Patent GB-459711-A (GB)
Title: Manufacture of shaped materials from highly polymeric compounds
IPC: D06P1/66
Filed: 1935-04-09
Abstract: Artificial threads, films, and other shaped articles made from cellulose derivatives or synthetic resins acquire an affinity for basic dyestuffs when there is incorporated in the solutions in organic solvents from which such articles are made, an artificial resin containing acid groups, either free or combined as a salt, including carboxyl groups, sulphonic acid groups, cyanamide and negatively substituted sulphamide groups.  As an alternative, the artificial resin so added may be such that carboxylic or sulphonic acid groups may be developed therein by hydrolysis, saponification or oxidation, the shaped article being subjected to such treatment.  As a further modification, in the place of the added artificial resin, there may be incorporated (a) an oxyethylated cellulose ester or acetyl-a -ketovaleroyl cellulose, in which case the desired acid groups are developed by oxidation of the shaped article, or (b) a condensation product from a lower alkylated ethyl cellulose and glycidic acid ethyl ester, in this case the acid groups being developed in the shaped article by saponification or hydrolysis. Suitable artificial resin components are those which are polycarboxylic acids or their sulphonic acids or esters, polyester acids, polyester anhydrides, p  amides, imides, and any derivatives containing substituents in the amide or imide group including such as contain basic constituents; also resins having oxidizable residues, for instance, mercapto, sulphocyano, disulphide, isothiourea, and bodies with hydroxyl and carbonyl groups capable of being oxidized to carboxylic acids. The added components may also contain basic groups such as amino or quaternary ammonium groups, or groups which become basic by alkylation, amination or hydrolysis; or the opposed affinities may be derived from bodies separately added.  The added artificial resins may be drawn from the following clases: (1) polycarboxylic acids, such as the high molecular polysuccinic acids or their derivatives obtained by splitting by hydrolysis, alcoholysis or aminolysis the mixed polymerization products from vinyl compounds such as vinyloxyalkyl ethers, vinyl halides, vinyl fatty acid esters, vinyl-halogen fatty acid esters, acrylic acid esters, acrylic acid nitriles, styrene and maleic acid anhydride; also high molecular homopolymeric carboxylic acids such as polysorbic acid or salts of such acid with feeble bases like urea, thiourea or pyridine; (2) mixed polymerisates of vinyl compounds and maleic anhydride which still contain acid anhydride groups, such as those described in Specification 376,479; (3) polyacrylic acid esters and polymethylacrylic acid esters &c. containing saponifiable ester groups; (4) soluble resins of the polyhydric alcohol-polybasic acid type, and their strongly acid intermediate products, the acid number in any case being higher than 120.  In cases where the acid groups are only developed on hydrolysis it is preferred to use those resins containing carboxyl groups combined with monohydric alcohol residues; (5) products of the reaction of halogenated condensation products from xylene and formaldehyde with potassium hydrosulphide; and products of the reaction of polyvinylchloracetate and other resinous substances having ester groups capable of being exchanged with mercapto-alkylamines; (6) condensation products obtained by the action of alkylene sulphides on polyamines or by reaction between halogenalkylpolyamines with alkali hydro-sulphide; (7) resinous condensation products containing accessible methylol groups as obtained by the action of formaldehyde on phenol resins such as are produced by condensation of phenol and acetone under acid conditions. The after - treatment to effect saponification may be carried out with caustic alkali, other inorganic alkalies, ammonia, or amines including alkylolamines, volatile agents being used if desired in the vapour phase preferably in the presence of moisture and preferably with rhythmical oscillation of pressure; and to the saponifying solutions or printing pastes which may also contain dyestuffs, there may be added saponification accelerators such as alkali salts and onium salts of organic bases such as dodecyl trimethylammonium chloride, and the saponification may be assisted by the addition of swelling agents or of agents having an hydrophilic effect, such as urea, urethane, sulphocyanide and sodium tetrahydronaphthalene sulphonate.  With bodies containing anhydride or imide groups, saponification may be effected by water or acidified water.  When saponification occurs in the presence of polyvalent amines, basic amide groups may be produced, the products then acquiring both acid and basic characteristics; and similar products are obtained if an amination occurs or amino groups are set free or formed, as in the process described in Specification 455,849.  For the oxidation of resins containing sulphur, and carbonyl or methylol, there may be used hypochlorous acid and its organic derivatives such as paratoluolsulpho-chloramide or -dichloramide, or hydrogen peroxide, permanganate, perchlorate, or chlorine dioxide.  The after-treatment to develop acid groups may be combined with the manufacture of the shaped article, or may be carried out subsequently to such manufacture.  Hydrolysis or saponification and dyeings may be arranged to take place simultaneously; and effects may be produced by the local application of the saponifying agent.  When piece-dyeing mixed materials, there may be added to the dyebath a substance such as a salt of a base of high molecular weight of the fatty series or a quaternary salt of such base, in order to reserve the parts containing the non-acid or feebly-acid components.  Dyeing may be carried out by first applying the bottom colour, then saponifying &c. the materials over their whole surface or locally, and finally top-dyeing or printing.  Suitable dyestuffs are the dispersion dyestuffs, water-soluble basic dyestuffs which normally only dye on mordants, mordant dyestuffs such as gallocyanine and alizarine, and diazonium compounds such as diazotized Fast Blue B base, which after adsorption are developed by suitable coupling components. In some cases the affinity for direct cotton dyestuffs is enhanced.  When dyeing mixed fabrics, yarns or fibres, uniform tints are obtained if regard is had to the temperature, pH value of the liquor, or to the addition of textile assistants such as swelling agents or agents having an amine basis; in this latter connection substances may be selected which have an affinity for hydrophobe fibres such as anthraquinone-1-pyridinium chloride, or there may be used amines which on account of their high molecular weight or of a branched structure cannot penetrate into hydrophobe fibres, in particular substances which have attached to a N-atom both a residue with more than 8 C-atoms and a residue with more than 4 C-atoms, for example, didodecylamine, methyldidodecylammonium bromide, benzyloctadecenylaminoacetate, benzyloctadecyltrimethylammonium-methosulphate.  The fastness of dyeings may be improved by after-treating with coloured or colourless organic carboxylic acids or sulphonic acids or their condensation products, tannin, &c.  In addition to an increased affinity for basic dyestuffs, the materials possess an affinity for other basic treatment agents such as dispersed pigments, for example, zinc sulphide, and for resins, and for matting agents such as compounds of aluminium, tin or titanium, or resin intermediates; thus, the material may be printed with dimethylolurea in the presence of substances which yield acid, such as diethyltartrate, or with the primary condensation product of formaldehyde and urea, urea derivatives, cynamic acid, &c.  The materials also exhibit a good stability to ironing, and a modified susceptibility to the matting effect of hot aqueous liquids.  The enhanced hydrophilic nature of the acid-containing materials may be diminished or suppressed by subsequent treatment with an amine or quaternary ammonium salt of high molecular weight, for example, dodecyltrimethylammonium bromide, cocoalcoholacetate-o -pyridinium chloride, or with an aluminium or other metal salt.  If an addition containing halogen has been used, damage to the material by the separation of acid may be obviated by the addition of calcium naphthenate, phenoxy- or naphthoxy-propene oxide, or other stabilizing agent.  In examples, a cellulose acetate artificial silk contains the polymerization product from maleic anhydride and vinyl chloride, thereby acquiring an affinity for methylene Blue, Alizarine Direct Blue A, &c., and an affinity for Chromium Blue BMI after pretreating with a chromium salt; to the spinning solution for making ethylcellulose artificial silk is added polyacrylic acid ethyl ester, and the resulting silk partly saponified by concentrated ammonia; a clear film capable of being deeply dyed by methylene Blue, Tannocyanine and Auramine is obtained from a solution of cellulose acetate to which is added a highly viscous aqueous solution of the polymeric carboxylic acid obtained by splitting by heating with an equal weight of water, the polymerization product of maleic anhydride and vinyl chloride; a cellulose acetate silk containing the polymerization product from polyvinylchloracetate and maleic anhydride, is suspended in trimethylamine vapour thereby acquiring an affinity for basic dyestuffs and some acid dyestuffs such as Orange II; a film having an affinity for basic dyestuffs is made from a solution in acetone-alcohol of cellulose acetate containing the alkyd resin (acid number =240) resulting from first reacting pentaerythrite with phthalic anhydride, thiodiglycollic anhydride or other anhydride of a dicarboxylic acid, and then condensing with 1 : 3-butylene glycol; a fabric made from a cellulose artificial silk containing a mixed polymerization product from vinylmethyl ether an