Patent GB-810548-A (GB)
Title: Process for fixing pigments on fibrous materials or foils
Inventor: HAAKH HERMANN
IPC: D06P1/44
Filed: 1955-03-31
Abstract: An aqueous bath or paste for use in dyeing or printing fibrous materials or films (see Group IV (c)) contains an organic or inorganic pigment, an alkali-soluble resinous polycarboxylic acid-polyhydric alcohol condensation product containing reactive carboxylic acid groups and a polyfunctional compound, the functional groups of which contain a three-membered ring containing a nitrogen or oxygen atom.  Suitable polyfunctional compounds are reaction products of epichlorhydrin with glycide or with polyhydric alcohols or with amines; diglycide ether, butadiene dioxide, ethylene imine compounds of the formula <FORM:0810548/IV (a)/1> in which R=a polyvalent aliphatic, isocyclic or heterocyclic radical, X=-NHCO-, -CO-, -SO2-, -OCO- or -OCH2- or of the formula <FORM:0810548/IV (a)/2> in which R=a polyvalent radical such as -CO-, -SO2-, -SO-, =PO-, =PS-, -(CH2)2NHCOCONH(CH2)2- or <FORM:0810548/IV (a)/3> Suitable pigments are titanium dioxide, zinc oxide, iron oxides, carbon black, ultramarine, lead colours, metal powders, vat dyestuffs, azo dyestuffs, phthalocyanines and finely-cut dyed textile fibres.  The aqueous bath or paste may also contain softeners such as dibutyl phthalate, emulsifiers, other resins and thickeners such as alginates, vegetable mucilages, carob bean flour, cellulose ether carboxylic acids, polyvinyl alcohol, polyacrylic acid salts or an oil-in-water type emulsion of a water-insoluble organic solvent, e.g. benzine, toluene, xylene or chlorinated hydrocarbons.  In examples, the alkyd resins employed are those obtained by condensing 1 : 3 : 5-hexane-triol with phthalic anhydride in the presence of boric acid, in one case together with pentaerythrite, by condensing pentaerythritol with phthalic anhydride and stearic acid and by condensing glycerine and 1 : 4-butylene glycol with phthalic anhydride and adipic acid. The polyfunctional compounds employed in the Examples are diglycide ether, diepoxybutane and the reaction products of ethylene imine with phosphorus oxychloride, propyl disulphochloride, hexane-1 : 6-diisocyanate, diethyl oxalate, phosphorus thiochloride, cyanuric acid chloride, the triisocyanate of 1 : 3-dimethyl - 2 : 4 : 6 - triaminobenzene and phosphoric acid diethylamide.  Other additions to the baths or pastes employed in the examples are di- and tri-ethanolamine, urea, ammonium thiocyanate, ammonium caseinate, ethyl glycol acetate, sodium pentachlorophenolate, tri-isobutyl phosphate, sodium lauryl sulphonate, cellulose glycollic acid ether, ethylene glycol, a dodecyl alcohol-ethylene oxide condensation product and tragacanth, an oil-in-water emulsion thickener being employed in some cases and additional high polymer substances being polyvinyl-acetate and -propionate and copolymers of vinyl acetate, acrylic acid butyl ester and acrylic acid and of vinyl propionate and crotonic acid, polyisobutylene and coumarone resin. Specifications 495,375 and 801,522 are referred to.ALSO:Fibrous materials or films are dyed or printed with an aqueous bath or paste containing an organic or inorganic pigment, an alkalisoluble resinous polycarboxylic acid-polyhydric alcohol condensation product containing reactive carboxylic acid groups, and a polyfunctional compound, the functional groups of which contain a three-membered ring containing a nitrogen or oxygen atom, the dyed or printed material being finally dried and heated, if desired, in the presence of steam.  In a modification, the polyfunctional compound may be applied before or after the bath or paste containing the other constituents.  Suitable polyfunctional compounds are reaction products of epichlorhydrin with glycide or with polyhydric alcohols or with amines; diglycide ether, butadiene dioxide, ethylene imine compounds of the formula <FORM:0810548/IV (c)/1> in which R = a polyvalent aliphatic, isocyclic or heterocyclic radical, x = -NHCO-, -CO-, -SO2-, -OCO- or -OCH2- or of the formula <FORM:0810548/IV (c)/2> in which R = a polyvalent radical such as -CO-, -SO2-, -SO-, =PO-, =PS-, -(CH2)2NHCOCONH(CH2)2- or <FORM:0810548/IV (c)/3> Suitable pigments are titanium dioxide, zinc oxide, iron oxides, carbon black, ultramarine, lead colours, metal powders, vat dyestuffs, azo dyestuffs, phthalocyanines, and finely cut dyed textile fibres.  The aqueous bath or paste may also contain softeners such as dibutyl phthalate, emulsifiers, other resins and thickeners such as alginates, vegetable mucilages, carob bean flour, cellulose ether carboxylic acids, polyvinyl alcohol, polyacrylic acid salts or an oil-in-water type emulsion of a water-insoluble organic solvent, e.g. benzine, toluene, xylene or chlorinated hydrocarbons. Films, paper, artificial leather, animal fibres and fibres of natural or regenerated cellulose, acetyl cellulose, polyacrylonitrile, polyvinyl chloride, polyamides, polyesters, glass and asbestos may be treated.  The firbrous material may first be padded with an oxidation dyestuff and then printed with the pigment composition, or a coupling component may first be applied and a stabilized diazo compound added to the pigment printing paste; alternatively, mixtures of stabilized diazo compounds and naphtholates or a sulphuric acid leuco ester of a vat dyestuff may be included in the paste, the final steaming operation serving to develop these additional dyestuffs.  Examples describe the padding of fabrics of cotton, cotton-regenerated cellulose, regenerated cellulose and polyacrylonitrile fibres and the printing of fabrics of cotton, regenerated cellulose, acetyl cellulose, polyamide, polyacrylonitrile and glass fibres, the alkyd resins employed being those obtained by condensing 1 : 3 : 5-hexane-triol with phthalic anhydride in the presence of boric acid, in one case together with pentaerythrite, by condensing pentaerythritol with phthalic anhydride and stearic acid and by condensing glycerine and 1 : 4-butylene glycol with phthalic anhydride and adipic acid. The polyfunctional compounds employed in the examples are diglycide ether, diepoxy butane and the reaction products of ethylene imine with phosphorus oxychloride, propyl disulphochloride, hexane 1 : 6-diisocyanate, diethyl oxalate, phosphorus thiochloride, cyanuric acid chloride, the triisocyanate of 1 : 3 - dimethyl - 2 : 4 : 6 - triaminobenzene and phosphoric acid diethylamide.  Other additions to the baths or pastes employed in the examples are di- and tri-ethanolamine, urea, ammonium thiocyanate, ammonium caseinate, ethyl glycol acetate, sodium pentachlorophenolate, tri-isobutyl phosphate, sodium lauryl sulphonate, cellulose glycollic acid ether, ethylene glycol, a dodecyl alcohol-ethylene oxide condensation product and tragacanth, an oil-in-water emulsion thickener being employed in some cases and additional high polymer substances being coumarone resin, rubber latex, polyisobutylene, polyvinyl-acetate and propionate and copolymers of vinyl acetate, acrylic acid butyl ester and acrylic acid and of vinyl propionate and crotonic acid. Specifications 495,375 and 801,522 are referred to.