MXPA06006466A - Oligocarbonate-containing coating compositions for scratch-resistant topcoats - Google Patents

Abstract

Coating compositions comprising polyisocyanates, aliphatic oligocarbonate polyols and polyacrylate polyols are provided. The compositions comprise A) a polyol component composed of a) 1%to 50%by weight of aliphatic oligocarbonate polyols having a number-average molecular weight Mnof 200 to 5000 g/mol and b) 50%to 99%by weight of hydroxy-functional polyacrylate polyols;and B) one or more OH-reactive (poly)isocyanate crosslinkers having an average NCO functionality of>=2.0. A process for preparing the coatings are also provided.

Description

COATING AGENTS CONTAINING OLIGOCARBONATE FOR SCRATCH-RESISTANT COVERING LACQUER DESCRIPTION OF THE INVENTION The present invention deals with new coating agents manufactured from polyisocyanates, aliphatic olicarbonatopolols and polyacrylate polyols, a process for their production and their use for the manufacture of coatings. Scratch-resistant coating lacquers, especially in the area of automotive coating lacquers, as well as automotive repair lacquers, have been of great interest for many years. In addition to the feature that coating lacquers of this type must show a low propensity for scratching, for example in a car wash, the requirement is also required that this lacquer system offers a marked resistance to abrasion. solvents and acids. Thus, especially during the last years, two polyurethane systems with two components have been imposed on the market, characterized mainly by the high resistance they present to solvents and chemical substances, as well as a high resistance to scratches. and an exceptional resistance to the weather. REF.:172866 Polyacrylates are often used, if appropriate, mixed with polyesters, as polyol-based binders, in these systems. Suitable crosslinking agents are aliphatic and / or cycloaliphatic polyisocyanates based on ephexamethylene diisocyanate and isopronioisocyanate. These two-component polyurethane-based coating agents have achieved a very good general level of properties, although it is frequently observed, especially in the case of dark color shades, than clear lacquer, after passing through frequent washing cycles in the washing tunnels, it spider. If, depending on the adjustment of the elasticity of the lacquer layer, scratches occur again with the passage of time, we refer to the so-called reflow. However, if, in order to improve the reflow behavior, the elasticity of the transparent lacquer layer is increased, then the hardness lacquer on the surface is lost and, above all, the resistance to solvents and chemicals deteriorates. , in particular the resistance to acids [Editorial Cari Hanser, Munich, MO Metalloberf lache 54 (2000) 60-64]. Thus, in the state of the art there are efforts to improve the scratch resistance of 2C PUR lacquers by increasing the elasticity of the polyol components, mainly by combinations of polyacrylates and elastic polyesters.

• - DE-A 198 24 118 describes low-solvent binders, based on polyester-acrylate, which can be cured with di- and / or polyisocyanates, to produce fast-drying coatings with good adhesion. However, due to the large proportion of polyester present, these only show an insufficient resistance to acids, and are not suitable for use in automotive coating lacquers. WO 96/20968 discloses a coating agent for automobiles and trucks containing a polyacrylate based on alkyl-substituted cycloaliphatic (meth) acrylate monomers or alkyl-substituted aromatic vinyl monomers, a polyhydroxy-functional oligoester and a polyisocyanate. Since the oligoesters, however, show a large number of secondary hydroxyl groups in addition to primary hydroxyl groups, and for the low viscosity coating agent (<3000 mPa-s / 23) ° C) very high amounts of these esters (> 60% by weight, based on the overall formulation) must be used, they only harden very slowly and in the presence of very high temperatures, so they are not suitable for sensitive substrates at the temperature. EP-A 0 896 991 describes coating agents based on polyacrylate and polyester mixtures with polyester proportions of <; 10% by weight and hydroxyl numbers of 40 to 125 mg KOH / g Due to the resulting reduced crosslink density, the PUR lacquers produced from these do not show sufficient solvents or guiding substances. In addition, the viscosity with values of 3000 to 5000 mPa-s / 23 ° C with a solid content of 70% by weight, is too high for the formulation of PUR lacquers rich in solid contents. In the state of the art, as well as in EP 1 101 780 A, EP 819 710 A and EP 778 298 A, the use of mixtures of polyacrylates with other polyols, such as polyesters and / or polyesters, is often mentioned. polycarbonates as binder based on polyol and reactant for polyisocyanate crosslinkers in the 2C Pur lacquers, without, however, going into details about the special advantages of these mixtures. In addition, no indication has been made about the quantitative composition or molecular weight and OH functionality of the polyocarbonate of this mixing system. Thus, it has been the object of the present invention to provide new coating agents which show an improvement in scratch resistance without, in this way, adversely affecting the resistance to acids and solvents of the coating coating systems. . It has been found that, with the use of oligocarbonatopolols in a given combination with polyacrylate polyols and polyisocyanates, coating agents can be produced which exhibit significantly improved scratch resistance, with simultaneous improvement of the solvent and acid resistance. Thus, the coating agents containing A) are a subject of the invention. A polyol component consisting of a) from 1 to 50% by weight of aliphatic oligocarbonatopolols with a number average molecular weight Mu of 200 to 000 g / mol and b) from 50 to 99% by weight of hydroxy-functional polyacrylate polyols and B) one or more reactive (poly) isocyanate cross-linking agents, compared to OH groups, with a functionality NCO media > 2.0. The amounts of a) and b), thus, total in this respect 100% of the weight. Preferably, in a), aliphatic oligocarbonatopolols having an average number-average molecular weight of 200 to 2000 g / mol, particularly preferably 200 to 1000 g / mol, are used. Preferably, in a), aliphatic oligocarbonatopolyoles of the abovementioned type are used, which show an OH functionality of 1.5 to 5, with particular preference of 1.7 to 3 and, with very special preference, of 1.9 to 2.5. . Preferably, the amount of component a) is from 1 to 20% by weight and that of component b) is from 80 to 99%, particularly preferably in a) quantities of 1 to 10% by weight are used and in b), amounts of 90 to 99% by weight. The production of the aliphatic oligocarbonates polyols used in a) can be carried out by transesterification of monomeric dialkyl carbonates, such as dimethyl carbonate, diethyl carbonate, etc., with polyols having an OH = 2.0 functionality, as 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-l, 5-pentanediol, 1, 12-dodecanediol, cyclohexanedi ethanol, trimethylolpropane, and the like, and is described, for example, in EP 1 404 740 Bl, in examples 1 to 5, and in EP 1 477 508 Al, in the example 3. For the coating agent according to the present invention, aliphatic oligocarbonate diols with a molecular weight of 200 to 2000 g / mol based on 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, are preferably used. cyclohexanedimethanol or its mixtures. The polyacrylate polyols b) used can be obtained copolymerized from each other, according to methods known to the skilled person, from 0 to 10% by weight of one or more functional polybutadienes, optionally, with an average molecular weight of 500 to 10,000. g / mol and with a proportion of 1.2 vinyl double sided bonds of at least 10 mol% with respect to all double ynyl bonds of polybutadiene, b2) from 1 to 30% by weight of one or more aromatic monomers not saturated, chosen from the group of styrene, methylstyrene and vinyltoluene, b3) from 20 to 80% by weight of one or more hydroxyalkyl esters of acrylic or methacrylic acid with primary hydroxyl groups. b4) from 0 to 30% by weight of one or more cycloaliphatic esters of acrylic or methacrylic acid and monoalcohols C3-C? , b5) of 10 to 60% of one or more aliphatic esters of acrylic or methacrylic acid and monoalcohols Ci-Cs, b6) of 0.1 to 5% of one or more C3-C, dicarboxylic or dicarboxylic acids. unsaturated or of one or more half esters of maleic acid or fumaric acid and monoalcohols Ci-C? and b7) from 0 to 30% by weight of other copolymerizable compounds other than the compounds of components bl) to b6), and the sum of the weight% of components b) to b7 being 100% by weight. Preferably, the copolymers of component b) are composed of b) 0.1 to 8% by weight of one or more functional polybutadienes, optionally with an average number-average molecular weight of 500 to 5,000 g / mol and with a of double side vinyl bonds of at least 20 mol% with respect to all vinyl double bonds of polybutadiene, b2) from 2 to 28% by weight of styrene, b3) from 25 to 70% by weight of one or more compounds of the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate and 1,4-butanediol monoacrylate, b4) from 0 to 25% by weight of one or more cycloaliphatic esters of acrylic or methacrylic acid and monoalcohols C3-C ? , b5) of 15 to 60% by weight of one or more esters of acrylic or methacrylic acid and of the aliphatic monoalcohols Ci-C8, b6) of 0.3 to 4% by weight of one or more compounds of the group formed by the acrylic acid, methacrylic acid, hemiesters of maleic acid and hemiesters of fumaric acid of the corresponding acids and of the monoalcohols Ci-Cs and b7) from 0 to 25% by weight of one or more compounds of the group consisting of acrylonitrile, methacrylonitrile, hydroxypropyl (meth) acrylate, vinyl esters of Ci-Cι aliphatic monocarboxylic acids, optionally branched, dialkyl or dicycloalkyl of maleic or fumaric acid and C3 to C8 monoalcohols, and the sum of% by weight of the components bl) to b7) 100% of the weight. In a particularly preferred manner, the copolymerites of component b) are composed of from 0.2 to 6% by weight of one or more functional polybutadienes, optionally with an average number-average molecular weight of 500 to 3,000 g / mole and with a proportion of 1.2 vinyl double side links of at least 30 mole% with respect to all the vinyl double bonds of the polybutadiene, b2) from 5 to 25% by weight of styrene, b3) from 30 to 65 % by weight of hydroxyethyl acrylate, hydroxymethyl methacrylate or mixtures thereof, b4) from 0 to 20% by weight of one or more compounds of the group consisting of isobornyl acrylate, isobornyl methacrylate, cyclohexyl (meth) acrylate, 3, 5, 5-trimethylcyclohexyl (meth) acrylate, 4-tert. (meth) acrylate. -butylcyclohexyl, b5) from 20 to 50% by weight of one or more esters of acrylic or methacrylic acid and of aliphatic monoalcohols Ci to C3, b6) from 0.5 to 3% by weight of acrylic acid, methacrylic acid or its mixtures, b7) from 0 to 20% by weight of one or more compounds of the group consisting of acrylonitrile, methacrylonitrile, hydroxypropyl (meth) acrylate, vinyl esters of C 1 -C 0 aliphatic monocarboxylic acids, optionally branched, and dialkyl or dicycloalkyl esters of maleic or fumaric acid and monoalcohols C 3 to Cs, where the sum of% by weight of the components bl) to b7) amounts to 100% of the weight. With very particular preference, the copolymers of component b) are composed of from 0.4 to 5% by weight of one or more functional polybutadioenes, optionally, with an average number-average molecular weight of 500 to 2,000 g / mol and with a proportion of 1.2 vinyl double bonds of at least 40 mol% with respect to all vinyl double bonds of polybutadiene, b2) from 5 to 20% by weight of styrene, b3) from 30 to 60% by weight of hydroxyethyl acrylate, hydroxyethyl methacrylate or mixtures thereof, b4) from 0 to 15% by weight of one or more compounds of the group consisting of isobornyl acrylate, isobornyl methacrylate, cyclohexyl (meth) acrylate, 3, 5, 5-trimethylcyclohexyl (meth) acrylate, 4-tert. (meth) acrylate. -butylcyclohexyl, b5) from 25 to 45% by weight of one or more esters of acrylic or methacrylic acid and of aliphatic monoalcohols Ci to C4, b6) from 0.5 to 2% by weight of acrylic acid, methacrylic acid or its mixtures, b7) from 0 to 15% by weight of one or more compounds of the group consisting of hydroxypropyl (meth) acrylate, vinyl esters of branched aliphatic monocarboxylic acids Ci-C9, optionally, and dialkyl or dicycloalkyl esters of maleic or fumaric acid and monoalcohols C3 to C6, where the sum of the weight% of the components bl) to b7) amounts to 100% by weight. The production of the resin of component b) is carried out by the copolymerization of constituents b) to b7) according to conventional methods familiar to the specialist [Houben-Weyl (editor): Methods of Organic Chemistry, fourth edition, E 20 /2. Thieme, Stuttgart 1987, p. 1156], with a solution polymerization of components a) to b7) being preferred at temperatures of 140 to 240 ° C in the presence of radical formers.

The oligomers b1) to b7) are generally used in the same proportions as those used for the polymerization, in which they are integrated into the copolymer. The integrated units are distributed in an essentially statistical way. As starting materials bl) for the copolymerization products b) which are essential for the invention, all polybutadienes with an average number-average molecular weight of 500 to 10,000 g / mol, which have a ratio of vinyl double bonds in one position, are substantially suitable. 12, at least 10% by mole, preferably at least 20% by mole, more preferably at least 40% by mole, with respect to all the vinyl double bonds found in the polybutadiene. Typically, as compounds of component b), isomeric mixtures of polybutadiene are used whose double vinyl bonds in the 1,2-position are from 10 to 90% by mol, in the 1,4-cis and / or 1,4-trans position of the 10 to 70% in moles, and in cyclic structures, they have from 0 to 30% in moles. The polybutadienes used can also optionally carry functional groups, such as, for example, hydroxyl groups and carboxyl groups. A synopsis of the appropriate polybutadienes of the type indicated above in "Makromoleküle" ("Macromolecules"), by H. G Elias, fourth edition, Hüthig und Wepf, Basel, Heidelberg, New York, pp. 676, 744-746, is given. 1012 and following. The production of the copolymerization products b) can be carried out in the presence of a solvent. For this purpose, for example, aliphatic, cycloaliphatic and / or aromatic hydrocarbons, such as alkylbenzenes, for example toluene, xylene, are suitable.; esters, such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-hexyl acetate, 2-hexyhexyl acetate, ethyl propionate, butyl propionate , pentyl propionate, ethylene glycol monoethyl ether acetate, the corresponding methyl ether acetate; ethers, such as ethylene glycol acetate onomethyl ether, ethylene glycol monoethyl ether of ethylene glycol acetate and monobutyl ether of ethylene glycol acetate; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone or mixtures of the same type of solvents. The production of the copolymerization products b) can be carried out continuously or discontinuously. In a continuous production, the monomer mixture and the initiator are dosed in a polymerization reactor, in a uniform and continuous manner, and, at the same time, the corresponding quantity of the polymerization product is continuously eliminated, so that products of very homogeneous copolymerization. In discontinuous production, the monomer mixture and the reactor are metered into the polymerization reactor, whereby the polymerization product is maintained in the reactor. To obtain the structured copolymers in the most homogeneous manner possible, the monomer mixture and the initiator are dosed at a constant speed in the reactor. By homogeneous copolymer, in the sense of the invention, the copolymers are understood to have a narrow molecular weight distribution and a low inhomogeneity (Mw / Mn) of, preferably, = 2.5, as well as with almost the same monomeric composition of the molecular chains. In general, the copolymerization is carried out in a temperature range of from 40 to 240 ° C, preferably from 145 to 220 ° C and, particularly preferably, from 150 to 200 ° C. The copolymerization can be carried out in this case under a pressure of up to 1500 kPa. The initiators are used in amounts of 0.05 to 15% by weight, preferably 1 to 10% by weight, especially 2 to 8% by weight, with respect to the total amount of the components bl) to b7). Suitable initiators for the production of the copolymerization products b) are initiators by conventional radicals based on peroxide or azoperoxides, but only those which have, within the aforementioned temperature range, a sufficiently long half-life for the polymerization, of about 5 seconds to approximately 30 minutes. Suitable, for example, are 2, 2'-azobis- (2-methylpropanonitrile), 2,2'-azobis- (2-methylbutanonitrile), 1,1''-azobis (cyclohexane-carbonitrile), peroxy-2-ethylhexanoate tere. -butyl, tere acetate. -peroxydiethybutyl, tere isobutyrate. -peroxybutyl, 1, 1-di-tert. -butylperoxy-3, 3, 5-trimethylhexanoate, 1, 1-di-tert. peroxy-3, 5, 5-trimethylhexanoate tere-butylcyclohexane. -butyl, carbonate of tere. -peroxybutyloisopropylbutyl, texaeacetate. -butyl, tert-butyl peroxybenzoate, dicumyl peroxide, tereperoxide. -butylcumyl, di-tert. peroxide. -butyl and di-tert. peroxide -amilo In a special embodiment, the polycrylatopolols are produced in the presence of at least one of the oligocarbonatopolyol a) according to the procedure described above. Thus, the polymerization can be carried out both in the absence of organic solvents, where the oligocarbonatopoliol represents the reaction medium for the radical polymerization, as well as in mixtures of organic solvents and oligocarbonatopolols a).

In the reactive (poly) isocyanate crosslinking agents, as opposed to the OH groups, these are discrete polyisocyanates formed from at least two diisocyanates and produced by the modification of simple aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates , with a structure of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione, as described, for example, in J. Prakt. Chem. 336 (1994) 185-200, the documents DE-A 16 70 666, 19 54 093, 24 14 413, 24 52 532, 26 41 380, 37 00 209, 39 00 053 and 39 28 503 or the EP- A 336 205, 339 396 and 798 299, by way of example. Suitable diisocyanates for the production of these polyisocyanates are all diisocyanates of the molecular weight range of 140 to 400 g / mol, accessible by phosgenation or, by phosgene-free processes, for example by thermal dissociation of urethane, with isocyanate groups aliphatic, cycloaliphatic, araliphatic and / or aromatically such as 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDl), 2-methyl-1, 5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2, 2, 4- 2, 4, 4-trimethyl-l, 6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis- (isocyanatomethyl) -cydohexane, l-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane, 1-isocyanato-l-methyl-4 (3) isocyanato-methylcyclohexane, bis- ( isocyanatomethyl) -norbornane, 1,3- and 1,4-bis- (2-isocyanato-prop-2-yl) -benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDl), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 1,5-diisocyanatophthalene or discretional mixtures of these diisocyanates. Preferably, they are polyisocyanates or mixtures of polyisocyanates of the designated type with isocyanate groups bound only aliphatically and / or cycloaliphatically. With very special preference, they are polyisocyanates or mixtures of polyisocyanates with isocyanurate structure based on HDI, IPDI and / or 4, '-diisocyanatodicyclohexylmethane. Thus, in addition, it is possible to use the so-called blocked polyisocyanates and / or isocyanates, preferably polyisocyanates and / or mixtures of blocked polyisocyanates, very particularly preferably polyisocyanates or mixtures of blocked polyisocyanates with isocyanurate structure based on HDI, IPDI and / or 4, 4. '-diisocyanatodicyclohexylmethane.

The blocking of (poly) isocyanates for temporary protection of the isocyanate groups is a working method that has been known for a long time and is described, for example, in Houben Weyl, "Methoden der organischen Chemie" ("Methods of organic chemistry ") XIV / 2, pp. 61-70. As a blogging agent, all the components that can be dissociated when heating the blocked (poly) isocyanate are considered, if necessary, in the absence of a catalyst. Suitable blocking agents are, for example, amines with spherical hindrance, such as dicyclohexylamine, diisopropylamine, N-tert. -butyl-N-benzylamine, caprolactam, butanone oxime, imidazoles with all possible substitution patterns, pyrazoles, such as 3,5-dimethylpyrazole, triazoles and tetrazoles, in the same way as alcohols such as isopropanol and ethanol. In addition, there is also the possibility of blocking the isocyanate group in such a way that, in a subsequent reaction, the blocking agent is not dissociated, but that the intermediately formed intermediate state reacts. This is especially the case of the ethyl ester of cyclopentane-2-carboxylic acid, which, in the thermal crosslinking reaction, reacts completely by integrating into the polymer network and does not re-dissociate. Especially in the use of the blocked polyisocyanates, other reactive compounds which show groups reactive towards the OH or NH groups, as additional crosslinking components, can be used in addition to the components B). For exampleThese are aminoplast resins. As aminoplast resins, the condensation products known in lacquer technology, melamine and formaldehyde, or urea and formaldehyde are considered. Suitable here are all conventional melamine and formaldehyde condensates with or without saturated onoalcohols of 1 to 4 carbon atoms. In the case of the use of other crosslinking components, the quantity must be adjusted correspondingly to the binder with hydroxyl groups reactive towards NCO. As catalysts for the reaction of the components A) with the component B) for the production of the coating agents according to the invention, catalysts can be used as the organometallic components for commercial use, of the elements aluminum, tin, zinc , titanium, manganese, iron, bismuth or also zirconium, such as dibutyltin laurate, zinc octoate, titanium tetraisopropylate. In addition, however, tertiary amines, such as 1,4-diazabicyclo [2.2.2] octane, are also suitable. In addition, it is possible to accelerate the transformation of component B) with component A), carrying out the curing at temperatures between 20 and 200 ° C, preferably between 60 and 180 ° C, particularly preferably between 70 and 150 ° C. . In addition to the mixture of polyols A) essential to the invention, it is also possible to use other organic polyhydroxy compounds or reactive amine diluents known to those skilled in the art of polyurethane coating technology.

In these other polyhydroxene compounds, it can be conventional polyester polyols, polyether polyols, polyurethane polyols, or other polycarbonatopolols and polyacrylate which have not been described so far. Preferably, as additional organic polyhydroxylic compounds, provided that they are used in addition to the polyol component A) essential to the invention, the known polyacrylate polyols and / or the polyester polyols of the state of the art are used. In the amine reactive diluent, it can be products with blocked amino groups, such as aldimines or ketimines, or those that show free amino groups, although attenuated in their reactivity, such as the aspartic acid esters. Generally, the reactive amine diluents show more than one (blocked) amino group, so that, during the crosslinking reaction, they contribute to the structuring of the network of the coating film. If, in addition to the polyol components A) according to the invention, other polyhydroxy compounds or reactive amine diluents of the type indicated above are used, the proportion of these compounds which are reactive towards the additional isocyanates reaches a maximum of 50% by weight. weight, preferably a maximum of 30% by weight, with respect to the amount of component A) essential for the invention. Preferably, however, the polyol component A) essential for the invention is used as the sole polyol component in the coating agent according to the invention. The proportion of component B) to component A) and, where appropriate, other crosslinking agents and hardening accelerators, is dimensioned in this respect in such a way as to result in an NCO / OH ratio of the free NCO groups and, if necessary, blocked, with respect to the groups reactive towards the isocyanate, from 0.3 to 2, preferably from 0.4 to 1.5, particularly preferably from 0.5 to 1.2. In the coating agents essential to the invention, in addition to the essential components for the invention A) and B), conventional coating technology, adjuvants, such as organic or inorganic pigments, other organic photoprotective agents, can also be used together radical scavengers, or lacquer additives, such as dispersing agents, leveling agents, thickeners, defoamers and other adjuvants, adhesive agents, fungicides, bactericides, stabilizers or inhibitors and other catalysts. The coating compositions according to the invention are preferably used in the field of plastic paint, industrial painting in general, lacquering of large vehicles, vehicle repair paint, first paint of the vehicle, coating of soles and / or wood / furniture varnishing. The coatings and coated substrates obtained using the coating agents according to the invention are therefore also subject. Examples; Desmophen® A 870: polyacrylate containing hydroxyl groups from Bayer MaterialScience AG, Leverkusen, Germany; approximately 70% in butyl acetate, with a hydroxyl content, according to DIN 53 240/2, of approximately 2.95%. Desmophen® VP LS 2971: Desmophen with elastifying polyester, containing hydroxyl groups, from Bayer MaterialScience AG, Leverkusen, Germany; approximately 80% in butyl acetate, with a hydroxyl content, according to DIN 53 240/2, of approximately 3.8%. Desmodur® N 3600: aliphatic polyisocyanurate from Bayer MaterialScience AG, Leverkusen, Germany; 100% by weight, with an NCO content, according to DIN EN ISO 11909, of 23% by weight. Desmodur® N 3390 BA: aliphatic polyisocyanurate from Bayer MaterialScience AG, Leverkusen, Germany; to the 90% by weight in n-butyl acetate, with an NCO content, according to DIN EN ISO 11909, of 19.6% by weight. The determination of the hydroxyl number (OH index) carried out according to DIN 53240-2. The determination of the viscosity made by the rotational viscometer "Rotovisco 1" from the manufacturer Haake, Germany, according to DIN EN ISO 3219. The determination of the acid number made according to DIN EN ISO 2114. The determination of the colorimetric index (APHA) made according to DIN EN 1557. Example 1 Production of an oligocarbonate diol aliphatic based on 1, 6-hexanediol with an average numerical molecular weight of 1000 g / mol In a 5-liter pressure reactor with distillation head, stirrer and vessel, 2943 g of 1,6-hexanediol are added with 0.7 g of ytterbium acetylacetonate (III), as well as 1051 g of dimethyl carbonate at 80 ° C. Then, the reaction mixture is heated, under a nitrogen atmosphere, for 2 hours, at 150 ° C, and then it is kept there for 2 hours, under stirring and reflux, increasing the pressure increases to 3.9o kPa (absolute). Then, the dissociation product methanol, in mixture with the dimethyl carbonate, is separated by distillation, the pressure being lowered continuously, during the following 4 hours, at 2.20 kPa total. Then, the distillation process is finished, and another 1051 g of dimethyl carbonate is pumped at 150 ° C, into the reaction mixture, and there it is kept for 2 hours, under agitation and reflux, increasing the pressure to 3.90. k Pa (absolute). Subsequently, the dissociation product methanol is again separated in the mixture with dimethyl carbonate, by distillation, reducing the pressure continuously to a total of 2.20 kPa .. The distillation process is then completed and pumped Another 841 g of dimethyl carbonate at 150 ° C, to the reaction mixture, and there it is kept for 2 hours, with stirring and reflux, increasing the pressure to 3.50 kPa (absolute). Subsequently, the dissociation product methanol is again separated in the mixture with dimethyl carbonate, by distillation, reducing the pressure, for 4 hours, until reaching normal pressure. Immediately afterwards, the reaction mixture is heated, for two hours, to 180 ° C, and kept under stirring at this temperature. Then, the temperature is reduced to 130 ° C and a stream of nitrogen (51 / h) is channeled through the reaction mixture, while the pressure is reduced to 0.2 kPa. Then, the temperature is increased for 4 hours. hours at 180 aC, and it stays there for 6 hours. Thus, the other separation of the methanol in the mixture with dimethyl carbonate from the reaction mixture is carried out. After cooling and cooling the reaction mixture to room temperature, a transparent, waxy oligocarbonate diol is obtained with the following characteristics: Mn = 1035 g / mol; OH number = 108.2 mg KOH / g; viscosity: 510 mPa-s at 75 ° C. Example 2 Production of an aliphatic oligocarbonate diol based on 3-Methyl-1,5-pentanediol with an average number-average molecular weight of 650 g / mol The same procedure as in Example 1, wherein, instead of 1,6-hexanediol, add 34092 g of 3-methyl-l, 5-pentanediol and 8.0 g of ytterbium acetylacetonate (III) in a pressure vessel of 60 1, and add dimethyl carbonate in three phases, two of which, with 10223 g, and the other, with 7147 g A colorless, liquid oligocarbonate diol is obtained, with the following characteristics: Mn = 675 g / mol; OH number = 166.0 mg KOH / g; viscosity: 4146 mPa-s at 23 ° C. Example 3 Production of an aliphatic oligosarbonate diol based on cyclohexanedi ethanol with an average number-average molecular weight of 500 g / mol The same procedure as in example 1, where, instead of 1, 6-hexanediol, add 3119 g of cyclohexanedi ethanol and dimethyl carbonate, in three phases, two of which with 659 g, and the other with 527 g A colorless, liquid oligocarbonate diol is obtained, with the following characteristics: Mn = 518 g / mol; OH number = 216.4 mg KOH / g; viscosity: 5700 mPa-s at 75 ° C. Example 4 Production of an aliphatic oligocarbonate diol based on cyclohexanedimethanol with a molecular weight of 650 g / mol The same procedure as in example 1, where, in place of 1,6-hexanediol, 2018 g of cyclohexanedimethanol and dimethyl carbonate are added in three phases, two of which with 1101 g, and the other with 881 g A colorless, liquid oligocarbonate diol is obtained, with the following characteristics: Mn = 625 g / mol; OH number = 179.3 mg KOH / g; viscosity: 14000 mPa-s at 75 ° C. EXAMPLE 5 Production of an aliphatic oligocarbonate diol based on 3-methyl-1,5-pentanediol with a number-average molecular weight of 500 g / mol The same procedure as in example 1, wherein, instead of 1,6-hexanediol, add 3018 g of 3-methyl-l, 5-pentanediol and dimethyl carbonate, in three phases, two of which with 835 g, and the other with 668 g A colorless, colorless oligocarbonate diol is obtained, with the following characteristics: Mn = 539 g / mol; OH number = 207.7 mg KOH / g; viscosity: 2500 mPa-s at 23 ° C Example 6: Production of an aliphatic oligoester based on trimethylolpropane In a reactor according to Example 7, 3155 g of trimethylpropane and 1345 g of e-caprolactone and 2.2 g of dibutyltin dilaurate (DBTL) are introduced. The contents of the container are heated to 160 ° C, stirred for 6 hours at 160 ° C and, when confined, cooled to 20 ° C, obtaining a clear resin with the following characteristics: solids content: 99 , 5% by weight, viscosity at 23 ° C: 4100 mPa-s, acid number: 0.5 mg KOH / g, hydroxyl number: 881 mg KOH / g, hydroxyl content: 26.7% by weight, color index of Hazen: 44 APHA. Example 7: Production specifications for the essential Al-A7 copolymerization products of the invention In a 5-liter stainless steel pressure reactor with a stirrer, a distillation device, a container for the monomer mixture and an initiator, with inclusion of dosing pumps, as well as the automatic regulation of temperature, part 1 is added, and heated to the desired polymerization temperature. Then, they are dosed, starting together, through different inputs, part 2 (the monomer mixture) for 3 hours, and part 3 (solution of the initiator) for 3 hours and a half, keeping the polymerization temperature constant (+ 2 ° C) ). Then, stirring is continued for 60 minutes, at the polymerization temperature. Then, if a part 4 is used, it is cooled to 80 ° C, this part 4 is dosed and stirred for 30 minutes at 80 ° C. Then, it is cooled to room temperature and the solids content is determined. The copolymerization products should have a solids content of 70 + 1%. With a solids content of < 68%, is then activated with 5% of the original amount of the initiator, for 30 minutes, at 150 ° C. With a solids content between 68 and 69%, it is distilled at 70 _ + 1%. Next, the copolymerization product is filtered through a filter (Supra T5500, pore size 25-72 μm, Seitz-Filter-Werke GmbH, Bad Kreuznach, Germany). The compositions of parts 1 through 4, as well as the characteristic data of the products obtained, are shown in Table 1.

Table 1: Copolymerization product Al A2 A3 A4 A5 A6 Kl Part 1 Butyl acetate 23.18 23.18 23.18 23.18 - - - Solvent naphthaOO1 '- - - - 22.49 22, 49 24.28 Oligocarbonate diol of Example 7,32 7,32 7,32 7,32 N.2: (3) (4) (5) 12) - - - Part 2 Styrene 16.45 16.45 16.45 16.45 9.72 9.72 10.49 Hydroxyethyl methacrylate 30.13 30.13 30.13 30.13 19.64 19.64 21.19 Butyl acrylate 15.26 15.26 15.26 15.26 30.15 30.15 32.55 Polybutadiene Nisso® B 10002 '0.66 0.66 0.66 0.66 0.86 0.86 0.93 Acrylic acid 0.66 0.66 0.66 0.66 0.98 0.98 1.05 Part 3 di-tert. Peroxide utilo 2,64 2,64 2,64 2,64 2,56 2,56 2,76 Butyl acetate 3.70 3.70 3.70 3.70 3.60 3.60 3.88 Part 4 Oligoester example n.2 6 6.40 5.70 2.87 Oligocarbonate example n.2 2 0.70 1.40 Solvent naphtha 1001 2.90 2.90 Polymerization temperature 170 170 170 170 ° C 160 160 165 Data Solids content% by weight 70.3 69.9 70.0 70.0 69.6 69.9 70.0 Viscosity at 23 ° C, mPa-s 3313 3503 2221 2642 3753 4754 4204 acid number, lff., Mg 8.2 KOH / g 7.8 8.3 7.7 8.9 8.8 9.5 index of OH, fs. mg KOH / g 143 144 149 132 132 134 113 Content of OH, FH,% by weight 6.16 6.30 6.50 5.71 5.75 5.81 4.89 Color index of Hazen, APHA 56 29 38 49 39 34 37 All data about quantities must understood in% by weight. 1) Commercial product of the DHC Solvent Chemie GmbH, D-45478 Mülheim, "from the Ruhr region 2) Commercial product of the Nippon Soda, Japan Examples of technical application: Example 8: Preparation of the mother varnish (component 8A) A 112.2 g of polyol A7, 8.7 g of the aliphatic oligocarbonate diol of Example 2, 1.34 g of Bay-silone® OL 17 (10% solution in MPA, Borchers GmbH, Langenfeld), 2.69 g are added. of Tinuvin® 292 (50% solution in MPA, Ciba Spezialitátenchemie Lampertheim GmbH, Lampertheim), 4,03 g of Tinuvin® 382/4 (50% solution in MPA, Ciba Spezialitátenchemie Lampertheim GmbH, Lampertheim), 1.34 g of Modaflow® (1% solution in MPA; Brenntag AG, Mülheim / R), 26.21 g of a 1: 1 mixture of 1-methoxypropyl 2-acetate and solvent naphtha 100 and stirred intimately. Preparation of the hardening accelerator solution (component 8B) To 47.2 g of Desmodur® N 3600, 26.21 g of a 1: 1 mixture of 1-methoxypropyl 2-acetate and solvent naphtha 100 are added and stirred intimately mixing Examples 9-13: The same procedure as in example 8A or 8B. However, the raw materials cited in table 2 are used: Table 2: Intermixing of the mother lacquer with the hardening accelerator and application: The components mentioned above A (mother lacquer) and B (hardening accelerator) are mixed and stirred mixing intimately. Then, the corresponding mixtures are applied with a compressed air gun in a roll coating plate precoated with a black basecoat layer, ventilated at room temperature and then dried for 30 minutes at 140 ° C. in forced ventilation stove. Particularly bright coatings are obtained, with a dry film layer thickness of approximately 40 μm. In Table 3, a synopsis is collected about the determined characteristics of the coating technique. Table 3: Characteristics of the coatings coating technique Test methods: Pendular hardness: The pnedular hardness is determined according to DIN EN ISO 1522. Resistance to gasoline: Test with FAM test fuel according to DIN 51 635, in accordance with VDA 621-412 (Testing A 4.1.1 Y and 4.1.3 Y) and xiol; charge duration, 10 min: Scratch resistance: Scratch resistance is determined in accordance with DIN 55668 (method for "scratch resistance testing of coatings with a laboratory wash facility"). The measurement of the degree of brightness as a reflectometer value according to DIN 67 530 is done before and after loading by 10 double passes, as well as, once again, after 2 hours of storage at 60 ° C (reflux behavior ). Resistance to chemical substances: The resistance to chemical substances is determined according to DIN EN ISO 2812/5 (draft) in the gradient furnace. The coatings according to the invention according to examples 8 to 13 show an improved scratch resistance (both before and after reflow), compared to comparative examples 1 and 2. The resistance to chemical substances and, especially, the resistance to the acids of the coatings according to the invention is, as a whole, better than that of the comparative examples mentioned. It is noted that in relation to this date, the best method known by the applicant to carry out the present invention is that which is clear from the present description of the invention.

Claims (9)

- - Claims Having described the invention as above, the content of the following claims is declared as property:

1. Coating agent characterized by contains A) A polyol component consisting of a) from 1 to 50% by weight of aliphatic oligocarbonatopolols with a number average molecular weight Mn of 200 to 5 000 g / mol and b) of 50 to 99% in weight of hydroxy-functional polyacrylate polyols and B) one or more reactive (poly) isocyanate crosslinkers, against OH groups, with an average NCO functionality of > 2.0.

2. Coating agent according to claim 1, characterized in that the amount of component a) amounts to 1 to 10% by weight and that of component b), to 90 to 99%. 3. Coating agent according to claim 1 or 2, characterized in that in a) aliphatic oligocarbonatopolols with a molecular weight of 200 to 2000 g / mol, based on 1,4-butanediol, 1,6-hexanediol, are used, -

3-methyl-l, 5-pentanediol, cyclohexanedimethanol or their mixtures.

4. Coating agent according to one of claims 1 to 3, characterized by b) copolymerization products of b) from 0.4 to 5% by weight of one or more functional polybutadienes, optionally with a weight, are used in b) number average molecular weight of 500 to 2,000 g / mol and with a proportion of 1.2 vinyl double side links of at least 40 mol% with respect to all double vinyl bonds of polybutadiene, b2) from 5 to 20% by weight of styrene, b3) from 30 to 60% by weight of hydroxyethyl acrylate, hydroxyethyl methacrylate or mixtures thereof, b4) from 0 to 15% by weight of one or more compounds of the group consisting of isobornyl acrylate, isobornyl methacrylate, (meth) cyclohexyl acrylate, 3,5,5-trimethylcyclohexyl (meth) -crylate and 4-tert-butylcyclohexyl (meth) acrylate, b5) from 25 to 45% by weight of one or more esters of acrylic or methacrylic acid and of aliphatic monolcohols Ci to C4, b6) from 0.5 to 2% by weight of acid or acrylic, methacrylic acid or mixtures thereof, and b7) from 0 to 15% by weight of one or more compounds of the group consisting of hydroxypropyl (meth) acrylate, vinyl esters of branched aliphatic monocarboxylic acids Ci-Cg, given the case, and dialkyl or dicycloalkyl esters of maleic or fumaric acid and C3 to C6 monoalcohols, the sum of the weight% of components bl) to b7) being 100% by weight. Coating agent according to one of claims 1 to 4, characterized in that the copolymers used in b) show a heterogeneity (Mw / Mn) of < 2.

5. Coating agent according to one of claims 1 to 5, characterized in that the polyol component A) is produced by the polymerization of the corresponding monomers of the copolymerization product b) in the aliphatic oligocarbonatopolols a). Coating agent, according to one of claims 1 to 6, characterized in that polyisocyanates and / or mixtures of polyisocyanates with an isocyanurate structure based on HDl, IPDI or 4,4'-diisocyanatodicyclohexylmethane are used in B). Coating agent, according to one of claims 1 to 7, characterized in that the NCO / OH ratio of the free and, where appropriate, blocked NCO groups, with respect to the groups reactive towards the isocyanate, is from 0.5 to 1.2. . The coatings characterized in that they are obtained using the coating agent according to one of claims 1 to 8. 10. The substrates characterized in that they are coated with coatings according to claim 9.