Patent GB-716542-A (GB)
Title: The hardening of films, fibres, filaments and fabrics made from non-cellulosic hydrophilic polymers
Inventor: EVANS JOHN GWYNANT
IPC: D01F1/10
Filed: 1950-07-14
Abstract: Filaments, fibres, fabrics, films of non-cellulosic hydrophilic polymers, e.g. proteins such as casein, zein, peanut and soyabean protein, alginic acid and its salts, polyvinyl alcohol and its partial esters and polyacrylic and polymethacrylic acids and their salts, partial esters and amides, are hardened or insolubilized and given a dimensional stability to washing by treatment with, or by the incorporation in the solutions from which the filaments or films are spun or cast of an alkali metal bisulphite-organic isocyanate or alkali-metal bisulphite-organic isothiocyanate reaction product and subsequently heating the article at a temperature at least as high as the decomposition temperature of the reaction product. The affinity of those polymers containing no nitrogen, e.g. polyvinyl alcohol, for acid or chrome dyes, e.g. Polar Brilliant Red G. and Chlorazol Sky Blue FF (see Examples II and XIII) is also improved by the treatment. Bisulphite reaction products of mono- and polyfunctional aliphatic and aromatic isocyanates and isothiocyanates may be employed, specified examples of which are those of phenyl isocyanate, hexamethylene di-isocyanate, m-toluylene di-isocyanate, m-phenylene di-isocyanate and the corresponding isothiocyanates, allyl isothiocyanate, toluene 2:4 di-isocyanate, toluene 2:4:6 tri-isocyanate, mixtures of toluene 2:4 and 2:6 di-isocyanates, methylene-bis-p-phenylene isocyanate and the mixture of poly-isocyanates known under the Registered Trade Mark "Vulcafor V.C.C."  The heat treatment is preferably effected for 3 to 15 minutes at 100 DEG  to 200 DEG C., by hot air, infra-red radiation, molten metal or steam.  The treated materials, prior to or simultaneously with the heating step, may have mechanical finishes applied thereto, including mechanically enforced stretching or shrinking by the machines of Specifications 359,759 and 372,803, [both in Group VIII].  Local or pattern effects may be obtained by printing the reaction product on the material, or alternatively, by the pre-application of resists or by the subsequent application of a discharge paste prior to the heating step.  Enhanced effects are obtained if the heating step is effected in the presence of an amide, thioamide, sulphonamide, amidine or aminotriazine, e.g., urea, thiourea, acetamide, p-toluene sulphonamide, benzene sulphonamide, dicyandiamide, guanidine, amino guanidine and melamine.  Treatment with other hardening agents, e.g., aldehydes, thermo-setting condensates, aluminium or chromium salts, may be applied before, simultaneously with or after the reaction product.  The process may also be employed to increase the retention of water-sensitive fillers, e.g. starches, gums, alginates, water soluble cellulose ethers, proteins, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, and polyacrylic acid and its salts, in the fibrous material, the filler being applied prior to the heating step. Numerous examples are given.  Specification 716,233 also is referred to.ALSO:Filaments, fibres, fabrics and films of non-cellulosic hydrophilic polymers, e.g., proteins such as casein, zein, peanut and soya bean protein, alginic acid and its salts, polyvinyl alcohol and its partial esters and polyacrylic and polymethacrylic acids and their salts, partial esters and amides, are hardened or insolubilized and given a dimensional stability to washing by treatment with, or by the incorporation in the solutions from which the filaments or films are spun or cast of, an alkali metal bisulphite-organic isocyanate or alkali-metal bisulphite-organic isothio-cyanate reaction product and subsequently heating the article at a temperature as least as high as the decomposition temperature of the reaction product.  The affinity of those polymers containing no nitrogen, e.g., polyvinyl alcohol, for acid or chrome dyes, e.g., Polar Brilliant Red G. and Chlorazol Sky Blue FF (see Examples II and XIII) is also improved by the treatment.  Bisulphite reaction products of mono- and polyfunctional aliphatic and aromatic isocyanates and isothiocyanates may be employed, specified examples of which are those of phenyl isocyanate, hexamethylene di-isocyanate, m-toluylene di-isocyanate, m-phenylene di-isocyanate and the corresponding isothiocyanates, alkyl isothiocyanate, toluene 2 : 4 di-isocyanate, toluene 2 : 4 : 6 tri-isocyanate, mixtures of toluene 2 : 4 and 2 : 6 di-isocyanates, methylene-bis-p-phenylene isocyanate and the mixture of poly-isocyanates known under the Registered Trade Mark "Vulcafor" V.C.C.  The heat treatment is preferably effected for 3-15 minutes at 100 DEG -200 DEG C., by hot air, infra-red radiation, molten metal or steam.  The treated materials, prior to or simultaneously with the heating step, may have mechanical finishes applied thereto, including mechanically enforced stretching or shrinking by the machines of Specifications 359,759 and 372,803, [both in Group VIII].  Local or pattern effects may be obtained by printing the reaction product on the material, or alternatively, by the pre-application of resists or by the subsequent application of a discharge paste prior to the heating step.  Enhanced effects are obtained if the heating step is effected in the presence of an amide, thioamide, sulphonamide, amidine or amino triazine, e.g., urea, thiourea, acetamide, p-toluene sulphonamide, benzene sulphonamide, dicyandiamide, guanidine, amino guanidine and melamine.  Treatment with other hardening agents, e.g., aldehydes, thermosetting condensates, aluminium or chromium salts, may be applied before, simultaneously with or after the reaction product.  The process may also be employed to increase the retention of water-sensitive fillers, e.g., starches, gums, alginates, water soluble cellulose ethers, proteins, polyvinyl alcohol, partially hydrolysed polyvinyl acetate, and polyacrylic acid and its salts, in the fibrous material, the filler being applied prior to the heating step. Numerous Examples are given.  Specification 716,233 also is referred to.