Abstract:
Printing inks are described which utilize a unique class of coloring agents which are the reaction products of free NCO group bearing resins and dyestuffs bearing reactive hydrogens. A novel class of such adducts which contain monocarboxylic acid residues are also described. These printing inks, which may also contain traditional pigments, find particular utility in letterpress or offset printing.

Description:
FIELD OF THE INVENTION 
     The present invention relates to printing ink based on a specific class of colouring agents and certain colouring agents which are particularly suitable in such a printing ink. 
     BACKGROUND OF THE INVENTION 
     Conventional printing inks, in particular letterpress and offset printing inks, are, in addition to other constituents, for example mineral oils, siccatives and anti-skinning agents etc., essentially composed of a varnish and pigments, there being used for four-colour printing, in addition to black, for which, for example, carbon black is used, organic pigments in the colours yellow, magenta and cyan. The varnish contains, for example, alkyd resins, hard resins and solvents or diluents. 
     The printing ink systems which are produced with the use of organic pigments, which is almost exclusively practiced nowadays, result in printing which is adequate in many respects on sheet-fed and rotary letterpress and offset printing, nevertheless there is a permanent requirement for further improvements, for example in colour strength, lack of hiding power (transparency) and brilliance as well as in the problems that derive from dispersions of particulate pigment bodies within the ink vehicle. 
     For example, with organic pigments these said properties cannot be improved beyond certain limits which are determined by, inter alia, the particle size of the dispersed pigments. 
     Dyestuff molecules have been immobilized in polyurethane matrices by chemical combination with the isocyanate reactant used to form the polyurethane. Typically the dyestuff was reacted with the isocyanate at the same time as the co-reactant used to form the polyurethane, typically a polyether or polyester polyol. U.S. Pat. No. 3,137,671 describes combining all the polyurethane forming reactants and the dyestuff simultaneously to obtain a fully cured polyurethane. It also describes premixing the dyestuff with some of the reactants before the final polyurethane forming reaction takes place. If the dyestuff is premixed with the isocyanate reactant a lower molecular weight adduct may be transiently formed. The finally cured high molecular weight polyurethane may be in the form of a foam or lacquer film or it may be ground and used as a pigment for colouring polyvinyl chloride molding resin. U.S. Pat. No. 3,228,780 describes simply adding a pigment with potentially isocyanate reactive amino groups to polyurethane forming reactants and obtaining a coloured foam. U.S. Pat. No. 3,994,835 discloses coloured polyurethane foams with chemically incorporated dyestuffs prepared by incorporating a dispersion of a dye with free amino or hydroxyl groups into the polyurethane foam forming reaction mixture. 
     In the present invention, printing inks, in particular letterpress and offset printing inks, are presented, which, compared with the conventional pigment-based printing inks, make possible considerable advantages in the lack of hiding power, the brilliance, the gloss of the printings or the depth of colour, and, where appropriate, offer advantages in several, or even all, of the said points. 
     SUMMARY OF THE INVENTION 
     The printing inks of the present invention are based upon a specific class of colouring agents obtained by reacting dyestuff molecules bearing reactive hydrogens with free NCO group bearing resins. The particularly suitable colouring agents of the present invention are obtained by utilizing free NCO group bearing resins which contain the residues of monocarboxylic acids and the residues of polyols. The printing inks of the present invention may also contain an independent varnish and common printing ink additives such as siccatives, anti-skinning agents and flow control agents. 
     These printing inks preferably contain a colouring agent obtained by reacting a dyestuff of the formula 
     
         F(Y&#39;H).sub.n                                               I 
    
     in which 
     F designates a dyestuff radical, 
     Y&#39; designates --O--, --S--, ##STR1## R 1  designates hydrogen, alkyl, preferably C 1  to C 4  alkyl, or cycloalkyl, preferably cyclopentyl or cyclohexyl and 
     n designates an integer between 1 and 6 inclusive 
     with a resin which carries at least one isocyanate group and at least eighteen carbon atoms. 
     The particularly suitable colouring agents are obtained from the reaction of between about 3 and 70 weight percent of the dyestuffs of formula I with between about 97 and 30 weight percent of a free NCO group bearing resin which is itself the reaction product of 
     (i) between about 8 and 35 weight percent of one or more polyalcohols bearing between 2 and 6 hydroxyl groups, 
     (ii) between about 15 and 80 weight percent of one or more monocarboxylic acids, 
     (iii) between about 0 and 50 weight percent of one or more dicarboxylic acids, 
     (iv) between about 0 and 50 weight percent of aliphatic, cycloaliphatic or aromatic diisocyanates whose isocyanate groups are fully reacted in the formation of said resin, and 
     (v) between about 9 and 75 weight percent of aliphatic, cycloaliphatic or aromatic diisocyanates who, on average, retain one unreacted isocyanate group after formation of said resin. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The printing inks of the present invention preferably contain colouring agents of the formula ##STR2## in which F designates a dyestuff radical, 
     Y designates a direct bond or the radical of a group --Y--H which can be added onto an NCO group, 
     R designates an organic radical, and 
     n designates 1, 2, 3, 4, 5 or 6, it being possible when n≧2 for the radicals ##STR3##  to be identical or different, with the proviso that the total number of C atoms in the n R radicals is ≧18, 
     and the particular suitable colouring agents of the formula ##STR4## in which R 2  and R 4  designate organic radicals, 
     R 3  designates an aliphatic radical, 
     m designates 1, 2, 3, 4 or 5, and 
     p designates 0, 1, 2, 3 or 4. 
     Also preferred are the particularly suitable colouring agents which have a structural element of the formula ##STR5## in which R 5  designates ##STR6## R 6  and R 7  designate organic radicals, and q 2  designates 2, 3, 4, 5, 6, 7, 8, 9 or 10. R 2  and R 7  preferably represent alkylene, cycloalkylene or arylene radicals, for example represent ##STR7## R 3  preferably represents an alkyl radical, particularly preferably a C 1  -C 8  -alkyl radical which can be interrupted by 0 atoms and substituted by, for example, C 1  -C 6  -alkoxy; in the case where R 3  is derived from a sugar alcohol, R 3  can also have a cyclic ether group. 
     R 4  preferably designates an aliphatic or an aromatic hydrocarbon radical which can have 4-23 C atoms and can be substituted by, for example, --OH, ═O, or halogen (chlorine). The aliphatic radical can be acyclic or cyclic, saturated or unsaturated; the unsaturated radical preferably contains 1-3 double bonds. An aromatic radical is preferably a phenyl radical. 
     R 6  preferably designates an aliphatic or an aromatic hydrocarbon radical which can have 1-16 C atoms and can be substituted by, for example, --OH, ═O, or halogen (chlorine). The aliphatic radical preferably contains 1-3 double bonds. An aromatic radical is preferably a phenylene radical. 
     The dyestuffs F(Y&#39;H) n  from which F is derived can belong to a very wide variety of dyestuff classes, for example to the triphenylmethane, oxazine, dioxazine, thiazine, nitro, anthraquinone, coumarin, quinophthalone, benzodifuranone, perylene and naphthalimide, but especially the azo, most especially the monoazo, phthalocyanine or methine, series. 
     In a typical embodiment, suitable colouring agents are prepared by reaction of 
     1. 3-70% by weight, preferably 3-55% by weight, particularly preferably 20 to 40% by weight, of an organic dyestuff of the formula F(Y&#39;H) n  with 
     2. 97-30% by weight, preferably 97-45% by weight, particularly preferably 80-60% by weight, of a NCO-functional compound. 
     The NCO-functional resin (2) should preferably be prepared from the following components: 
     (A) 8-35% by weight, particularly preferably 10-25% by weight, of one or more polyalcohols having 2-6 hydroxyl groups, 
     (B) 15-80% by weight, particularly preferably 24-70% by weight, of a monocarboxylic acid or of a monocarboxylic acid mixture selected from the groups of (a) the essentially unsaturated natural or isomerized natural fatty acid mixtures, (b) the essentially saturated natural fatty acids or (c) the synthetic aliphatic, straight-chain or branched fatty acids, (d) the monocyclic, cycloaliphatic monocarboxylic acid, (e) the polycyclic, optionally unsaturated natural (terpenoid) resin acids, or those obtained from the latter by isomerization, hydrogenation or partial dehydrogenation, and (f) the aromatic, optionally alkyl-substituted C 6  -C 14  -monocarboxylic acids, 
     (C) 0 to 50% by weight, particularly preferably 0 to 35% by weight, of one (or more) aliphatic, cycloaliphatic or aromatic dicarboxylic acid(s) or their esterifiable derivatives, 
     (D) 0 to 50% by weight, particularly preferably 0 to 35% by weight, of one (or more) aliphatic, cycloaliphatic or aromatic diisocyanate(s), essentially both NCO groups of which are reacted on formation of the NCO-functional resin, and 
     (E) 9 to 75% by weight, particularly preferably 20 to 60% by weight, of one (or more) aliphatic, cycloaliphatic or aromatic diisocyanate(s), very particular preference being given to those diisocyanates having two NCO groups of different reactivity, with the proviso that the total of (A), (B), (C), (D) and (E) is 100%, and the isocyanates of component (E) on average mainly react with only one of their NCO groups, and the second, which is, where appropriate, less reactive, remains essentially unreacted. 
     The reaction of components (A) to (E) to give the NCO-functional resin (2) is advantageously carried out in such a manner that initially (A) is reacted with (B), (C) and (D) to give a OH-functional precondensate which is then reacted with (E) to give the resin (2). If the intention is to prepare products of natural fatty acids--(B), groups (a) and (b)--then it may be advantageous to use these fatty acids in the form of the naturally occurring oils (triglycerides) and to transesterify the oils with polyalcohols (A) by the known processes to give hydroxy-functional partial ester intermediates which can then be reacted with (C), (D) and (E) and, where appropriate, directly with (E), to give the resin (2). 
     Examples of suitable polyalcohols (component (A)) which contain the radical R 3  are: ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butylene glycol, 2,3-butylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, 2,2,2&#39;,2&#39;-tetramethylol di-n-butyl ether, dipentaerythritol, diglycerol, sugar alcohols such as xylitol, mannitol and sorbitol, it being necessary to take account of the fact that on esterification with carboxylic acids the mean effective functionality of these alcohols is diminished by about 2 owing to the formation of cyclic internal ethers. 
     Examples of monocarboxylic acids R 4  --COOH (component (B)) from group (a) of drying and semi-drying natural fatty acids or those obtained from the natural fatty acids by isomerization: Linseed oil fatty acid, soya oil fatty acid, cottonseed oil fatty acid, peanut oil fatty acid, (con)juvandol fatty acid, ricinenic acid (obtained from natural castor oil or ricinoleic acid by dehydration), oiticica oil fatty acid, tall-oil fatty acid and safflower oil fatty acid. 
     An example of monocarboxylic acids (B) R 4  --COOH from group (b) of essentially saturated natural fatty acids is coconut fatty acid. The fatty acid cuts which are obtained from the natural fatty acid mixtures, for example by fractionation, and which mainly contain C 22  -monocarboxylic acid (behenic acid), C 18  -monocarboxylic acid (stearic acid) or C 16  -monocarboxylic acid (palmitic acid) in addition to acids of higher or lower C number, ought also to be mentioned here by way of example. 
     Examples of monocarboxylic acids (B) R 4  --COOH from group (c) of synthetic saturated fatty acids are isooctanoic acid, isononanoic acid and isotridecanoic acid. 
     Typical monocarboxylic acids (B) R 4  --COOH from group (d) of cycloaliphatic, optionally olefinically unsaturated, monocarboxylic acids are the C 6  - and C 7  -carboxylic acids, cyclopentanecarboxylic acid, cyclohexane carboxylic acid and 1,4,5,6-tetrahydrobenzoic acid. 
     Examples of monocarboxylic acids (B) R 4  -COOH from group (e) of optionally substituted aromatic monocarboxylic acids are benzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 4-tert.-butylbenzoic acid, 4-chlorobenzoic acid and anisic acid. 
     Examples of monocarboxylic acids (B) R 4  --COOH from group (f) of resin acids or colophony derivatives are abietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, isopimaric acid, laevopimaric acid etc. 
     Examples of suitable dicarboxylic acids (C) corresponding to HOOC--R 6  --COOH or their esterifiable derivatives are succinic acid (anhydride), glutaric acid (anhydride), adipic acid, pimelic acid, azelaic acid, suberic acid, sebacic acid, dodecanedioic acid, cyclohexane-1,2-dicarboxylic acid (anhydride), 1,2,3,6-tetrahydrophthalic acid (anhydride), phthalic acid (anhydride) and isophthalic acid. Possible, but less preferred, examples are unsaturated aliphatic acids such as fumaric acid, maleic acid (anhydride) and itaconic acid. 
     In the case where the printing ink according to the invention contains a colouring agent and, where appropriate, one or more additives, but no varnish, the colouring agent is a dyestuff-modified resin, that is to say the colouring agent is chemically incorporated in the varnish. 
     However, the printing inks according to the invention preferably contain the colouring agent mixed with a varnish. The varnish contains, for example, alkyd resins, urethane-alkyds, hard resins, linseed oil, stand oils and mineral oils, which can be mixed together or boiled down. 
     The printing inks according to the invention can be used in known manner for printing. 
     The letterpress or offset printing inks can be used by the customary processes for sheet-fed, but preferably for rotary letterpress and offset printing. In this context, it is possible to prepare four-colour prints with suitable black pigments (carbon black) and the three hues of trichromatic printing, in which all three hues (magenta, cyan and yellow) are generated by means of the colouring agents of the invention. However, it is equally possible to provide only two hues, preferably yellow and magenta, with the colouring agents of the invention. Finally, it is also possible, for one or more hues, to use printing ink pigments and the color bodies described in this invention in conjunction with each other. 
     The combined use of colouring agents of the present invention and pigments in printing inks can, for example, be advantageous where the object is to obtain a particularly homogeneous large-area printing, to shade a printing ink, to improve the brilliance of a printing with organic pigments, to reduce the hiding power of a pigment print, to improve the properties of carbon black in respect of brilliance and gloss and transparency in four colour printing, or to improve the rheology and printing characteristics of the conventional sheet-fed or rotary letterpress or offset printing inks. 
     Since the conventional pigment-based letterpress and offset printing inks are fully compatible with the colouring agents of the present invention, addition thereof is possible in any desired ratio. 
     Accordingly, the invention also relates to printing inks, in particular letterpress and offset printing inks, containing a colouring agent mixture, where appropriate a varnish and, where appropriate, one or more additives such as siccatives, anti-skinning agents and flow-control agents, characterized in that the colouring agent mixture contains at least one colour body of the present invention in addition to a coloured pigment or carbon black. 
     In the following text, some dyestuff types of the formula F(Y&#39;H) n  which can preferably be used for the preparation of colouring agents of the present invention are listed by way of example. 
     A. Pyridone-azo dyestuffs of the formula ##STR8## in which D designates the radical of a diazo component, 
     T 1  designates alkyl, aryl or --COOT 4 , 
     T 2  designates H, --CN, --COOT 4  or --CONH--T 5  (OH) 1 , 
     T 3  designates aliphatic or araliphatic radicals which can be interrupted by one or more oxygen atoms, 
     T 4  designates hydrogen or alkyl, 
     T 5  designates aliphatic or araliphatic radicals which can be interrupted by one or more oxygen atoms, and 
     k and l designate 0, 1, 2, 3 or 4, with the proviso that the total of k+1 is 1, 2, 3 or 4. 
     D preferably represents a phenyl radical which can carry 1-4 substituents from the series comprising optionally substituted C 1  -C 12  -alkyl, C 2  -C 12  -alkenyl, cyclohexyl, cyclopentyl, cyclohexenyl, halogen such as Cl, Br or F, C 1  -C 6  -alkoxy, optionally substituted phenoxy, --CN, --CF 3 , --NO 2 , optionally substituted C 1  -C 18  -alkylsulphonyl, optionally substituted phenylsulphonyl, optionally substituted benzylsulphonyl, optionally substituted phenoxysulphonyl, optionally substituted carbamoyl and optionally substituted sulphamoyl. 
     The alkyl radicals in C 1  -C 12  -alkyl and C 1  -C 18  -alkylsulphonyl can be substituted by, for example, --OH, C 1  -C 6  -alkoxy or --CN. The phenyl radicals in phenoxy, phenylsulphonyl, phenoxysulphonyl and benzylsulphonyl can be substituted by, for example, C 1  -C 4  -alkyl or halogen such as Cl and Br. 
     The carbamoyl groups preferably carry two identical or different substituents from the series comprising C 1  -C 18  -alkyl, which can be substituted by, for example, --OH, C 2  -C 18  -alkenyl, aryloxyalkyl, C 9  -C 11  -aralkoxyalkyl, C 7  -C 11  -aralkyl, C 4  -C 13  -acyloxyalkyl, C 6  -C 14  -alkoxycarbonyloxyalkyl, C 6  -C 12  -alkylaminocarbonyloxyalkyl and C 4  -C 9  -dialkylaminoalkyl; appropriate diazo components are disclosed in German Patent Specification Al No. 3,111,648. 
     The sulphamoyl groups preferably carry 1 or 2 substituents from the series comprising C 1  -C 18  -alkyl, or C 7  -C 11  -aralkyl or C 1  -C 12  -alkyl which is optionally interrupted by 0 and optionally substituted by hydroxyl or phenoxy; appropriate diazo components are disclosed in European Patent Specification Al No. 18,567. 
     The following may be mentioned as examples of diazo components: aniline, o-, m- and p-toluidine, o- and p-ethylaniline, 2,3-dimethylaniline, 3,4-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, o-i-propylaniline, p-i-propylaniline, 2,4,5- and 2,3,5-trimethylaniline, 2-methyl-5-i-propylaniline, 4-tert.-butylaniline, 4-sec.-butylaniline, aniline which is substituted in the o- or p-position by straight-chain or branched C 12  -C 25  -alkyl, 4-cyclohexylaniline, 4-cyclohexyl-2-methylaniline, 4-(1-cyclohexen-1-yl)-aniline, o-, m- and p-chloroaniline, 2,3-, 2,4-, 2,5- and 3,4-dichloroaniline, 5-chloro-2-methylaniline, 4-chloro-2-methylaniline, 3-chloro-2-methylaniline, 2-chloro-5-methylaniline, 4-chloro-3-methylaniline, 3-chloro-4-methylaniline, 2-chloro-3,4-dimethylaniline, 5-chloro-2,4-dimethylaniline, 4-chloro-2,5-dimethylaniline, o-, m- and p-nitroaniline, 2-chloro-4-nitroaniline, 2-nitro-4-chloroaniline, 2-methyl-4-nitroaniline, 4-methyl-2-nitroaniline, 2,4-dimethyl-5-nitroaniline, 2,5-dimethyl-4-nitroaniline, 4-i-propyl-2-nitraniline, 4-tert.-butyl-2-nitroaniline, 4-cyclohexyl-2-nitroaniline, o-, m- and p-methoxyaniline, 2-ethoxy and 4-ethoxyaniline, 2-phenoxyaniline, 2-(2-methylphenoxy)-aniline, 5-chloro-2-methoxyaniline, 5-chloro-2-phenoxyaniline, 5-chloro-2-(4-chlorophenoxy)-aniline, 4,5-dichloro-2-methoxyaniline, 2-methoxy-5-nitroaniline, 2-methoxy-4-nitroaniline, 3-chloro-4-methoxyaniline, 4-methoxy-2-nitroaniline, 4-ethoxy-2-nitroaniline, 4-ethoxy-3-nitroaniline, 3-methoxy-4-methylaniline, 4-methoxy-2-methylaniline, 2-methoxy-5-methylaniline, 2-ethoxy-5-methylaniline, 4-chloro-2-methoxy-5-methylaniline, 4-chloro-2,5-dimethoxyaniline, 2,5-dimethoxy-4-nitroaniline, 2 -(phenylsulphonyl)-aniline, 2-(methylsulphonyl)-4-nitroaniline, 2-methoxy-5-(phenylsulphonyl)-aniline, 5-(benzylsulphonyl)-2-methoxyaniline, 5-(ethylsulphonyl)-2-methoxyaniline, ##STR9## 
     In the case where k in formula (V) is &gt;0, that is to say the diazo component has 1-4 hydroxyl groups, D preferably represents a phenyl radical which can be substituted by hydroxy-C 1  -C 18  -alkoxy, --NO 2 , --CN, F, Cl, Br or C 1  -C 4  -alkyl, or by a radical of the formulae ##STR10## 
     In which 
     T 6  and T 8  designate aliphatic radicals which can be interrupted by one or more O atoms and 
     T 7  designates hydrogen or an aliphatic or araliphatic radical which may be interrupted by one or more O atoms. 
     It is equally possible to use dyestuffs which, together with the diazo components indicated for formula V, contain coupling components from the pyrimidone, pyrazolone, aminopyrazole or indole series. 
     B. Aminoazobenzene dyestuffs of the formula ##STR11## in which A 1 , A 2  and A 3  designate hydrogen, halogen such as Cl, Br or F, --CN, --NO 2 , C 1  -C 6  -alkyl, in particular methyl and ethyl, cycloalkyl, in particular cyclopentyl and cyclohexyl, C 1  -C 6  -alkoxy, in particular methoxy and ethoxy, optionally substituted phenoxy, optionally substituted C 1  -C 18  -alkylsulphonyl, optionally substituted phenylsulphonyl, optionally substituted sulphamoyl, optionally substituted carbamoyl, optionally substituted phenylazo, C 1  -C 6  -alkoxycarbonyl, --CF 3 , --SCN, C 1  -C 12  -alkylmercapto, C 1  -C 6  -alkylcarbonyl, optionally substituted phenylcarbonyl, or --OH, A 4  and A 5  designate hydrogen, halogen, such as Cl, Br or F, optionally substituted C 1  -C 6  -alkyl, in particular methyl and ethyl, optionally substituted C 1  -C 6  -alkoxy, in particular methoxy and ethoxy, optionally substituted --NH--CO--C 1  -C 6  -alkyl, in particular --NH--CO--CH 3  and --NH--CO--C 2  H 5 , or optionally substituted --NH--SO 2  --C 1  -C 6  -alkyl, in particular --NH--SO 2  --CH 3  and --NH--SO 2  --C 2  H 5 , A 6  and A 7 , independently of one another, designate hydrogen, optionally substituted C 1  -C 12  -alkyl or C 3  -C 12  -cycloalkyl, for example substituted with --OH, --NH 2  or --CN, or radicals of the formulae ##STR12##  with the proviso that the dyestuff has at least one substituent which can react with an isocyanate. The following compounds of the formula VI are preferably used: 
     1. Compounds in which ##STR13## A 8  designating Cl, Br or CN, X designating H, CH 3 , C 2  H 5 , C 6  H 12 , tert.-butyl, C 1  -C 4  -alkoxy, Cl or Br, 
     X 1  designating --NO 2 , --CN, --CF 3  or C 1  -C 12  -alkylsulphonyl, and 
     X 2  designating --NO 2  or --CN. 
     2. Compounds in which ##STR14## A 9  designating hydrogen, chlorine, C 1  -C 4  -alkyl, in particular methyl and ethyl, and C 1  -C 4  -alkoxy, in particular methoxy and ethoxy, and A 10  representing hydrogen, halogen such as Cl, Br or F, optionally substituted C 1  -C 6  -alkyl, in particular methyl and ethyl, optionally substituted alkoxy, in particular methoxy and ethoxy, optionally substituted --NH--CO--C 1  -C 6  -alkyl, in particular --NH--CO--CH 3  and --NH--CO--C 2  H 5 , and optionally substituted --NH--SO 2  --C 1  -C 6  -alkyl, in particular --NH--SO 2  --CH 3  and --NH--SO 2  --C 2  H 5 . 
     It is equally possible to use dyestuffs of the formula ##STR15## in which D 1  designates the radical of a diazo component from the thiophene, thiazole, thiadiazole, benzothiazole or benzisothiazole series. 
     C. Methine dyestuffs of the formula ##STR16## in which Z 1  designates --CN, --COOCH 3 , --COOC 2  H 5 , --COOC 2  H 4  OH, --SO 2  CH 3 , --SO 2  C 2  H 5  or --SO 2  C 2  H 4  OH, 
     Z 2  designates H or CN, 
     Z 3  designates C 1  -C 6  -alkyl, 
     Z 4  designates C 1  -C 6  -alkyl, hydroxy-C 1  -C 6  -alkyl, phenyl or benzyl, and 
     Z 5  designates hydroxy-C 1  -C 6  -alkyl. 
     D. Copper phthalocyanine dyestuffs of the formula 
     
         CuPc(SO.sub.2 NX.sub.3 X.sub.4).sub.1-6                    IX 
    
     in which 
     X 3  designates hydrogen, C 1  -C 6  -alkyl, hydroxy-C 1  -C 6  -alkyl or amino-C 1  -C 6  -alkyl, and 
     X 4  designates hydroxy-C 1  -C 6  -alkyl or amino-C 1  -C 6  -alkyl. 
     E. Rhodamine dyestuffs of the formula ##STR17## in which X 5 , X 7 , X 8  and X 9  designate hydrogen, or C 1  -C 6  alkyl which is optionally substituted by hydroxyl, 
     X 6  and X 10  designate C 1  -C 6  -alkyl which is optionally substituted by hydroxyl, 
     X 11  designates hydrogen, or C 1  -C 6  -alkyl which is optionally substituted by hydroxyl, 
     X 12  designates hydroxy-C 1  -C 6  -alkyl, and 
     An.sup.⊖ designates an anion. 
     Individual examples of dyestuffs of the formula F(Y&#39;H) n  are: ##STR18## Complex chromium compound composed of 1 atom of Cr and 2 mol of the dyestuff of the formula ##STR19## Complex chromium compound composed of 1 atom of Cr and 2 mol of the dyestuff of the formula ##STR20## Complex chromium compound composed of 1 atom of Cr and 2 mol of the dyestuff of the formula ##STR21## Complex cobalt compound composed of 1 atom of Co and 2 mol of the above mentioned dyestuff. ##STR22## 
    
    
     The examples which follow serve further to illustrate the invention but should not be understood to be restrictive. Parts are always parts by weight. (Examples 1-49: precursors; Examples 50-119: products according to the invention). 
     EXAMPLES 1 AND 2 
     Preparation of a NCO-functional resin 
     EXAMPLE 1 
     Preparation of a trimethylolpropane ester of linseed oil fatty acid 
     1,946 parts of linseed oil fatty acid and 469 parts of trimethylolpropane are heated, while passing nitrogen through, to 140° C. in 1 h and then to 220° C. in 8 h, the water of reaction being distilled via a distillation apparatus under a reflux condenser into a receiver. The acid number after 3 h at 220° C. was 4.2. 
     EXAMPLE 2 
     Preparation of the NCO-functional resin 
     186.9 parts of the resin from Example 1 and 52.5 parts of toluylene diisocyanate (technical mixture with about 80% by weight of the 2,4-isomer in addition to about 20% by weight of 2,6-diiocyanatotoluene) are reacted together under N 2  at 80° C. for 1 h. The content of free isocyanate is then 5.28% by weight (theory: 5.27% by weight). 
     EXAMPLES 3-21 AND 22-49 
     Preparation of NCO-functional resins corresponding to (2) 
     EXAMPLES 3-21 
     Hydroxy-functional precursors 
     In analogy to Example 1, OH-functional precursors for the NCO-functional resins are prepared from carboxylic acids and polyalcohols, see Table 1 (abbreviations: 
     TMP=trimethylolpropane, penta=pentaerythritol, 
     NPG=neopentylglycol, and adipol=1,6-hexane diol). 
     
                                           TABLE 1__________________________________________________________________________            Parts      Parts                           Measured                                 MeasuredEx-              by         by  OH    Acidample    Carboxylic acid            Weight                Polyalcohol                       Weight                           Number                                 Number__________________________________________________________________________3   Soya oil fatty acid            560 TMP    134 72    44   Soya oil fatty acid            1400                Penta  227 56    45   Linseed oil fatty acid            1390                Penta  227 64    46   Linseed oil fatty acid            1112                Penta  272 81    3    Benzoic acid 2447   Linseed oil fatty acid            1112                Penta  272 82    4    4-tert.-butylbenzoic            328    acid8   Linseed oil fatty acid            278 Penta   68 54    4    abietic acid 1609   Linseed oil fatty acid            1043                Penta  204 40    5    Adipic Acid  11010  Linseed oil fatty acid            1112                Adipol 472 154   211  Linseed oil fatty acid            556 NPG    208 134   112  Linseed oil fatty acid            1390                Penta  340 142   413  Hydrogenated abietic acid            726 TMP    134 48    614  Conjuvandol fatty acid            1390                TMP    335 87    415  Hydr. abietic acid            362 TMP    134 62    4    Linseed oil fatty acid            27816  Hydr. abietic acid            724 Penta  136 35    5    Linseed oil fatty acid            27817  Hydr. abietic acid            362 Penta  136 40    4    Linseed oil fatty acid            55618  Stearic acid 569 Penta  272 96    3    Benzoic acid 48819  Stearic acid 1280                Penta  204 56    420  Soya oil fatty acid            560 TMP    268 371   421  Linseed oil fatty acid            834 Penta  272 89    4    Benzoic acid 366__________________________________________________________________________ 
    
     EXAMPLES 22-49 
     Preparation of NCO-functional resins corresponding to (2) from the precursors 3-21 
     In analogy to Example 2, NCO-functional resins are prepared from the precursors 3-21 with isocyanates, see Table 2 (abbreviations in the following tables: 
     IPDI=isophorone diisocyanate, HDI=hexamethylene diisocyanate, TDI 100=2,4-diisocyanatotoluene, TDI 80=toluylene diisocyanate isomer mixture with about 80% of 2,4-diisocyanatotoluene and about 20% of 2,6-diisocyanatotoluene). 
     
                                           TABLE 2__________________________________________________________________________NCO-func.product     OH-precursorExample   from Example             Parts by weight                     Diisocyanate                            Parts by Weight__________________________________________________________________________22        3       131.6   IPDI   44.423        4       184.4   IPDI   44.424        5       181.2   IPDI   44.425        6       304     TDI 80 69.626        7       320.8   TDI 80 69.627        8       189.6   TDI 80 33.128        9       255     HDI    25.229        10      264.6   HDI    117.630        11      182     TDI 80 8731        12      147.6   TDI 80 69.632        13      46.7    TDI 80 7.033        14      98.1    TDI 80 26.134        15      127.5   TDI 80 26.135        16      143.5   TDI 80 17.436        17      190     TDI 80 26.137        18      122.1   TDI 80 34.838        19      280.7   TDI 80 52.239        20      69.2    IPDI   88.8__________________________________________________________________________ 
    
     Furthermore, the following NCO-functional resins 40-49 are prepared from the precursors of Table 1 in analogous manner (see Example 2) with diisocyanates changed compared with Table 2 (Table 3). 
     
                                           TABLE 3__________________________________________________________________________NCO-funct. product     OH precursorExample   from Example             Parts by weight                     Diisocyanate                            Parts by Weight__________________________________________________________________________40        3       131.6   HDI    33.641        4       276.6   HDI    50.442        5       181.2   HDI    33.643        5       137.1   TDI 80 26.144        1       91.6    TDI 100                            17.445        1       130.8   IPDI   44.446        1       128.8   HDI    33.647        21      272.8   TDI 80 69.648        9       182.3   IPDI   28.949        1       196.2   TDI 100                            52.2__________________________________________________________________________ 
    
     EXAMPLE 50 
     306.3 g of the precursor from Example 2 and 96.96 g of a yellow methine dyestuff of the following structure (1) ##STR23## are reacted together in 3,000 ml of dry cyclohexanone at 80° C. for 12 h; undissolved portions of the dyestuff (1) dissolve during the course of the reaction. Subsequently, cyclohexanone is removed by distillation at 15 Torr, finally at about 1 Torr/120° C. internal temperature. The product is a glass-like solid mass which is very slightly sticky and is miscible with commercially available varnishes and mineral oils for sheet-fed and rotary letterpress and offset printing. 
     A formulation of the following composition, for example, can be used for testing and printing: 
     
         ______________________________________56 parts by weight          of a 50% strength solution of a          commercially available rotary off-          set varnish based on a long-oil          linseed oil alkyd resin and a          resin ester, as described in the          Lackrohstoff-Tabellen (Tables of          Raw Materials for Surface Coat-          ings) by Karsten, 7th edition,          1981,23 parts by weight          of a pigment, for example          according to Example 50,21 parts by weight          of a mineral oil of limited          aromatic content and narrow          boiling range, for example          210/230° C. or 230/260° C..100 parts by weight______________________________________ 
    
     In the same manner as in Example 50, dyestuffs (1)-(24) are reacted with precursors 2 and 22 to 49 (variant I). If the batch sizes are changed, the amount of cyclohexanone is corrected correspondingly. In addition, two process variants are indicated, in which a commercially available offset printing varnish (stated amount: varnish based on the total solids content) is admixed before removal of the cyclohexanone by distillation, specifically in variant II a varnish based on a urethane-alkyd (Desmalkyd® L 181) and in variant III a resin based on a long-oil linseed oil alkyd resin combined with a resin ester and/or a phenol resin modified with colophony. 
     The products are then obtained as highly viscous pastes or glass-like masses which can be mixed with (other) commercially available offset printing ink vehicles. 
     EXAMPLES 51-119 
     In Examples 51-119, the following dyestuffs (2) to (24) are additionally used: ##STR24## 
     
                                           TABLE 4__________________________________________________________________________                     Parts by                     weight of  Parts by       Precursor               Parts by                     unreactedEx- Dye-  weight of       NCO-functional               Weight of                     dyestuff removed                                   % by weightample    stuff  dyestuff       from Example               precursor                     by filtration                              Variant                                   of Varnish__________________________________________________________________________51  (1)  8.3  2       24.8  --       II   2552  (1)  8.3  34      24.8  Trace    I    --53  (1)  6.9  35      29.1  0.34     II   2554  (1)  6.9  36      32.8  Trace    I    --55  (2)  5.5  22      17.6  0.62     II   8056  (2)  8.3  22      13.2  Trace    II   7557  (2)  5.5  23      22.9  --       II   5058  (2)  5.5  24      22.8  --       II   5059  (2)  11.0 24      22.6  --       II   6760  (2)  41.3 25      165.0 --       III  2561  (2)  77.3 26      232.0 --       III  2562  (2)  41.3 27      175.8 --       III  2563  (2)  27.5 37      89.7  --       I    --64  (2)  22.0 38      98.9  --       I    --65  (2)  38.5 38      86.6  2.0      I    --66  (2)  11.0 39      15.8  Trace    II   5067  (2)  5.5  40      16.5  --       II   5068  (2)  66.0 41      261.6 --       II   5069  (2)  11.0 41      21.8  Trace    II   6770  (2)  5.5  42      21.5  --       II   5071  (2)  41.3 43      190.9 --       III  2572  (2)  5.5  45      17.5  0.03     II   5073  (2)  5.5  46      16.2  --       II   5074  (2)  27.5 46      81.2  --       III  2575  (2)  41.3 47      143.3 --       III  2576  (3)  39.8 23      183.0 12.6     II   5077  (3)  69.6 23      160.2 2.65     III  2578  (3)  29.8 27      114.6 3.75     III  2579  (3)  49.7 31      54.3  6.8      III  25       43      121.780  (3)  37.3 43      176.0 0.39     III  --81  (4)  14.1 22      35.2  --       II   5082  (5)  15.3 2       38.7  --       II   2583  (5)  26.8 2       139.6 1.7      II   2584  (5)  34.5 43      114.5 0.23     II   2585  (5)  7.7  44      49.9  Trace    II   2586  (5)  7.7  44      49.4  Trace    III  2587  (5)  11.5 49      53.6  Trace    III  2588  (6)  15.2 28      141.7          III  2589  (6)  20.2 48      142.1 Trace    I    --90  (7)  10.5 2       29.3  0.08     II   2591  (7)  7.0  25      21.0  Trace    II   2592  (7)  27.9 29      43.7  --       III  5093  (7)  17.4 31      60.9  --       II   2594  (7)  7.0  31      24.3  Trace    II   25       43      28.195  (7)  8.7  32      37.5  --       I    --96  (7)  34.9 43      111.1 --       II   2597  (7)  7.0  44      26.0  0.11     II   2598  (8)  7.0  43      22.2  1.78     II   2599  (9)  8.7  2       37.3  0.16     II   25100 (10)  6.0  2       26.0  --       II   25101 (10)  10.1 30      26.9  --       I    --102 (11)  6.0  2       26.0  --       II   25103 (12)  10.4 2       26.0  --       II   25104 (13)  9.8  2       21.6  --       II   25105 (14)  10.1 2       21.0  --       II   25106 (15)  9.9  2       35.7  --       II   25107 (15)  12.4 2       22.3  --       II   25108 (16)  4.8  22      16.6  --       II   25109 (16)  4.8  2       8.3   --       II   25110 (17)  8.0  2       27.4  --       II   25111 (18)  7.7  2       27.4  --       II   25112 (19)  8.4  2       27.4  --       II   25113 (20)  8.4  2       24.8  --       II   25114 (20)  8.4  33      24.8  --       II   25115 (21)  8.9  2       24.8  --       II   25116 (22)  11.2 2       24.8  3.8      II   25117 (23)  11.6 2       33.5  0.2      I    --118 (1)  48.8 2       302.4 --       I    --119 (24)  124.7       2       298.3 --       I    --__________________________________________________________________________ 
    
     Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.