Patent Publication Number: US-4259224-A

Title: Copolymer solution of acrylic resin, process for its manufacture and use thereof in reactive lacquers

Description:
BACKGROUND OF THE INVENTION 
     (1) Field of the Invention 
     It is a further object of the present invention to provide a process for the manufacture of the copolymer solutions and for the use thereof as a binder component, wherein the sheet-like structures which can be produced therefrom have considerably improved porperties in various respects. This includes the property that the lacquer which has been applied to a metallic substrate and which contains the new copolymer solutions in combination with organic polyisocyanates, shall, after drying in the air for three to four days at temperatures of about 20° C., cure in such a way that the film no longer swells under the influence of water and also cannot be removed mechanically by scratching, even if the film is exposed to water for a brief period at temperatures of 50°-70° C. 
     It is a further object of the present invention to provide an acrylic resin, containing hydroxyl groups, which, in combination with polyisocyanates, provides the binder foundation for air-drying lacquers and also stoving lacquers which are suitable for top coats of lacquer in the automobile industry, the top lacquer being present after stoving in layer thicknesses of about 40 to 80 μm and the top lacquer being located directly on top of the stoved primer of electro-coating lacquer. 
     In the modern methods of the present time for lacquering motor vehicles in the automobile factory, the coachwork parts are usually provided, after phosphating, with a primer of electrocoating lacquer and the latter is stoved to give a plastic coating. A spraying lacquer or a coating composition, which is usually designated a filler, is then applied to this plastic coating, usually by a spray process, and is again stoved. 
     The pigmented formulation of automobile lacquer is then applied, in the desired pigmentation, to this two-layer coat of lacquer or primer, by spraying, and the automobile body is stoved again. 
     The complete coating, which, as explained above, consists of three layers, has a layer thickness of 70-100 μm after stoving, of which the proportion relating to the outer layer of top lacquer is 30 to 40 μm. In the course of methods of rationalisation in the automobile industry efforts are being made to change over from the three-layer system to a two-layer build-up. In this, the electrocoating lacquering or another equivalent primer is intended to form the first coating layer and the final lacquering with the pigmented lacquer is intended to be built up thereafter, the total thickness of the layers applied being intended, however, to have the same layer thickness. Using the conventional automobile top lacquers, however, it is not possible to produce, from pigmented lacquer formulations in the customary spraying and stoving treatment, coatings of a type which, after drying in the air or after stoving, give lacquer films which are completely uniform (that is to say free from so-called curtaining and free from craters and blisters). 
     It is the object of the present invention to provide an acrylic resin, containing hydroxyl groups, which, in combination with polyisocyanates, provides the binder foundation for air-drying lacquers and stoving lacquers which are suitable for top coats of lacquer in the automobile industry, the top lacquer being present after stoving in layer thicknesses of about 40 to 80 μm and the top lacquer being located directly on top of the stoved primer of electrocoating lacquer or on top of another suitable primer. 
     In addition, the less viscous copolymer solutions used according to the invention exhibit a better absorption of pigment both when using inorganic pigments, such as, for example, titanium dioxide, or organic pigments, such as, for example, carbon black. When titanium dioxide is used as the pigment, the copolymers manufactured according to the invention, and the reactive lacquer manufactured therefrom, still produce high-gloss films at a pigment/binder ratio of 1.5 to 2:1, whilst the known copolymers and the known reactive lacquers manufactured therefrom exhibit a distinct falling off in gloss at the same level of pigmentation. In addition, it has been found that the copolymers manufactured according to the invention and the reactive lacquers manufactured therefrom produce high-gloss lacquers with carbon black, whilst the known copolymers and the reactive lacquers manufactured therefrom display matt films at the same level of pigmentation. 
     It is a further object of the invention to provide a process for the manufacture of soluble organic copolymers which are obtained as a solution with a solids content of 65 to 75% by weight, the copolymer solutions, when they have been adjusted to be ready for spraying, having a viscosity, at 25° C., of 25 seconds, measured in the DIN cup with a four mm flow orifice, and a solids content of 40 to 65% by weight, preferably 45 to 65% by weight. In this way the copolymer solutions manufactured according to the invention take account of the demands of environmental protection for binders of high solids content and low solvent content. 
     The upstanding advantage of the copolymer solutions manufactured according to the invention is the possibility that the hydroxyl groups of the copolymers are crosslinked with polyisocyanates at room temperature and at elevated temperatures and give lacquers which have a high solids content when adjusted to the ready-to-spray state, at a viscosity of 40 seconds, measured in the DIN cup having a 4 mm flow orifice, at 25° C., and a solids proportion of 61 to 80% by weight, preferably 65 to 80% by weight, in the clear lacquer. 
     (2) Prior Art 
     Numerous proposals have been disclosed to manufacture solvent-resistant and alkali-resistant lacquers by reacting polyisocyanates and copolymers containing hydroxyl groups and to convert them into coatings. DT-AS No. 1,247,006 describes a process for the production, by the polyisocyanate polyaddition process, of alkali-resistant sheet-like structures which are obtained from copolymers containing hydroxyl groups, and polyisocyanates, but which are not adequately water-resistant after a reaction time of three to four days at 20° C. These coatings, obtained by this known process, are, therefore, not suitable as top lacquers for external lacquering which are resistant to weathering, since blistering takes place after a very short time and the adhesion of the lacquer to the various metallic substrates falls off and as a result, the lacquer is detached from the substrate. 
     It is also known that polyhydroxy compounds of polyols can be cured with polyisocyanates in order to obtain crosslinked lacquer coatings with good resistance properties. These combinations also display too low a resistance to water and a fairly low resistance to weathering of the cured lacquer films. 
     The particular advantage of the copolymer solutions manufactured according to the invention is that the viscosity falls when the hydroxyl group content in the copolymers is increased. On dilution with xylene to 25 seconds at 25° C., measured in the DIN cup having a 4 mm flow orifice, the solids content of the copolymer solutions manufactured according to the invention then increases. 
     It is found, suprisingly, that the copolymers which have been manufactured according to the invention and have a hydroxyl group content of 3.5 to 6.5, preferably 4.5 to 5.5,% give lower viscosities than the known copolymers which have the same hydroxyl group content. Thus, in a 70% strength by weight solution in ethylglycol acetate, the copolymer solutions manufactured according to the invention give viscosities of U to Z 4 , preferably X to Z 3 , measured by the Gardner-Holdt method at 20° C. This observation is proved by a comparison between the copolymer solution, manufactured according to the invention, from Example 1 and the known comparison copolymers 3 and 4. As 70% strength by weight solutions in ethylglycol acetate, the comparison copolymers 3 and 4 giver higher viscosities in excess of Z 6 , measured by the Gardner-Holt method at 20° C. 
     When combined with polyisocyanates, the copolymers manufactured according to the invention have the following advantages, compared with the known copolymers: better resistance to solvents, higher abrasion resistance and better resistance to weathering in the Florida climate. In addition, the copolymers manufactured according to the invention, when combined with polyisocyanates and diluted with acetone, xylene or butyl acetate to a viscosity of 40 seconds at 25° C., measured in a DIN cup having a 4 mm flow orifice, give lacquers of higher solids content which have a solids content of 61 to 80% by weight, preferably from 65 to 80% by weight, in the clear lacquer. When such clear lacquers or pigmented lacquers are applied to steel sheets by spray application and are exposed to the air for a brief period and subsequently stoved, high dry film layer thicknesses of 70 to 80 μm are obtained, which do not exhibit crater-formation or blistering. 
     The known lacquer combinations which are described in French patent Specification No. 1,556,309, give only a solids content from 10 to 60% by weight in the clear lacquer, when they are diluted with acetone, butyl acetate or xylene to 40 seconds at 25° C. When such clear lacquers or pigmented lacquers are applied to steel sheets by spray application and are exposed to the air for a brief period and subsequently stoved, lower dry film layer thicknesses of 40 to 50 μm are obtained which, in addition, exhibit crater-formation and blistering. 
     SUMMARY 
     The subject of the invention is a copolymer solution consisting of 
     (A) 25 to 35% by weight of inert organic solvents customary in the lacquer industry and 
     (B) 65 to 75% by weight of copolymers which contain hydroxyl groups and have hydroxyl numbers of 130 to 200 and which are manufactured from: 
     (a) 20 to 45% by weight of unsaturated polyesters having acid numbers of 10 to 20 and having hydroxyl numbers of 100-250, which are synthesised from saturated dicarboxylic acids having 6-10 carbon atoms, unsaturated dicarboxylic acids having 4 carbon atoms or the anhydrides thereof and diols having 2-15 carbon atoms, it being possible for the saturated dicarboxylic acids having 6-10 carbon atoms to be replaced, to the extent of up to 20%, by saturated, dimeric fatty acids which have 36 carbon atoms and contain two carboxyl groups, together with 
     (b) 55-80% by weight of a mixture of monomers composed of α,β-ethylenically unsaturated compounds, it being necessary that the % by weight of unsaturated polyester and the % by weight of the mixture of monomers add up to 100% by weight, the said mixture consisting of 
     (b 1 ) 50-70% by weight of styrene and/or methyl methacrylate and 
     (b 2 ) 30-50% by weight of hydroxyethyl acrylate and/or hydroxyethyl methacrylate and/or hydroxypropyl acrylate and/or hydroxy-n-butyl acrylate, 
     the components (a) and (b) having been employed in such quantities that their total adds up to 100% by weight and it being necessary that the components (b 1 ) and (b 2 ) in the mixture (b) of monomers add up to 100% by weight, and the additional condition applying that the components (a) and (b) have been employed in such quantities that the copolymers have hydroxyl numbers of 130 to 200, 
     it being necesssary that the components (A) and (B) add up to 100% by weight. 
    
    
     A particularly preferred embodiment of the copolymer solution is characterized in that it contains the component (A) in the form of a solution consisting of 20-35% by weight of inert organic solvents which are customary in the lacquer industry and 65-80% by weight of copolymers, it being necessary that the % by weight add up to 100%. 
     A particularly preferred embodiment of the copolymer solution of the invention is characterized in that the component (A) which is employed consists of a copolymer which has a hydroxyl number of 140 to 175 and which has been manufactured from a mixture consisting of: 
     (a) 20-45% by weight of unsaturated polyesters having hydroxyl numbers of 150-240, formed from 28-60% by weight of saturated dicarboxylic acids having 6 to 10 C atoms, 2-20% by weight of unsaturated dicarboxylic acids having 4 C atoms or the anhydrides thereof and 38-70% by weight of diols having 2-4 C atoms, it being necessary that the % by weight add up to 100% by weight, and 
     (b) 55-80% by weight of a mixture of monomers composed of α,β-ethylenically unsaturated compounds. 
     The inert solvents with no active hydrogen atoms which are used are the organic solvents which are customary in the lacquer industry, individually or as mixtures, such as, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, ethyl acetate, butyl acetate, glycol monomethyl ether-acetate, glycol monoethyl ether-acetate, glycol monobutyl ether-acetate, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, aceotoacetic acid butyl ester, benzene, toluene, xylene and/or mixtures of aromatic solvents having a boiling range of 150° to 200° C. 
     Preferred organic inert solvents are those which, individually or as mixtures, have a boiling range of 150° to 200° C. These include, for example, ethylglycol acetate, acetoacetic acid methyl ester, acetoacetic acid ethyl ester and mixtures of aromatic solvents having a boiling range of 150° to 180° C. Ethylglycol acetate is particularly suitable for the manufacture of the copolymers A. It can be removed, partly or wholly, by distillation and can be replaced by low boiling solvents which have a better solubility for the copolymers used. The following are particularly suitable for this purpose: acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and butyl acetate. 
     Unsaturated polyesters which are synthesized from saturated dicarboxylic acids having 6 to 10 carbon atoms, saturated, dimeric fatty acids which have 36 carbon atoms and contain two carboxyl groups in the molecule, unsaturated dicarboxylic acids having 4 carbon atoms or the anhydrides thereof and diols having 2-15 carbon atoms, are obtained as the component (a). Saturated dicarboxylic acids which can be used are adipic acid, pimelic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid and methyl-endomethylenetetrahydrophthalic acid or the anhydrides thereof. The cycloaliphatic dicarboxylic acids tetrahydrophthalic acid or hexahydrophthalic acid or the anhydrides thereof, which impart a high resistance to weathering to the copolymers, especially in two-coat metal effect lacquers, are preferred. Maleic acid, maleic anhydride, fumaric acid and the partially or completely isomerised forms which are produced in the manufacturing process, starting from maleic acid or maleic anhydride, are used as the unsaturated dicarboxylic acids having 4 carbon atoms. Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butane-1,3-diol, butane-1,4-diol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol and 4,4&#39;-dihydroxyisopropylidenedicyclohexane are used as the diols. Ethylene glycol, 1,2-propylene glycol, neopentyl glycol and 2,2,4-trimethylpentane-1,3-diol are particularly preferred. 
     The mixture of monomers of the α,β-unsaturated compounds contains the following compounds: styrene and/or methyl methacrylate are used as (b 1 ). 50 to 70% by weight of hydroxyethyl acrylate and/or hydroxyethyl methacrylate and/or 2-hydroxypropyl acrylate and/or hydroxy-n-butyl acrylate and/or 2-hydroxypropyl methacrylate and/or hydroxy-n-butyl methacrylate are employed as the component (b 2 ). 
     The hydroxyalkyl acrylates mentioned impart a high degree of elasticity to the copolymers. This is required particularly where the metal substrates are shaped by an impact process. A further outstanding property of the hydroxyalkyl acrylates in the copolymers used consists in promoting the wetting of pigments, especially with organic pigments and carbon black. Hydroxyalkyl methacrylates give the copolymers used a particularly high degree of film hardness, which is required particularly in the formulation of polyisocyanate reactive clear lacquers for two-coat metal effect lacquering. 
     30 to 50% by weight of hydroxyethyl acrylate and/or hydroxyethyl methacrylate are used particularly preferentially as the component (b 2 ) since they produce particularly low viscosities and a high solids content in the state ready for spraying. 
     Mixtures of peroxides, consisting of at least two peroxides, are used as the polymerisation initiators in the manufacture of the copolymers used. The mixtures of peroxides have various chemical structures. Peroxides of the first group are represented by diacyl peroxides, such as dibenzoyl peroxide, or peresters, such as tert.-butyl perbenzoate, tert.-butyl peroctoate or tert.-butyl perisononanate. Peroxides of the second group are represented by alkyl hydroperoxides, such as tert.-butyl hydroperoxide and cumene hydroperoxide or dialkyl peroxides, such as di-tert.-butyl peroxide or dicumyl peroxide. 1 to 3.5% by weight of a peroxide from the first group and 1 to 3% by weight of a peroxide from the second group, relative to 100% by weight of the components (a) and (b) are used in each case as the peroxide mixtures. 
     The following combinations of peroxides from groups one and two are employed: dibenzoyl peroxide/tert.-butyl hydroperoxide, dibenzoyl peroxide/cumene hydroperoxide, dibenzoyl peroxide/dicumyl peroxide, tert.-butyl perbenzoate/butyl hydroperoxide, tert.-butyl perbenzoate/cumene hydroperoxide, tert.-butyl perbenzoate/di-tert.-butyl peroxide, tert.-butyl perbenzoate/dicumyl peroxide, tert.-butyl peroctoate/tert.-butyl hydroperoxide, tert.-butyl peroctoate/cumene hydroperoxide, tert.-butyl peroctoate/di-tert.-butyl peroxide, tert.-butyl peroctoate/dicumyl peroxide, tert.-butyl perisononanate/tert.-butyl hydroperoxide, tert.-butyl-perisononanate/cumene hydroperoxide, tert.-butyl perisononanate/di-tert.-butyl peroxide or tert.-butyl perisononanate/dicumyl peroxide. 
     The preferred embodiment includes the following combinations of peroxides: dibenzoyl peroxide/cumene hydroperoxide, dibenzoyl peroxide/di-tert.-butyl peroxide, tert.-butyl peroctoate/cumene hydroperoxide, tert.-butyl peroctoate/di-tert.-butyl peroxide, tert.-butyl perbenzoate/cumene hydroperoxide and tert.-butyl perbenzoate/di-tert.-butyl peroxide. 
     In the preferred embodiment, mixtures of peroxides are used in quantities of 1.0 to 2.5% by weight of dibenzoyl peroxide and 1.5 to 3.0% by weight of di-tert.-butyl peroxide, relative to 100 percent by weight of the unsaturated polyester (a) and the mixture (b) of monomers. 
     The mixtures of peroxides are generally dissolved in the monomers or are added separately to the polymerisation medium, solvent or solvent mixture. In some cases it is also possible to dissolve small proportions of the mixtures of peroxides, up to 20% by weight of the quantity of peroxides employed, in the solvent or solvent mixtures and to add the residual quantity of the mixtures of peroxides uniformly to the polymerisation medium, solvent or solvent mixture, separately from the monomers or dissolved in the latter. The acid number of the copolymers is 4 to 10 and depends on the polyester constituent and on the organic acids which are formed as a scission product in the decomposition of the peroxides and which are to be regarded as extraneous acid. 
     The hydroxyl number of the copolymers is 130 to 200, preferably 140 to 175. 
     The copolymers (B) which are used are manufactured by copolymerisation, by heating at 165° to 180° C., the solvents or solvent mixtures, which preferably have a boiling range of 150° to 200° C., together with 
     (a) 20 to 45% by weight of unsaturated polyesters having acid numbers of 10 to 20 and having hydroxyl numbers of 100 to 250, which are synthesized from saturated dicarboxylic acids having 6-10 carbon atoms, unsaturated dicarboxylic acids having 4 carbon atoms or the anhydrides thereof and diols having 2 to 15 carbon atoms, it being possible for the saturated dicarboxylic acids having 6 to 10 carbon atoms to be replaced, to the extent of up to 20%, by saturated, dimeric fatty acids which have 36 carbon atoms and contain two carboxyl groups, together with 
     (b) 55-80% by weight of a mixture of monomers composed of α,β-ethylenically unsaturated compounds, it being necessary that the percentage by weight of unsaturated polyester and the percentage by weight of the mixture of monomers add up to 100% by weight, the said mixture consisting of 
     (b 1 ) 50-70% by weight of styrene and/or methyl methyacrylate and 
     (b 2 ) 30-50% by weight of hydroxyethyl acrylate and/or hydroxyethyl methacrylate and/or hydroxypropyl acrylate and/or hydroxy-n-butyl acrylate, 
     the components (a) and (b) having been employed in such quantities that their total adds up to 100% by weight and it being necessary that the components (b 1 ) and (b 2 ) in the mixture (b) of monomers add up to 100% by weight, and the additional condition applying that the components (a) and (b) have been employed in such quantities that the copolymers have hydroxyl numbers of 130 to 200, and employing a mixture of peroxides as polymerisation initiators. It is preferable to carry out the polymerisation in such a way that the mixture of polyester and solvent mixture is heated at 165° to 180° C. and the mixtures of monomers (b 1 ) and (b 2 ) and the polymerisation initiators, separately or, preferably, jointly, are added slowly and uniformly, over a space of time of 4 to 10 hours to this heated mixture in the reaction vessel, the polymerisation temperature not being allowed to fall below 165° C. After the monomers and peroxides have been added, polymerisation is continued for a further 2 to 3 hours at reflux temperature until the solids content of the solution has reached the theoretical value between 65 and 75% by weight. The copolymers used must have a predetermined test viscosity of H to W, measured by the Gardner-Holdt method, for 60% strength by weight copolymer solutions in ethylglycol acetate. 
     These copolymers B are used as the component B in reactive lacquers together with a polyisocyanate component C. 
     The following polyisocyanates, for example, can be employed as the component C: ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,3-dimethylbenzene diisocyanate, 1,4-dimethylcyclohexane diisocyanate, 1-methylcyclohexane 2,4-diisocyanate, 4,4&#39;-methylene-bis(cyclohexyl diisocyanate), phenylene diisocyanate, 2,4-toluylene diisocyanate, naphthylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, lysine diisocyanate, triphenylmethane triisocyanate, trimethylbenzene 2,4,6-triisocyanate, 1-methylbenzene 2,4,6-triisocyanate and diphenyl 2,4,4&#39;-triisocyanate; diisocyanates or triisocyanates which are manufactured by reacting a polyisocyanate with a low-molecular diol or triol (for example ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, hexanediol, trimethylolpropane or trimethylolethane); and cyanurates which have been obtained by reacting the said diisocyanates so as to form a ring. A particularly valuable polyisocyanate is the triisocyanate which contains biuret groups and which is obtained by reacting 3 mols of hexamethylene diisocyanate and one mol of water. 
     Instead of the polyisocyanates, it is also possible to use compounds which split off polyisocyanates, and also reaction products, containing isocyanate groups, of polyhydric alcohols with polyisocyanates, for example the reaction product of 1 mol of trimethylolpropone with 3 mols of toluylene diisocyanate, and also trimerised or polymerised isocyanates such as are described, say, in German patent specification 951,168. 
     In addition, a reaction product from 1 mol of water and 3 mols of hexamethylene diisocyanate, having a NCO content of 16-17% by weight is also suitable. The last-mentioned reaction product of water and hexamethylene diisocyanate is particularly preferred. The NCO content of the reaction product applies to a 75% strength solution in xylene/ethylglycol acetate. 
     When they are used in reactive lacquers, the reaction of the copolymers B which contain hydroxyl groups, with the organic polyisocyanates C can, depending on the end use of the reaction products, be carried out with 0.5 to 1.3 NCO groups per hydroxyl group. The reaction is preferably carried out in such a way that the quantities of the organic polyisocyanate, relative to the total hydroxyl content of the components present in the reaction mixture, are present in a quantity of 0.7 to 1.0 isocyanate group per hydroxyl group. 
     In order to use the copolymers, the mixtures of copolymers B containing solvents and containing hydroxyl groups and of polyisocyanate C are applied to the appropriate substrates in the simplest manner imaginable, by spraying, dipping, pouring, brushing or other suitable measures, possibly after the addition of known auxiliaries, such as levelling agents, pigments or dyestuffs, and the sheet-like structures are dried at room temperature; in special cases, say when using compounds which split off isocyanate, stoving of the coatings can be carried out, which depends essentially on the substrates used and on the demands made on the coatings by practical use. 
     For the production of coatings or coverings, the copolymers used in the process can be employed in the reactive lacquers already illustrated, together with polyisocyanates, on substrates of the most diverse kind, for example porous or non-porous substrates such as textile nonwovens, leather or plastics. The production of coatings on wood or metals should be singled out particularly. In all cases, high-gloss, pore-free, elastic and solvent-resistant coatings of high surface hardness are obtained, which can be treated both with strong inorganic acids and with strong alkalis, without the coatings being attacked even to the slightest extent. In addition, coatings of this type exhibit an outstanding resistance to weathering and resistance to yellowing. 
     In pigmented coating compositions based on the polyisocyanate/reactive lacquer/binder solutions according to the invention, the total content of solids in the coating composition is between 60 and 80% by weight, preferably between 65 and 80% by weight. The ratio of pigment to binder can be between 1:20 and 2:1. The following can be added as pigments: inorganic pigments, such as chrome yellow, Prussian blue, Brunswick green and titanium pigments, for example titanium dioxide, extended titanium pigments (which are extended either with precipitated or natural extenders, such as alkaline earth metal sulphates, for example calcium sulphate and barium sulphate), tinted pigments and titanates, such as barium, tin, lead and magnesium titanates. Other types of inorganic pigments can also be used, for example zinc sulphide pigments, such as zinc sulphide, lithopone, extended zinc sulphide pigments, such as lithopone with a calcium base, or zinc sulphide extended with natural extenders, zinc oxide or antimony oxide, or organic pigments, that is to say organic dyestuffs which are free from sulphonic acid or carboxylic acid groups, or other groups which impart solubility in water. Pigments also include, conceptually, other water-insoluble organic dyestuffs, for example calcium or barium lakes of azo dyestuffs. 
     The ingredients for the stoving lacquers to be used can be processed to give lacquers by customary processes, preferably as follows. The pigment and a suitable quantity of solvent are mixed with a part of the copolymer according to the invention to give a pasty or solid pigment paste. After the mixture has been well dispersed in a stirred ball mill, the residual copolymer and other additives are added to the resulting paste or dispersion and the product is then formulated with the solvents, preferably xylene, butyl acetate and/or ethylglycol acetate or acetone, to give a sprayable viscosity at a solids content of 60 to 80% by weight, preferably between 65 and 80% by weight, relative to the nonvolatile substances. 
     Manufacture of the polyesters 
     A. 0.66 g of sodium acetate, 1,322 g of tetrahydrophthalic anhydride, 191 g of maleic anhydride and 1,140 g of 1,2-propylene glycol are heated under nitrogen, at first slowly to about 160° C. in order to prevent losses of glycol, in a glass flask equipped with a stirrer, a reflux condenser and a water separator. The mixture is heated further until, at a kettle temperature of about 180° C., separation of water takes place. As a result of further heating, during an esterification time of 15 hours, the kettle temperature rises to about 210° to 220° C. The unsaturated polyester has an acid number of 15 and a viscosity of H-I on the Gardner-Holdt scale, measured as a 70% strength solution in ethylglycol acetate at 23° C. 
     The following polyesters B to S are obtained according to these manufacturing instructions, but using other raw materials or other quantities of raw material: 
     
                                           TABLE 1                                 
__________________________________________________________________________
                         Ethyl-                                           
            Iso- Adipic                                                   
                     Tetra-                                               
                         ene  1,2-Pro-                                    
                                   1,4-                                   
    MA.sup.+                                                              
        PA.sup.++                                                         
            PS.sup.+++                                                    
                 acid                                                     
                     hydro-                                               
                         glycol                                           
                              pylene                                      
                                   Butane-                                
    in %                                                                  
        in %                                                              
            in % in %                                                     
                     PA in                                                
                         in % glycol                                      
                                   diol in                                
Poly-                                                                     
    by  by  by   by  % by                                                 
                         by   in % by                                     
                                   % by                                   
ester                                                                     
    weight                                                                
        weight                                                            
            weight                                                        
                 weight                                                   
                     weight                                               
                         weight                                           
                              weight                                      
                                   weight                                 
__________________________________________________________________________
B   2   59.5             38.5                                             
C   4   57.4             38.6                                             
D   6   55.4             38.6                                             
S   8   53.4             38.6                                             
P   0   51.4             38.6                                             
O   14  45.5             40.6                                             
H   18  40.7             41.3                                             
I   7.3 49.1                  43.6                                        
J   7.2 24.4         25       43.4                                        
K   7.32                                                                  
        24.64    24.33        43.71                                       
L   6.88    52                41.12                                       
M   2.2 46.6                                                              
N   2.3 49.9                       47.8                                   
O   2.5 34.8                                                              
P   2.0 28.1                                                              
Q   6.8 20.2     22.6         40.4                                        
R       24.3     24.0         43.1                                        
S   6.7 22.5                  40.0                                        
__________________________________________________________________________
                          Dimer-    Visc-                                 
                          ic        osity                                 
    4,4&#39;-Di-              fatty     in                                    
    hydroxy-              acid      ethyl-                                
    isopro-                                                               
         Neo-                                                             
             2,2,4-Tri-                                                   
                  Fum-                                                    
                      Seb-                                                
                          having    glycol                                
    pylidene-                                                             
         pentyl                                                           
             methyl-                                                      
                  aric                                                    
                      acic                                                
                          36 C      acetate                               
    dicyclo-                                                              
         glycol                                                           
             pentane-                                                     
                  acid                                                    
                      acid                                                
                          atoms     at 70%                                
    hexane                                                                
         in %                                                             
             1,3-diol                                                     
                  in %                                                    
                      in %                                                
                          in %                                            
                              Acid                                        
                                 OH solids                                
Poly-                                                                     
    in % by                                                               
         by  in % by                                                      
                  by  by  by  num-                                        
                                 num-                                     
                                    con-                                  
ester                                                                     
    weight                                                                
         weight                                                           
             weight                                                       
                  weight                                                  
                      weight                                              
                          weight                                          
                              ber                                         
                                 ber                                      
                                    tent                                  
__________________________________________________________________________
B                             14 220                                      
                                    E-F                                   
C                             13 218                                      
                                    G-H                                   
D                             15 208                                      
                                    H-I                                   
S                             17.5                                        
                                 200                                      
                                    I                                     
P                             16 195                                      
                                    J                                     
O                             16 230                                      
                                    I                                     
H                             18 230                                      
                                    I                                     
I                             16 200                                      
                                    L-M                                   
J                             15 198                                      
                                    I-J                                   
K                             15 205                                      
                                    D-E                                   
L                             16 200                                      
                                    T-U                                   
M        51.2                 12 195                                      
                                    M-I                                   
N                             20 160                                      
                                    U                                     
O            62.7             19 170                                      
                                    Q-R                                   
P   69.9                      19 175                                      
                                    R                                     
Q                         10  12 170                                      
                                    E                                     
R                 8.6         12 175                                      
                                    E                                     
S                     30.8    13 180                                      
                                    D                                     
__________________________________________________________________________
 .sup.+ Maleic anhydride                                                  
 .sup.++ Phthalic anhydride                                               
 .sup.+++ Isophthalic anhydride                                           
 
    
     Manufacture of copolymers 1-30 
     Copolymer 1: 
     322 g of an aromatic solvent having a boiling range of 150° to 170° C., 108 g of ethylglycol acetate and 400 g of the unsaturated polyester A (=40% by weight) are heated to reflux temperature in a flask equipped with a stirrer, a reflux condenser and a water separator, and the following mixture b of monomers (=60% by weight) consisting of: 235 g of hydroxyethyl methacrylate, 100 g of styrene, 265 g of methyl methacrylate, 20 g of dibenzoyl peroxide, as a 75% strength suspension in water, and 20 g of di-tert.-butyl peroxide is added uniformly in the course of 7 hours, the temperature of reflux falling from 162° C. to 145° C. during the addition. When the addition is complete, polymerisation is continued for a further 2 hours until a solids content of 68 to 69% is reached. The product has a viscosity on the Gardner-Holdt scale of Q, measured as a  60% strength solution at 23° C., after being diluted with ethylglycol acetate. The copolymer has an acid number of 5 and a hydroxyl number of 155. 
     Table 2 
     In the manufacture of copolymers 2-30 which follow, the process used is that described for the manufacture of copolymer 1. 
     
         __________________________________________________________________________
                                                    Viscosity             
                                                    of the co-            
                                                    polymers              
                                                    as a                  
                                                          Solids          
                                                    tion of               
                                                          content         
                                                    solids                
                                                          of the          
                                         Dibenzoyl                        
                                               Hydroxyl                   
                                                    tent                  
                                                          copoly-         
Co-          Methyl  Hydroxy-            peroxide,                        
                                               number                     
                                                    being                 
                                                          mer solu-       
poly-                                                                     
    Poly-    meth-   ethyl                                                
                          Hydroxy-                                        
                               Dodecyl-                                   
                                    Di-tert.-                             
                                         75%   of the                     
                                                    ted                   
                                                          tions in        
mer ester                                                                 
         Poly-                                                            
             acryl-                                                       
                 Sty-                                                     
                     meth-                                                
                          ethyl                                           
                               mercap-                                    
                                    butyl                                 
                                         strength                         
                                               copoly-                    
                                                    ethylglycol           
                                                          % by            
No. type ester                                                            
             ate rene                                                     
                     acrylate                                             
                          acrylate                                        
                               tan  peroxide                              
                                         in water                         
                                               mer  acetate               
                                                          weight          
__________________________________________________________________________
2   B    200 g   435 g                                                    
                     365 g     16 g 20 g 20 g  190   R-S  69              
3   B    300 g   400 g                                                    
                     300 g     16 g 20 g 20 g  188  N     68.5            
4   B    400 g   355 g                                                    
                     245 g     16 g 20 g 20 g  186  I-J   70              
5   C    200 g   435 g                                                    
                     365 g     16 g 20 g 20 g  187  O-P   69              
6   C    400 g   355 g                                                    
                     245 g     16 g 20 g 20 g  176  H-I   70              
7   D    200 g   435 g                                                    
                     365 g     16 g 20 g 20 g  179  T-U   68.5            
8   D    400 g   355 g                                                    
                     245 g     16 g 20 g 20 g  178  I-J   69              
9   E    200 g   435 g                                                    
                     365 g     16 g 20 g 20 g  171  T+    69.5            
10  E    400 g   355 g                                                    
                     245 g     16 g 20 g 20 g  165  M+    68.5            
11  F    200 g   435 g                                                    
                     365 g     16 g 20 g 20 g  174  T-U   70              
12  F    400 g   355 g                                                    
                     245 g     16 g 20 g 20 g  165  R-S   69.5            
13  G    200 g   435 g                                                    
                     365 g     16 g 20 g 20 g  175  U-V   70              
14  G    400 g   355 g                                                    
                     245 g     16 g 20 g 20 g  178  T-U   69.5            
15  H    200 g   435 g                                                    
                     365 g     16 g 20 g 20 g  179  W-    69              
16  H    400 g   355 g                                                    
                     245 g     16 g 20 g 20 g  171  V-W   69              
17  I    400 g                                                            
             265 g                                                        
                 100 g                                                    
                     235 g          20 g 20 g  155  H-I   70              
18  I    400 g                                                            
             291 g                                                        
                 100 g    209 g     20 g 20 g  160  I     68.5            
19  J    400 g                                                            
             265 g                                                        
                 100 g                                                    
                     235 g          20 g 20 g  162  J     69              
20  J    400 g                                                            
             291 g                                                        
                 100 g    209 g     20 g 20 g  165  M-N   69.5            
21  K    400 g                                                            
             265 g                                                        
                 100 g                                                    
                     235 g          20 g 20 g  165  H-I   69.5            
22  K    400 g                                                            
             291 g                                                        
                 100 g    209 g     20 g 20 g  162  T     69.5            
23  A    400 g   365 g                                                    
                     235 g          20 g 20 g  158  T-U   68.5            
24  A    400 g   391 g    209 g     20 g 20 g  160  X     69              
25  L    400 g                                                            
             265 g                                                        
                 100 g                                                    
                     235 g          20 g 20 g  150  L-M   70              
26  L    400 g                                                            
             291 g                                                        
                 100 g    209 g     20 g 20 g  152  K     69.5            
27  Q    400 g                                                            
             270 g                                                        
                 100 g                                                    
                     230 g          20 g 20 g  148  G     69.5            
28  R    410 g                                                            
             260 g                                                        
                  90 g                                                    
                     240 g          20 g 20 g  155  H-I   70              
29  S    380 g                                                            
             230 g                                                        
                 150 g                                                    
                     240 g          20 g 20 g  162  H     68.5            
30  S    400 g                                                            
             265 g                                                        
                 100 g                                                    
                     235 g          20 g 20 g  158  J     69.5            
__________________________________________________________________________
 
    
     Copolymers 1-30, which are illustrated in Table 2, have the following composition, which is shown in Table 3. 
     
                       TABLE 3                                                     
______________________________________                                    
                        Methyl          Hydroxy-                          
Co-   Poly-             meth-  Hydroxyethyl                               
                                        ethyl                             
poly- ester    Styrene  acrylate                                          
                               methacrylate                               
                                        acrylate                          
mer   in % by  in % by  in % by                                           
                               in % by  in % by                           
No.   weight   weight   weight weight   weight                            
______________________________________                                    
1     40       10       26.5   23.5                                       
2     20       43.5            36.5                                       
3     30       40              30                                         
4     40       35.5            24.5                                       
5     20       43.5            36.5                                       
6     40       35.5            24.5                                       
7     20       43.5            36.5                                       
8     40       35.5            24.5                                       
9     20       43.5            36.5                                       
10    40       35.5            24.5                                       
11    20       43.5            36.5                                       
12    40       35.5            24.5                                       
13    20       43.5            36.5                                       
14    40       35.5            24.5                                       
15    20       43.5            36.5                                       
16    40       35.5            24.5                                       
17    40       10       26.5   23.5                                       
18    40       10       29.1            20.9                              
19    40       10       26.5   23.5                                       
20    40       10       29.1            20.9                              
21    40       10       26.5   23.5                                       
22    40       10       29.1            20.9                              
23    40       36.5            23.5                                       
24    40       39.1                     20.9                              
25    40       10       26.5   23.5                                       
26    40       10       29.1            20.9                              
27    40       10       27.0   23.0                                       
28    41       9        26.0   24.0                                       
29    38       15       23.0   24.0                                       
30    40       10       26.5   23.5                                       
______________________________________                                    
 
    
     The following are the proportions, as percentages by weight, in the mixture of copolymerised monomers contained in the copolymers illustrated in Tables 2 and 3: 
     
                       TABLE 4                                                     
______________________________________                                    
      (Mixture of      (Mixture of                                        
Co-   monomers from b.sub.1)                                              
                       monomers from b.sub.2)                             
poly- Styrene   Methyl     Hydroxyethyl                                   
                                    Hydroxyethyl                          
mer   % by      methacrylate                                              
                           methacrylate                                   
                                    acrylate                              
No.   weight    % by weight                                               
                           % by weight                                    
                                    % by weight                           
______________________________________                                    
1     16.68     44.16      39.16                                          
2     54.37                45.63                                          
3     57.14                42.86                                          
4     59.16                40.84                                          
5     54.37                45.63                                          
6     59.16                40.84                                          
7     54.37                45.63                                          
8     59.16                40.84                                          
9     54.37                45.63                                          
10    59.16                40.84                                          
11    54.37                45.63                                          
12    59.16                40.84                                          
13    54.37                45.63                                          
14    59.16                40.84                                          
15    54.37                45.63                                          
16    59.16                40.84                                          
17    16.68     44.16      39.16                                          
18    16.68     48.5                34.82                                 
19    16.68     44.16      39.16                                          
20    16.68     48.5                34.82                                 
21    16.68     44.16      39.16                                          
22    16.68     48.5                34.82                                 
23    60.84                39.16                                          
24    65.18                         34.82                                 
25    16.68     44.16      39.16                                          
26    16.68     48.5                34.82                                 
27    16.68     45.0       38.32                                          
28    15.25     44.06      40.69                                          
29    24.21     37.1       40.69                                          
30    16.68     44.16      39.16                                          
______________________________________                                    
 
    
     When the new copolymers are used in reactive lacquers, the components A and B are preferably used in the following quantities: 
     A. 60 to 80% by weight of copolymers containing hydroxyl groups, manufactured in accordance with the invention, 
     B. 20 to 40% by weight of aliphatic triisocyanate. 
     In order to demonstrate the technical progress achieved, the curing of the lacquer films at room temperature is determined, as a function of time and at a stoving temperature of 80° C. for 30 minutes, by means of the pendulum hardness (PH), determined by Konig&#39;s method. In addition, the &#34;pot life&#34; of the lacquer solution and the solids content of the lacquer solution were determined. For this purpose, the reactive lacquers listed in Table 5 and prepared according to the invention from copolymers 1-30, were mixed with 1% by weight of diethylethanolamine, relative to copolymer, and with the aliphatic triisocyanate which is obtained by reacting* 3 mols of hexamethylene diisocyanate and 1 mol of water. Relative to the solids content, the mixing ratios of the copolymers with the polyisocyanate were 65% by weight of copolymer: 35% by weight of polyisocyanate. The mixtures were diluted with a solvent mixture consisting of xylene and butyl acetate in a weight ratio of 1:1, to a viscosity of 25 seconds flow time at 23° C., measured in a DIN cup having a 4 mm flow orifice, and the increase in viscosity was determined as a function of time. In order to determine the pendulum hardness, wet films 90 μm thick are applied to sheets of glass and are dried. The solids content of the lacquer solution was determined at 125° C. after 60 minutes. 
    
     
                                           TABLE 5                                 
__________________________________________________________________________
Reactive lacquers                                                         
          Pendulum hardness by Konig&#39;s                                    
          method, in seconds                                              
          Stoving temperature   Flow time                                 
                                       Solids content                     
Example                                                                   
     Copoly-                                                              
          80° C. for 30 minutes after                              
                       Drying in the air                                  
                                after 4 hours                             
                                       of the lacquer                     
1 to 27                                                                   
     mer  1 d   5 d    1 d                                                
                          5 d                                             
                             8 d                                          
                                at 23° C.                          
                                       solution                           
__________________________________________________________________________
1    1    119   216    84 206                                             
                             213                                          
                                46     58.2%                              
2    2    196   218             45     57.2%                              
3    3    187   210    105                                                
                          191                                             
                             206                                          
                                40     58.0%                              
4    4    140   200    93 174                                             
                             199                                          
                                35     59.4%                              
5    5    187   205    102                                                
                          184                                             
                             202                                          
                                45     56.8%                              
6    6    147   195    51 141                                             
                             185                                          
                                45     60.5%                              
7    7    185   205    121                                                
                          200                                             
                             205                                          
                                50     55.8%                              
8    8    129   185    59 142                                             
                             180                                          
                                39     59.2%                              
9    9    200   210    95 160                                             
                             202                                          
                                42     55.5%                              
10   10   158   181    41 123                                             
                             173                                          
                                38     59.2%                              
11   11   198   203    118                                                
                          196                                             
                             200                                          
                                48     55.2%                              
12   12   163   178    51 150                                             
                             183                                          
                                42     58.0%                              
13   13   196   205    132                                                
                          186                                             
                             204                                          
                                41     54.0%                              
14   14   168   185    90 170                                             
                             182                                          
                                42     56.1%                              
15   15   201   206    134                                                
                          186                                             
                             202                                          
                                46     51.5%                              
16   16   187   203    98 175                                             
                             198                                          
                                45     52.6%                              
17   17   109   202    33 192                                             
                             203                                          
                                42     60.5%                              
18   18    89   214    21 189                                             
                             196                                          
                                44     58.7%                              
19   19   142   213    30 163                                             
                             178                                          
                                38     60.2%                              
20   21    68   135    17 125                                             
                             137                                          
                                35     61.0%                              
21   22    38   157    11 151                                             
                             165                                          
                                40     58.7%                              
22   25   160   220    50 192                                             
                             206                                          
                                42     60.0%                              
23   26   126   215    38 190                                             
                             208                                          
                                44     59.8%                              
24   27    85   180    17 110                                             
                             140                                          
                                37     61.2%                              
25   28    90   185    21 115                                             
                             155                                          
                                40     60.3%                              
26   29    92   188    23 120                                             
                             160                                          
                                41     60.0%                              
27   30   138   201    30 160                                             
                             188                                          
                                44     58.8%                              
__________________________________________________________________________
 1 d = 1 day                                                              
 
    
     EXAMPLE 28 
     80 g of copolymer solution 1, dissolved to form a 70% strength solution in a mixture of an aromatic solvent and ethylglycol acetate, in a weight ratio of 3:1, are mixed with 0.6 g of diethylethanolamine, 0.3 g of dibutyl-tin dilaurate, dissolved to form a 1% strength solution in xylene, 11.4 g of butyl acetate, 5.7 g of ethylglycol acetate, 2 g of silicone oil OL, dissolved to form a 10% strength solution in xylene, and 40 g of an organic triisocyanate which is dissolved to form a 75% strength solution in xylene and ethylglycol acetate, in a weight ratio of 1:1, and which has a NCO content of 16 to 17% by weight and which has been prepared from 3 mols of hexamethylene diisocyanate and 1 mol of water. The lacquer combination according to the invention is diluted with 10 parts by weight of a mixture of butyl acetate and ethylglycol acetate, in a weight ratio of 1:1, to give a flow time of 25 seconds, measured at 25° C. according to DIN 53,211, in a flow cup having a 4 mm orifice. The clear lacquer, ready for spraying, is then applied at a dry film layer thickness of 40-45 μm to an undercoating containing aluminum bronze and is dried in the air for 10 days or for 30 minutes at 80° C. The properties, from the point of view of lacquer technology, of the resulting coating are listed in Table 6. 
     EXAMPLE 29 
     27 g of copolymer solution 1, 26.5 g of chrome yellow Supra 600 L of Messrs. Siegle &amp; Co. of Stuttgart, 0.4 g of diethylethanolamine, 0.2 g of dibutyl-tin dilaurate, dissolved to form a 1% strength solution in xylene, 2 g of Bentone 38 of Messrs. Kronos Titan GmbH of Leverkusen, as a 10% strength suspension in 86 parts by weight of xylene and 4 parts by weight of anti-settling agent (Bykumen), 5.4 g of butyl acetate and 5 g of ethylglycol acetate are weighed out into a stirred ball mill and are dispersed to give a particle size of &lt;10 μm. 26.5 g of copolymer solution 1, 5 g of butyl acetate, 2 g of silicone oil OL of Messrs. Bayer of Leverkusen, dissolved to form a 10% strength solution in xylene, and 27 g of an organic triisocyanate having a NCO content of 16 to 17% by weight are then mixed in. The lacquer combination according to the invention is diluted with 1.5 g of butyl acetate and 1.5 g of ethylglycol acetate to a flow time of 25 seconds, measured at 25° C. according to DIN 53,211, in a flow cup having an orifice of 4 mm. The pigmented lacquer, ready for spraying, is then applied at a dry film layer thickness of 40-45 μm to a steel sheet which has been primed and treated with a filler, and drying is carried out in the air for 10 days or for 30 minutes at 80° C. The properties, from the point of view of lacquer technology, are listed in Table 6. 
     
                       TABLE 6                                                     
______________________________________                                    
                         Yellow top                                       
               Clear lacquer                                              
                         lacquer                                          
               Example 28                                                 
                         Example 29                                       
______________________________________                                    
Drying in the air and in an                                               
oven, determined by pendulum                                              
hardness measured by Konig&#39; s                                             
method                                                                    
after 24 hours    81 seconds  63 seconds                                  
after 10 days    170 seconds 178 seconds                                  
after 30 minutes at 80° C.                                         
                  60 seconds  42 seconds                                  
after a further 24 hours                                                  
drying in the air                                                         
                 160 seconds 113 seconds                                  
Solids content, determined                                                
at 125° C. after 1 hour, of the                                    
lacquer, ready for spraying                                               
                 57.5%       65%                                          
Erichsen deep-drawing value                                               
                  7.9 mm      7.9 mm                                      
Mandrel bending test*                                                     
                  0           0                                           
Resistance to xylene after                                                
exposure for 6 minutes*                                                   
                  0           0                                           
Gloss determination by                                                    
Gardner&#39;s method, 60° angle                                        
                 99%         94%                                          
Gloss retention in an Atlas                                               
weatherometer with a 6,000                                                
watt xenon lamp and inner and                                             
outer quartz filter, exposure                                             
time 200 hours   90%         83%                                          
Crazing formation in the                                                  
lacquers according to the                                                 
invention*        0           0                                           
______________________________________                                    
  *0 = highest value                                                      
 5 = lowest value                                                         
 
    
     In the absence of crosslinking catalysts the reactive lacquers of the invention are stable to storage at room temperature for about 2 days. When stored at 0° to -5° C., the reactive lacquers of the invention can be stored in a usable condition for 10 to 14 days in the absence of crosslinking catalysts. 
     The reactive lacquers are catalysed, for example with 1% by weight of diethylethanolamine, in order to bring about crosslinking at room temperature. The processing time of these catalysed reactive lacquers is about 4 hours, that is to say the viscosity of the reactive lacquer mixture increases from an initial flow time of 25 seconds, measured at 23° C. in a DIN cup having a 4 mm flow orifice, to a maximum flow time of 50 seconds. In order to prevent the freshly-mixed, catalysed reactive lacquer mixture from gelling, the lacquer can be stored for several days in a refrigerator at 0° to -5° C. without any increase in viscosity being detectable. A residue of a ready-to-use catalysed reactive lacquer which is still left at the end of a working day and which has already lost its workability through increasing viscosity, but has not yet gelled, can be stored at 0° to -5° C. or lower and can be re-processed to give a ready-to-use reactive lacquer by adding fresh components A and B, so that losses of lacquer due to exceeding the pot life can be avoided in this way.