Patent GB-1065961-A (GB)
Title: A new reactive coloring matter,processes for producing the same and processes for coloring articles with the same
IPC: C08F4/00
Filed: 1963-08-16
Abstract: Reactive colouring matters containing at least 2 chromogenic groups, in which are contained no sulpho, sulphate, carboxyl or alkali metal carboxylate groups, and containing at least 2 reactive radicals as defined below, and at least one solubilizing or dispersing group, are prepared by introducing a diazonium radical into a chromogenic compound containing no sulpho, sulphate, carboxyl or alkali metal carboxylate groups, then mixing and decomposing this with an addition-polymerizable monomer or a condensation-polymerizable monomer or a polymer containing condensable radicals, the reactive radicals being present in the monomer or introduced after the reaction, and the solubilizing or dispersing radical, if not already present in the product, also being introduced later.  The reactive radicals are methylol, epoxy, chlorohydrin, ethyleneimine, ethyleneurea, acid chloride, chlorotriazinyl, ketene, isocyanate, acid azide, malonate added isocyanate or sodium bisulphite added isocyanate radicals.  There may also be present other hydroxy, amino, imino, and carboamide radicals, and mercapto, carboxyl, sulpho, sulphamide, urea, ureido, urethane and methylene dicarboxyl groups. Suitable polymer components of the reactive colouring matters include (1) heat or acid hardenable methylol compounds, e.g. (a) urea-, melamine-, guanidine-, aniline-, carboamide-, phenol- and caseinformaldehyde resins, (b) methylolated polyamides, polyureas, polyacrylamide, and polydiaminovinyl triazines, (c) polymers and copolymers of N-methylolacrylamide, N,N1-dimethylol diaminovinyl triazine; (2) heat or alkaline-hardenable methylol compounds, e.g. acetone- and methylethyl ketone-formaldehyde resins; (3) cross-linkable epoxy or halohydrin compounds, e.g. condensates of polyamines, polyalcohols, polyphenols, polyamides, polycarboxylic acids and polyureas with epihalohydrin, dihalohydrin, butadiene dioxide, dicyclopentadiene dioxide, vinylcyclohexene dioxide or dipentene dioxide; or polyglycidyl phenolic resins or polybutadiene polyoxide; or polymers and copolymers of glycidyl methacrylate or allyl glycidyl ether; (4) addition polymers, e.g. of diallyl phthalate, ethylene glycol diacrylate, diacrylylmethane, N,N1-methylene-bis-acrylamide, unsaturated polyesters, drying oils and unsaturated fatty acid modified alkyls.  Suitable chromogens include copper phthalocyanine blue and green, vat pigments, thioindigo pigments, anthraquinone, perinone and perylene pigments, dioxazine, quinacridone, and azo pigments, sulphur pigments and basic lake pigments.  The reactive colouring matter must contain at least one group permitting it to be soluble or dispersible in water or oil. This solubilizing or dispersing group may be one of the reactive radicals already specified, or a hydrophilic radical, e.g. carboxyl, sulpho, and sulphate; hydroxyl, ether and carboamide; primary, secondary and tertiary ammonium and pyridinium radicals; or a hydrophobic hydrocarbon radical, which may contain ester, ether, amide, urea or urethane residues.  When this group has to be introduced into the reactive colouring matter, this may be done by reacting e.g. acrylic acid with hydroxy, mercapto or amine groups in the polymer; sodium bisulphite with -Br, -Cl or <FORM:1065961/C3/1> sulphamic acid with methylol; vinyl isothiocyanate with hydroxyl, mercapto, amine or carboxyl; ethylene oxide with -OH, -SH or <FORM:1065961/C3/2> glycerol with hydroxyl, epoxy, ethyleneimine, acid chloride, chlorotriazine or isocyanate; glycidal with -OH, <FORM:1065961/C3/3> -COOH or -CONH-; acrylamide with -OH, epoxy or chlorhydrin; NH3 or amine with acid chloride; pyridine hydrochloride with methylol; ethyleneimine with -OH or -CONH- groups in the polymer.  The reactive colouring matter may be reacted before or after application to a substrate with a cross-linking reactive compound, e.g. formaldehyde, glyoxal, tri- and hexa-methylolmelamine, polyamines, alkylenebis-ethyleneurea and polycarboxylic acids, and/or a primary condensate of a thermosetting polymer, and/or a thermoplastic resin, and/or a vinyl polymer latex. In examples reactive colouring matters are prepared by mixing diazotized copper phthalocyanine blue with acrylamide and methyl acrylate (1), and diazotized copper phthalocyanine green with methyl methacrylate, ethyl acrylate and glycidyl methacrylate (5).  The product of (1) is methylolated (1), or reacted with melamine and formaldehyde (2) and (4), and these products may be further reacted with a latex of butyl acrylate, vinyl acetate and vinylidene dichloride (3).  The product of (5) is reacted with glycerol, linseed oil and phthalic acid (6). In Example (7) diazotized copper phthalocyanine blue is reacted with a melamineformaldehyde resin.  In Examples (8-36) these products are used in a variety of colouring compositions. These range from simple dyeing or spraying solutions in water, a vinyl polymer latex, acetic acid, or xylene, through printing inks and pastes, to various forms of paint. The printing inks comprise mixtures of a product with printing ink varnish and BaSO4 or gum arabic or glycerol or an alkyd resin in butanol/toluene.  The printing pastes comprise mixtures of aqueous solutions of products of the invention with mineral spirits and a polyethyleneoxy compound, and/or with vinyl polymer latices or methylcellulose or a long oil alkyd resin in toluene solution or aqueous Rongalite, other additives mentioned being urea, hexamethylene bis-ethyleneurea, NH3, ZnO and SnCl2.  The paints comprise the products in linseed oil, polyvinyl acetate emulsion, casein-starch solution, a butylated MF-alkyd resin thinned with toluene and a UF resin, TiO2 sometimes being added.  The products are incorporated in a paper pulp, a cellulose xanthate solution, a polyvinyl alcohol solution, a rubber latex and in solid rubber to give coloured paper, filaments and rubber after processing.ALSO:Polymers containing chemically bound chromogenic groups and reactive groups (defined), which are soluble or dispersible in a medium (see Division C3) are used in colouring processes.  In Examples a resin obtained by polymerizing acrylamide and methyl acrylate i.p.o. diazotized copper phthalocyanine blue and adding CH2O, or the resin obtained by further reacting this with melamine and formaldehyde, is used in aqueous solution alone or mixed with a vinyl latex emulsion or a methyl cellulose solution and/or a mineral spirit and a polyoxyethylene compound and optionally urea, SuCl2, ammonia, ZuO or hexamethylene bis-ethyleneurea as dyeing [Ex 15, 18] or printing agent [Ex 8-14, 25] for cloth or leather [Ex 23, 24].  The same resins are incorporated into a paper pulp [Ex 17], or into glycerin or gum arabic for printing paper or cloth [Ex 22, 25]. In Examples 28, 29 and 36 chipboard, wood and concrete are stained with solutions in acetic acid, water or xylene of similar resins or one obtained by condensing diazotized copper phthalocyanine blue with a melamine formaldehyde resin.ALSO:Polymers containing chemically bound chromogenic groups and reactive radicals, and soluble or dispersible in a liquid medium (see Division C3) may be incorporated in paints and applied to paper, textiles, leather, wooden articles, hardboard, concrete walls, metal, glass plates.  In Example 30-33 a resin produced by polymerizing acrylamide and methyl acrylate i.p.o. diazotized copper phthalocyanine blue and treating the product with formaldehyde is incorporated into a casein-starch paint and used for coating chipboard, or is incorporated in a UF resin and used for coating a wooden veneer, or is further reacted with melamine and formaldehyde and then incorporated with TiO2 in a polyvinyl acetate emulsion paint and used to coat wood, and a resin obtained by polymerizing methyl and glycidyl methacrylates with ethyl acrylate i.p.o. diazotized copper phthalocyanine green is mixed with a soya oil alkyd, a butylated melamine formaldehyde resin, TiO2 and xylene and used to coat aluminium.