Patent GB-1119662-A (GB)
Title: Printing inks and varnishes
IPC: C09D11/06
Filed: 1965-07-02
Abstract: High gloss, quick-setting ink varnishes comprise (a) 5-60% by weight of a salt of a solid acidic resin of acid number at least 40 with a nitrogenous base of basic dissociation constant > 1 x 10-6, (b) 10-90% by weight of a liquid salt of an acidic modified drying oil of acid number at least 40 with a nitrogenous base as above, and (c) 5-70% by weight of a water-miscible aliphatic organic solvent selected from alcohols, glycols, glycol ethers, glycol esters and mixtures thereof with water, all weights being based on the total composition, said resin salt (a) being soluble in (b) and (c), said modified drying oil salt (b) being soluble in (c), but said acidic resin per se being insoluble in (b) and (c) and said acidic modified drying oil per se being insoluble in (c).  Resin (a) may be rosin, polymerized, disproportioned or hydrogenated rosin, copal, sandarac, an alkyd resin, a partly esterified resin, or an adduct of rosin or a terpene with an a ,b -unsaturated dicarboxylic acid such as citroconic, mesaconic, aconitic, itaconic or, particularly, maleic or fumaric acid.  Modified oil (b) is the reaction product of a drying oil and a similar acid. Solubilizing bases for (a) and (b) include ammonia, primary amines, ethylene diamine, polyalkylene polyamines, ethanolamines, morpholine and piperidine.  Numerous common solvents (c) are listed, ethylene glycol \sB water or glycerine, and dibutyl carbitol being preferred. Printing inks are prepared from 30-95% by weight varnish as above and correspondingly 70-5% colouring matter. In Examples 2 and 7 a triethylamine salt of tung oil modified with fumaric acid is mixed with a solution of a monoethanolamine salt of a maleic resin derived from maleic anhydride, glycerine and rosin, and mixed with monastral blue, TiO2, and ethylene glycol to form a printing ink, and in Examples 4 and 9 the ammonia salt of tung oil modified with itaconic acid is mixed with a solution of a dimethyl ethanolamine salt of the same maleic resin, and mixed with molybdate orange, calcium lithol, glycerine and ethylene glycol to form an ink. In other examples, the modified drying oil salt predominates over the maleic (Examples 1 and 6) or alkyd resin (Examples 3 and 8) or modified ester of rosin (Examples 5 and 10), and further colorants used are Lithol red, carbon black and Alkali blue (green shade), other additives including a wax, Co, Mn and Pb driers, and a clay extender.ALSO:High gloss, quick-setting ink varnishes comprise (a) 5-60% by weight of a salt of a solid acidic resin of acid number at least 40 with a nitrogenous base of basic dissociation constant >1 x 10-6, (b) 10-90% by weight of a liquid salt of an acidic modified drying oil of acid number at least 40 with a nitrogenous base as above, and (c) 5-70% by weight of a water-miscible alipathic organic solvent selected from alcohols, glycols, glycol ethers, glycol esters and mixtures thereof with water, all weights being based on the total composition, said resin salt (a) being soluble in (b) and (c), said modified drying oil salt (b) being soluble in (c), but said acidic resin per se being insoluble in (b) and (c) and said acidic modified drying oil per se being insoluble in (c).  Resin (a) may be natural or synthetic, e.g. rosin, polymerized, disproportioned or hydrogenated rosin, copal, sandarac, an alkyd resin, a partly esterified resin, or an adduct of rosin or a terpene with an a -b unsaturated dicarboxylic acid such as citraconic, mesaconic, aconitic, itaconic or, particularly, maleic or fumaric acid. Modified oil (b) is the reaction product of, e.g. linseed, tung, cotton seed, sunflower or perilla oil with a -b  ethylenically unsaturated carboxylic acids or their anhydrides, e.g. maleic acid or anhydride, fumaric, itaconic, acrylic or citraconic acid. Particularly suitable solubilizing bases for (a) and (b) are ammonia, methyl-, dimethyl-, ethyl-, diethyl-, triethyl-, propyl-, i-propyl-, n-butyl-, di-n-butyl, i-butyl-, hexyl-, and laurylamines, ethylene and propylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, ethanolamine, di-and triethanolamines, dimethyl ethanolamine, morpholine, and piperidine.  Numerous common solvents (c) are listed, ethylene glycol \sB water or glycerine, and dibutyl carbitol being preferred.  Printing inks are prepared from 30-95% by weight of a varnish as above and correspondingly 70-5% colouring matter.  In examples colourants used are lithol red, molybdate orange, monastral blue, calcium lithol, alkali blue (green shade), TiO2, and carbon black, and conventional driers (Co, Mn, Pb) solvents (ethylene glycol, water, glycerine) and extenders (clay) are included.