Patent GB-930762-A (GB)
Title: Pigment resin printing paste
IPC: C09D11/10
Filed: 1961-09-27
Abstract: A pigment resin printing paste contains as the binder resin component a polymeric material having an active bromine atom, said polymeric material being obtained by partial bromination of either an unsaturated polymer formed by the polymerization of a 1,3-diolefinic monomer, of either an unsaturated polymer formed by the polymerization of a 1,3-diolefinic monomer, e.g. isoprene, butadiene, chloroprene, or an unsaturated copolymer formed by copolymerizing said above monomer with another ethylenically unsaturated monomer or monomers, e.g. butadiene copolymerized with isobutylene, vinyl chloride, acrylonitrile, acrylic acid, methyl acrylate, styrene, vinylidene chloride or vinyl acetate. When a copolymer is used it should contain more than 50 mol. per cent of the 1,3-diolefinic monomer.  Commercially available so-called synthetic rubbers (before curing or vulcanization) may be used as the binder resin component. The bromination is carried out in a solvent inert to halogens, e.g. hydrocarbon and halogenated hydrocarbon solvents and the amount of bromine adsorbed should be from 3 to 25 mol. per cent per mole of total monomer units in the polymer.  The solution of the polymeric material having an active bromine atom may be used directly or it may be diluted with a solvent or it may be emulsified, the emulsion being an O/W or W/O type.  When an emulsion is used, 1 to 5% by weight (based on the weight of resin) of a stabilizer may be added, suitable stabilizers being epoxy compounds, metal soaps and organotin compounds.  Surface active agents used for the emulsion preparation are usually non-ionic but anionic ones may also be used, e.g. salts of aliphatic alcohol-sulphuric acid esters.  In addition to the binder resin of the invention auxiliary binders may be present, e.g. partially acetalized polymeric compounds obtained by reacting polyvinyl alcohol with acrolein, dimeric acid obtained by dimerization of drying oil fatty acid or the polyol esters thereof, acetal resins, ketone resins and various aminoplasts and mixtures thereof.  In addition the pigment resin printing paste may contain a thermoplastic resin latex, e.g. a butadiene-acrylonitrile copolymer latex, or the latices of homopolymers of vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, acrylonitrile, styrene, vinylidene chloride or butadiene, or copolymers of more than two of these monomers.  Polybasic compounds such as polyamines may be added as cross-linking agents.  In the preferred embodiment a cationic aminoplast may be added which acts both as a cross-linking agent and as the auxiliary binder.  Typical cationic aminoplasts are cationic melamine-formaldehyde resins and cationic urea-formaldehyde resins which are obtained by addition of a basic polyamine or the condensation product thereof (e.g. condensation products of ammonia or polyfunctional amines with difunctional halohydrins, and reaction products of tertiary alkanol amines with aldehydes) to melamine or urea-formaldehyde condensate.  Preferably a polyhydric alcohol-modified cationic aminoplast is used.  The cationic melamine-formaldehyde resins contain formalin with a molar ratio of 3 to 12 moles per mole of melamine, and the polyfunctional aliphatic polyamine or condensation product thereof is used in such an amount to provide 0.3 to 10 basic nitrogen atoms per mole of melamine.  The cationic aminoplast resin is added to the printing paste emulsion and it is preferably used in an amount of 1/3 to 3 times that of the polymeric compound having an active bromine atom.  A buffer may be added and the pigments which may be used are those commonly used in conventional printing pastes.ALSO:Cellulosic fibre articles and synthetic fibre articles, e.g polyamide, polyester, polyacrylic and polypropylene types or mixed spun or mixed woven products thereof are dyed with a pigment resin printing paste (see Group IV(a)) which has as the binder resin component a polymeric material having an active bromine atom, the polymeric material being obtained by the partial bromination of either an unsaturated polymer formed from a 1,3-diolefinic monomer, e.g. isoprene, butadiene, chloroprene, or an unsaturated copolymer formed from the said monomer plus another ethylenically unsaturated monomer or monomers, e.g. butadiene copolymerized with isobutylene, vinyl chloride, acrylonitrile, acrylic acid, methyl acrylate, styrene, vinylidene chloride or vinyl acetate. When a copolymer is used it should contain more than 50 mol. per cent of the 1,3-diolefinic monomer.  The bromination is carried out in an inert solvent and the amount of bromine adsorbed should be from 3 to 25 mol. per cent per mole of total monomer units in the polymer.  The binder resin may be used directly or may be diluted with a solvent or it may be emulsified and stabilizers, surface active agents, auxiliary binders, thermoplastic resin latices and polybasic compounds may be added.  The pigment resin printing pastes obtained can be printed on to the fabrics by known methods, e.g. mechanical printing, screen printing, and after printing the fabrics are usually cylinder dried, e.g. 100 DEG  to 110 DEG C., and heat-treated to set the paste on the fabric, e.g. by dry heat treatment at 120 DEG  to 150 DEG C., or immersion in an aqueous alkali solution at 80 DEG  to 90 DEG C.  In Example 3 the binder resin component is a brominated butadiene-styrene copolymer and in all the other examples it is a brominated poly-2-chlorobutadiene polymer.  Pigments are added to the paste.