823), (2) incorporating the same polymerizate and treating successively with tetra-(g -chloro-b -hydroxypropyl) ammonium chloride for 1 hour at 70 DEG  C. and with an atmosphere at 70 DEG  C. containing ethylene imine vapour for 4-8 hours, (3) incorporating the same polymerizate and treating with C-methyl-ethylene imine for 8 hours at 75 DEG  C., (4) and (25) incorporating a condensation product from phenol (10 mols.) and formaldehyde (7 or 8 mols.) and treating for 7 or 8 hours in a moist atmosphere at 70 DEG  C. containing ethylene imine vapour, (5) incorporating an anhydric condensation product from xylene and maleic anhydride and treating for 4 hours with an atmosphere at 60 DEG  C. containing ethylene imine vapour, (6) incorporating acetyltannin and treating for 14 hours in an atmosphere at 80 DEG  C. containing ethylene imine vapour, (8) incorporating polyvinyl chloracetate and an interpolymerizate as in (1) and treating for 8 hours at 75 DEG  C. with an amount of N-methylethylene imine equivalent to the reactive chlorine and the free carboxyl groups, (9) incorporating an interpolymerizate as in (1) and treating with an aqueous solution at 30-35 DEG  C. of p  ethylene imine, preferably after a preliminary treatment, in presence of sodium acetate, with a reaction product from N-butylamine hydrochloride and epichlorhydrin, (12) incorporating an acetylcellulose esterified with maleic or succinic anhydride partially saponifying by treatment for 8 hours with a moist atmosphere at 70 DEG  C. containing ammonia and treating for 8 hours in an atmosphere at 60 DEG  C. containing ethylene imine vapour, (19) incorporating an interpolymerizate from vinyl chloride (1 mol.) and maleic anhydride (1 mol.) and treating successively with the reaction product at 50-70 DEG  C. from ethylene diamine (1 mol.) and 1 : 2-propylene sulphide (4 mols.) in presence of sodium hydrosulphite and with an aqueous solution of ethylene imine at 40 DEG  C., (23) incorporating an interpolymerizate as in (1) and treating for 12 hours in a closed vessel at 90 DEG  C. with N-cyclohexylethylene imine, (24) incorporating a product of the action of maleic anhydride on acetyl cellulose of low acetyl content and treatment for 7 hours with a moist atmosphere at 70 DEG  C. containing ethylene imine vapour, (26) incorporating an interpolymerizate as in (1) or that from vinyl acetate (1 mol.) and maleic anhydride (1 mol.) and a condensation product from phenol (10 mols.) and formaldehyde (8 mols.) and treating with ethylene imine at 70 DEG  C.; acetylcellulose films are adapted to be dyed with acid dyes by incorporating an interpolymerizate as in (1) and (7) treating for 16 hours with an atmosphere at 80 DEG  C. containing ethylene imine vapour or (10) suspending overnight at 60 DEG  C. above ethylene imine, (18) incorporating acetyl pectin and treating with moist ethylene imine vapour; (11) cellulose nitrate artificial silk is adapted to be dyed with acid dyes by incorporating an interpolymerizate from vinyl ethyl ether (1 mol.) and maleic anhydride (1 mol.), denitrating and treating at 40-80 DEG  C. with an aqueous solution of ethylene imine and, preferably after-treating with an alkylating agent e.g. epichlorhydrin (cf. Specification 472,630); (13) viscose artificial silk is adapted to be dyed with acid or substantive dyes by mordanting with tannin and tartar emetic and treating with ethylene imine in aqueous solution or as vapour, preferably after a preliminary treatment with hexa-(g -chloro-b -hydroxypropyl)ethylenedi-ammonium chloride in presence of sodium acetate at 20-70 DEG  C., the fastness of the substantive dyeings being improved by a treatment, prior to dyeing, with an alkylating agent or with an isothiourea ether or cyanamide; (14) a cellulose film is adapted to be dyed with acid dyes by incorporating the interpolymerizate from vinyl ethyl ether (1 mol.) and maleic anhydride (1 mol.) and suspending for 2 hours in ethylene imine vapour at 80 DEG  C.; (15) a bundle of continuous viscose fibre is treated successively with a sulphurized phenol and with tetra(g -chloro-b -hydroxypropyl)ammonium chloride, in presence of sodium acetate, cut to staple and treated with an aqueous solution at 40 DEG C. of ethylene imine; films of cellulose ethyl ether are adapted to be dyed with acid dyes by (16) incorporating the interpolymerizate from vinyl chloride (1 mol.) and maleic anhydride (1 mol.) and treating successively with water at 60-70 DEG  C. and with C-methyl-ethylene imine vapour, (17) incorporating the interpolymerizate from vinyl ethyl ether (1 mol.) and maleic anhydride (1 mol.) and treating with a moist atmosphere containing ethylene imine vapour or (20) incorporating a chlorinated resin from xylene and formaldehyde, which has been reacted with potassium hydrosulphide and acetylated, and heating for 8 hours at 60 DEG  C. with ethylene imine and trimethylamine in presence of alcohol vapour; (18) a film of polyvinyl formal is adapted to be dyed with acid dyes by incorporating a novolak from phenol (1 mol.) and formaldehyde (6,5 mols.) and treating with aqueous ethylene imine; cuprammonium artificial silk is adapted to be dyed with acid dyes by swelling with caustic soda, (21) impregnating with a solution of ammonium glycerine-tris-phthalate, or equivalent derivatives of aromatic tricarboxylic or polyoxycarboxylic acids, or pyridine polycarboxylic acids, souring with hydrochloric acid or heating, and suspending for 4 hours in ethylene imine vapour at 60 DEG  C., or (22) impregnating with a solution of sodium pentaerthritetetraphthalate, treating with a solution of the reaction product from dodecyltriethylenediamine hydrochloride (1 mol.) and epichlorhydrin (9 mols.) and suspending in ethylene imine vapour; (27) a film of alkali-soluble oxyethylcellulose is adapted to be dyed with acid dyes by incorporating cellulose glycollic acid ether and treating for 4 hours with ethylene imine vapour at 60 DEG  C. preferably after a preliminary treatment with a solution of tetra(y-chlor-b -hydroxypropyl) ammonium chloride. Specifications 454,320 455,602, and 455,849, also are referred to.