Patent GB-745356-A (GB)
Title: Printing and decorating of fibrous sheet material
IPC: D06P1/44
Filed: 1952-08-19
Abstract: A printing paste consists of (a) an emulsion of a water-insoluble copolymer which contains reactive hydrogen or halogen atoms and is obtained from a polymerizable vinyl compound containing reactive hydrogen or halogen atoms and an acrylate or methacrylate of an alcohol carrying at least 4 carbon atoms, or a butadiene, or a chlorobutadiene, (b) a polyfunctional compound capable of being reacted with the reactive hydrogen or halogen atoms of the copolymer, (c) a pigment, (d) a thickening agent and (e) water.  The copolymers (a) may also contain other monomers such as styrene, a lower aliphatic acrylate or methacrylate, acrylonitrile, or ethylene glycol diacrylate.  The polymerizable vinyl compound may be acrylic acid, methacrylic acid, acrylic or methacrylic amide which may be substituted by alkyl groups such as methyl, butyl, hexyl and dodecyl, vinyl methyl ketone, alpha-ethyl acrolein, methyl, butyl, or hexyl alpha-chloroacrylates, 1:1-dichloroethene, or the addition compound of 1 mol. of a primary amine to 1 mol. of hexahydro - 1,3,5 - triacrylyl - s - triazine.  Polyfunctional compounds mentioned are polyisocyanates, or compounds which react as polyisocyanates at elevated temperatures, formaldehyde and substances yielding formaldehyde, diamines, polyamines, and the addition product of formaldehyde and acrylonitrile.  Exemplified polyfunctional compounds are hexamethylene diamine, an aqueous solution of the acetate of a basic polyurea prepared from diethylene triamine, g ,g  - diaminodipropylmethamine and hexane diisocyanate, formaldehyde, hexahydro-1.3.5-triacrylyl-s-triazine, and the reaction product of malonic acid and hexamethylene diisocyanate. The thickening agent may be tragacanth, an alkali metal alginate, turpentine alone, or admixed with benzyl-o-hydroxy diphenyl polyglycol ether.  Specified pigments are Helio Fast Blue paste, naphthol AS/IFR, and blue copper phthalocyanine.  In example (2), a terpolymer of butadiene, methyl methacrylate, and alpha-ethyl acrolein is made by polymerizing an emulsion of the monomers in an aqueous solution of the sodium salt of sulphonic acids obtained by the sulphochlorination of long chain paraffins, in the presence of a catalyst system consisting of the sodium salt of the sulphinic acids of long chain paraffins and sulphuric acid; in example (3), a terpolymer of acrylonitrile, 1.1-dichloroethene and acrylic acid monobutylamide is prepared by a similar process; in example (4) a tetrapolymer of acrylonitrile, 1.1-dichloroethene, butyl acrylate, and methacrylic acid is made by a similar process; in example (5) a terpolymer of butadiene, methyl methacrylate, and alpha-cyanosorbinic acid ethyl ester is made by polymerizing in an aqueous solution of the sodium salt of dibutyl naphthalene sulphonic acid in the presence of a redox system consisting of sodium hydrosulphite and potassium persulphate; and in example (6) the preparation of a five component copolymer of butadiene, styrene, butyl acrylate, acrylonitrile and acrylamide is described, utilizing the process of example (2).  The pastes are used for printing fabrics and paper, e.g. wall paper.ALSO:Textiles are decorated by applying to the textiles a printing paste consisting of a water-insoluble copolymer comprising a vinyl monomer containing reactive hydrogen or halogen atoms and an acrylate or methacrylate of an alcohol carrying at least 4 carbon atoms or a butadiene or chlorobutadiene, a pigment, a thickening agent and water, and optionally a polyfunctional compound capable of reacting with the reactive groups of the copolymer. If the polyfunctional compound is not included in the paste the textile is either pretreated with the compound or the compound applied after the paste.  Polyfunctional compounds mentioned are polyisocyanates or compounds which react as polyisocyanates at elevated temperatures, formaldehyde and substances yielding formaldehyde, diamines and polyamines, and the addition product obtainable from formaldehyde and acrylonitrile.  Exemplified polyfunctional compounds are hexamethylene diamine, an aqueous solution of the acetate of a basic polyurea prepared from diethylene triamine, g ,g  - diaminodipropylmethamine and hexane diisocyanate formaldehyde, hexahydro-1.3.5-triacrylyl-n-triazine, and the addition product of malonic acid and hexamethylene diisocyanate.  The thickening agent may be tragacanth, an alkali metal alginate, turpentine alone, or admixed with benzyl-o-hydroxy diphenyl polyglycol ether.  Specified pigments are Helio Fast Blue past, naphthol AS/IFR, and blue copper phthalocyanine.  The textiles may be made of cotton, or rayon.