MXPA01008578A - Utilization of tricyclodecandimethanol for producing multilayer lacquers - Google Patents

Abstract

The invention relates to the utilization of tricyclodecandimethanol for producing multilayer lacquers, in particular, multilayer transparent lacquer coatings, and as a binding agent in multilayer lacquers. The invention also relates to a coating substance, especially transparent lacquer, containing at least one binding agent, at least one cross-linking agent and tricyclodecandimethanol. In addition, the invention relates to a method for improving the adherence of the intermediate layer in multilayer transparent lacquer coatings.

Description

USING TRICICLODECANDIMETHANOL FOR THE PRODUCTION OF MULTIPLE LAYER LACQUERS The present invention relates to the novel use of tricyclodecanedimethanol for the production of multi-layered lacquers, particularly multilayer transparent lacquer coatings, and as a multilayer lacquer bonding agent. . Furthermore, the present invention relates to a coating material, especially a new transparent lacquer, containing tricyclodecanedimethanol. The present invention also relates to a novel process for improving intercoat adhesion in multi-layered clearcoats. The present invention also relates to a novel multilayer lacquer containing a multi-layered transparent lacquer. In addition, the present invention relates to a process for the production of multilayer lacquering which is based on a wet-on-wet process. The present invention also relates to the use of new multi-lacquered coatings, in particular in the automotive lacquering of automobiles, automotive repair lacquering and in industrial lacquering, including container coating and coil coating. The requirements regarding the stability of the coating lacquers that are exposed to the weather, especially solar radiation and acid rain, and increasingly frequent mechanical attacks, especially through the washing devices of vehicles with brushes, are each higher times. This is especially true in the case of lacquered vehicles that must meet these requirements and also must have a satisfactory optical appearance in terms of brightness, surface smoothness and color. To date these problems have been solved insofar as a multi-lacquered lacquer consisting essentially of aqueous coating materials that meet the highest environmental care requirements is applied to the substrates. In the case of metallic substrates, a water-based filler, a water-based lacquer and a solvent-containing clear lacquer are prepared in a known manner from an aqueous elassion lacquer. The electrodeposition lacquer and aqueous filler are baked in each case after application and form the preparation layer. A water-based lacquer is applied to this layer and partially dried. The transparent lacquer is applied to this uncured layer, after which the two layers are hardened together (wet-on-wet process). If plastics are used as substrates, hydropreparation is used in a known manner instead of electrodeposition lacquer. The wet wet process for the manufacture of multilayer coating lacquer is described, for example, in the documents of US-A-3, 639, 147, DE-A-33 33 072, DE-A-38 14 853, GB-A-2 012 191, US-A-3, 953, 644, EP-A-0 260 447, DE-A-39 03 804, EP-A-0 320 552, DE-A-36 28 124, US-A-4,719,132, EP-A-0 297 576, EP-A-0 069 936, EP-A-0 089 497, EP-A-0 195 931, EP-A-0228 003, EP- A-0 038 127 and DE-A-28 18 100. The two upper layers of the multilayer lacquers are mainly responsible for the optical or visual appearance of the weather resistance. The water-based lacquer of the multi-lacquered lacquer provides the color and / or the optical effects such as for example metal effects or interference effects, while the transparent lacquer in addition to the resistance to scratches and chemical attacks, ie the stability against the harmful substances of the environment, provides what is known as appearance, that is, brightness and smoothness. The water-based lacquer and the clear lacquer must correspond very precisely to one another in order to provide a link with the desired profitable property profile. Aqueous-based lacquers as well as the corresponding lacquers that comply with these requirements in an essential manner are apparent from the patent documents EP-A-0 089 497, EP-A-0 256 540, EP-A-0 260 447, EP-A-0 297 576, WO 96/12747, EP-A-0 523 610, EP-A-0 228 003, EP-A- 0 397 806, EP-A-0 574 417, EP-A-0 531 510, EP-A-0 581 211, EP-A-0 708 788, EP-A-0 593 454, DE-A-43 28 092, EP-A-0 299 148, EP-A-0 394 737, EP-A-0 590 484, EP-A-0 234 362, EP-A-0 234 361, EP-A-0 543 817, WO 95/14721, EP-A-0 521 928, EP-A-0 522 420, EP-A-0 522 419, EP-A-0 649 865, EP-A-0 536 712, EP-A-0 596 460, EP-A-0 596 461, EP-A-0 584 818, EP-A-0 669 356, EP-A-0 634 431, EP-A-0 678 536, EP-A-0 354 261 , EP-A-0 424 705, WO 97/49745, WO 97/49747 or EP-A-0 401 565. These aqueous-based lacquers contain, in particular, anionically stabilized polyurethanes, wherein polyfunctional amines are used as the neutralizing agent. or aminoalcohols such as for example triethylamine, methylethanolamine and / or dimethylethanolamine. In the modern lacquering in series of cars or in the case of car repairs, many different transparent lacquers are used, such as, for example, one component (IC), two component (2C) or multi-component clearcoats (3C, 4C), which contain solvent, two-component aqueous clearcoats (2C) or various components (3C, 4C), clearcoats in powder form, clearcoats in powdery paste or UV clearcoats in particular lacquers without solvents or in powder form. All these transparent lacquers have very specific advantages that can be used for each specific purpose.

For example, one-component clearcoats (IC) provide multi-layered coatings that are satisfactory in terms of compliance with the highest optical requirements and abrasion resistant, however clearcoat layers are often not sufficiently resistant to the weather. On the contrary, the clearcoat layers based on two component clearcoats (2C) or several components (3C, 4C) are stable to the weather but are often not sufficiently resistant to abrasion. It would therefore be desirable, within the framework of a multilayer lacquer, to combine the specific advantages of transparent lacquer layers having different constituents in such a way that layers of clear multilayer lacquers are obtained which, for example, have stability to the lacquer. weathering and also resistance to abrasion. This must also be done without additional expenses for the user. However, this can not be achieved in a simple manner since the combination of the known transparent lacquers in layers of multi-layered transparent lacquers poses difficult problems of adhesion between the layers. These problems can cause that not only the top transparent lacquer layer is detached, but also the layer that is underneath it. These problems are especially evident in the case of automotive repair lacquering where the clear repair lacquer must form a firm bond with the transparent lacquer layer of the car's serial lacquering. To date, this problem of the adhesion between the layers could only be solved by grinding the transparent lacquer layer to be repaired. However, this process presents an additional work step in the lacquering installation, which basically represents a drawback. The object of the present invention is to present a new lacquering of several layers which does not present the drawbacks of the state of the art, but which provides an optical property profile or excellent appearance in addition to a high hardness, a strong resistance to scratches, and a high stability to chemical attacks, so that there are no superficial disorders and detachments. Furthermore, the object of the present invention is to offer a novel process for the production of multi-layered lacquers which in a simple manner provides safe and reliable multi-layered lacquering. Accordingly, the new coating material was found, especially the new transparent lacquer containing at least one binder and at least one crosslinking agent as well as tricyclodecanedimethanol. Next, the new coating material will be known as "coating material according to the present invention". In addition, the new lacquering of several layers applied on optionally prepared substrate contains (A) a base lacquer layer (B) a first transparent lacquer layer as intermediate layer and (C) a second clear lacquer layer as upper layer, and it is characterized in that at least one of the coating materials used (B) and (C) for the production of the clearcoat layers (B) and (C) contains effective amounts of tricyclodecanedimethanol. Next, the multilayer lacquering which is highly resistant to novel scratches will be known as "lacquering of several layers according to the present invention". Furthermore, the novel process for the production of a multilayer lacquer comprises at least the following process steps: (I) application of a base lacquer (A) on a substrate optionally prepared (II) partial drying of the base lacquer applied (A), (III) application of a first clear lacquer (B), (IV) joint hardening of the layers (A) and (B) applied in the process steps (I) and (III) (humid wet process), (V) ) application of a second layer of clear lacquer (B) different from the first transparent lacquer layer (B) as regards its components on clear lacquer layer (C) hardened in process step (IV) and (VI) hardening of the clear lacquer layer (C) applied in the process step or alternatively (I) the application of a base lacquer (A) on a possibly prepared substrate, (II) partial drying of the applied base lacquer (A), (III) application of a first clear lacquer (B), (IV) partial drying of the applied clear lacquer (B), (V) application of a second layer of clear lacquer (C) on the transparent lacquer layer (B) partially dried in process step (IV) and (VI) joint hardening of lacquer layers (A), (B) and (C) (moist wet process) characterized in that at least one of the coating materials used (B) and (C) for the production of the clearcoat layers (B) and (C) contains effective amounts of tricyclodecanedimethanol.

Next, the new process for the production of a multi-layer lacquering will be known briefly as "a process according to the present invention". Taking into account the state of the art, it was surprising and not foreseeable for the person skilled in the art that the object forming the basis of the present invention could be achieved through the novel use of tricyclodecanedimethanol within the framework of the lacquering of several layers of the present invention and the process according to the present invention. It was particularly surprising that, despite the multi-layered structure of the clear lacquer layer, there were no problems of adhesion between the layers and consequently detachment. Even more surprising is the fact that based on the novel use of tricyclodecandimethanol, it was possible to vary widely in terms of its components the transparent lacquer layer (B) and (C) in such a way that profiles of different profitable properties can be adjusted in a manner simple and elegant In this way, the multilayer lacquers according to the present invention can be adapted particularly easily and precisely to the requirements of the specific purposes of use. The essential constituent of the coating material according to the present invention, especially of the clearcoat according to the present invention, is tricyclodecanedimethanol. Furthermore, the coating material according to the present invention contains at least one binder and at least one crosslinking agent. Regarding this aspect, the content of tricyclodecanedimethanol can vary widely. According to the present invention, however, it is advantageous if the amounts used are within a range of 0.2 to 20% by weight, preferably 1.0 to 7.0% by weight and especially 2.0 to 5.0% by weight, each time with relation to the coating material according to the present invention. In accordance with the present invention, all oligomers and polymers which are commonly used as binders in the field of lacquers are contemplated as binders. Binders used in clearcoat materials are particularly suitable. Accordingly, all the compounds commonly used in the field of lacquers are contemplated as crosslinking agents according to the present invention. Crosslinking agents used in clearcoat materials are particularly suitable. The coating material according to the present invention is therefore preferably used as a clearcoat, in particular as a one-component clearcoat (IC), a two-component clearcoat (2C) containing a clear multi-component clearcoat solvent (3C). , 4C), clear two-component (2C) aqueous lacquer or multi-component (3C, 4C), clear lacquer powder, clear lacquer made of powder paste or transparent UV lacquer, especially as UV transparent lacquer in the form of powder or without solvent. The coating material according to the present invention can be used only for the production of lacquers. For example, it can be used as a coating for prepared or unprepared metal, glass, wood, plastic or paper with a clear lacquer of one layer or several layers. The special advantages of the coating material according to the present invention, however, are found in their use for the production of multilayer lacquers according to the present invention in a particularly evident manner. For the lacquering of several layers according to the present invention, it is essential that at least two, preferably two layers of clear lacquer are applied one on top of the other. For this purpose it is possible to employ a coating material according to the present invention, that is to say that the transparent lacquer layers do not differ among themselves in terms of their constituents.

According to the present invention, however, it is advantageous for the clearcoat layers to differ from each other in terms of their constituents, that is to say that at least one first clearcoat layer (B) and a second layer of clearcoat are used. transparent (C) in such a way as to obtain the desired combination according to the present invention of useful properties of different transparent varnishes. In this case, at least one transparent lacquer layer (B) or the clear lacquer layer (C) is prepared from a coating material according to the present invention. For this reason it is found in effective amounts, especially in the quantities presented above, tricyclodecanedimethanol in the clear lacquer (B) which is used for the formation of the clear lacquer layer (B) or in the clear lacquer (C) used for the formation of the transparent lacquer layer (C). In accordance with the present invention it is an advantage that the tricyclodecanedimethanol is present in the clearcoat according to the present invention (B). According to the present invention, transparent coating materials (B) and (C) can be treated with coating materials that are different in their constituents. Preferred variants in specific cases will depend on the profile of desired properties of the multilayer lacquer according to the present invention and after the importance of the adhesion problems between layers to be solved. The preferred bases according to the present invention of the coating materials according to the present invention are therefore all the usual and known transparent lacquers which are hardened by actinic radiation and / or thermal management. Within the framework of the present invention, the term actinic irradiation refers to electronic irradiation and UV irradiation, especially UV irradiation. The clearcoats contain reactive functional groups in the binders and in the crosslinking agents that exhibit crosslinking reactions between them (complementary groups principle). Suitable examples according to the present invention of complementary reactive functional groups to be used are the groups presented in the following synoptic table. In the synoptic table the variable R represents an acyclic or aliphatic cyclic radical, an aromatic radical and / or an aromatic-aliphatic (araliphatic) radical; the variables R1 and R2 represent the same or different aliphatic radicals or are linked to each other to form an aliphatic or heteroaliphatic ring.

Synoptic table: examples of complementary functional groups in binder and crosslinking agent or crosslinking agent and binder -SH -CÍO) -OH -NH2 -C (0) -0-C (0) - -0H -NCO -NH- C (0) -0R-CH2-0H-CH2-0-CH3 -NH-C (O) -CH (-C (O) OR) 2 -NH-C (O) -CH (-C (O) OR ) (-C (O) -R) -NH-C (0) -NR: R2 = Si (OR) 2 O / \ -CH-CH: -C (0) -OH O / \ -CH-CH: -0-C (0) -CR = CH2 -OH -0-CR = CH2 -NH2 -C (0) -CH2-C (0) -R-CH = CH2 Examples of one-component clearcoats (IC), two components (2C) or several suitable components (3C, 4C) are presented, for example, from the document DE-A-42 04 518, US-A-5, 74, 811, US-A- 5, 356, 669, US-A-5,605,965, WO 94/10211, WO 94/10212, WO 94/10213, EP-A-0 594 068, EP-A-0 594 071, EP-A-0 594 142 , EP-A-0 604 992, WO 94/22969, EP-A-0 596 460 or WO 92/22615. The one component clearcoats (IC) contain especially binders containing hydroxyl groups and crosslinking agents such as blocked polyisocyanates, tris (alkoxycarbonylamino) triazine and / or aminoplast resins. In a further variant, polymers containing carbamate and / or allophanate side groups and aminoplast resins modified with carbamate and / or allophanate are binders. Two-component clearcoats (2C)or several components (3C, 4C) contain as essential parts binders containing known hydroxyl groups and polyisocyanates as crosslinking agents which are stored in a divided manner until their use. Examples of suitable binders for these clearcoats are oligomers and / or polymers with at least two carbamate groups and / or side or end-allophanate groups of formulas: -0- (CO) -NH2 -0- (CO) -NH- ( CO) -NH2 As oligomers and / or polymers, basically all common and known oligomers or polymers can be considered. Examples of suitable oligomers and polymers are linear and / or crosslinked and / or block, pectin and / or statistical copolymers of ethylenically unsaturated monomers, especially poly (meth) acrylates, as well as polyesters, alkyds, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, polyethers, epoxide-amine (meth) acrylamide resin adducts, partially saponified polyvinyl esters or polyureas, among which the copolymers of ethylenically unsaturated monomers, especially poly (meth) acrylates, are particularly advantageous and therefore are used preferably. The introduction of carbamate groups can be effected through the incorporation of monomers containing these groups. Examples of suitable monomers of this type are ethylenically unsaturated monomers containing a carbamate group or an allophanate group. Examples of suitable ethylenically unsaturated monomers containing a carbamate group are described in EP-A-0 675 141, US-A-3, 479, 328, US-A-3,674,838, US-A-4, 126 , 747, US-A-4, 279, 833 or US-A-4,340,497.

The introduction of the carbamate group can also be carried out through polymerization-type reactions in the oligomers and / or polymers. Examples of suitable methods of this type are known from Patent Documents US-A-4,758,632, US-A-4, 301, 257 or US-A-2, 979, 514. Examples of poly (meth) acrylates to be used with particular preference are disclosed in patent documents US-A-5, 474, 811, US-A-5, 356, 669, US-A-5, 605, 965, WO 94/10211, WO 94. / 10212, WO 94/10213, EP-A-0 594 068, EP-A-0 594 071 or EP-A-0 594 142. For the introduction of allophanate groups, oligomers and polymers exhibiting at least two are transalphaanatized , preferably at least three primary and / or secondary hydroxyl groups, especially primary, with alkyl and aryl esters of allophane acid at a temperature of 30 to 200 ° C, preferably 50 to 160 ° C, especially 60 to 150. ° C and more preferably from 80 to 140 ° C. The reaction is carried out in solution or in bulk, preferably in solution. Addition to the reaction mixture of known and customary inhibitors such as trialkyl phosphites, especially triisodecylphosphite, is recommended. It is also advantageous to use conventional and known esterification catalysts, for example tin compounds, especially dibutyltin dioxide. Examples of suitable allophanates to be used according to the present invention are allophane methyl ester, allophane ethyl ester, allophane propyl ester, allophane butyl ester, allophane pentyl ester or allophane acid phenyl ester, among which the allophalic acid methyl ester and the allophanic acid ethyl ester are particularly advantageous and are therefore preferably used within the framework of the present invention. As oligomers and polymers to be used according to the present invention which have at least two, preferably at least three, primary and / or secondary, especially primary, hydroxyl groups, preferably linear and / or crosslinked copolymers and / or blocks, pectin and / or statistics of ethylenically unsaturated monomers, especially poly (meth) acrylates, such as polyesters, alkyds, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, polyethers, epoxide-amine resin adducts, (met acrylatdiols, partially saponified polyvinyl esters, polyureas, oligomeric polyols which are obtained from oligomers by means of methylene reactions of acyclic monoolefins and cyclic monoolefins, by hydroformylation and subsequent hydrogenation; or aliphatic polyols, among which copolymers of ethylenically unsaturated monomers, especially poly (meth) acrylates, are particularly advantageous and therefore are especially preferred within the scope of the present invention. In addition to the hydroxyl groups, the oligomers and polymers mentioned may also contain functional groups such as acryloyl, ether, amide, imide, thio, carbonate or epoxide groups. Other binders which are particularly suitable for one component clearcoats (IC), two components (2C) or several components (3C, 4C) are polyacrylate resins with an OH number of 80 to 200 mgKOH / g and a lower acid number. that 20 mgKOH / g. Preferred are polyacrylate resins having an average molecular weight M n of 1,500 to 30,000, preferably 2,000 to 15,000, and especially 2,500 to 5,000. Especially preferred are polyacrylate resins which are obtained by copolymerization of the following monomers in an organic solvent or a mixture of solvents and in the presence of at least one polymerization initiator and optionally in the presence of regulators: (a) an ester of (meth) acrylic acid other than (a2), (a3), (a4), (a5), (aß) and (a7) which can be copolymerized with (a2), (a3), (a4), (a5), (aß), and (a7) essentially free of acid groups or a mixture of such monomers, (a2) an ethylenically unsaturated monomer which can be copolymerized with (a), ( a3), (a4), (a5), (aß) and (a7) different from (a5) carrying at least one hydroxyl group per molecule and essentially free of acid groups or a mixture of such monomers, (a3) an ethylenically unsaturated monomer carrying at least one acid group which is introduced into the corresponding acid anion group per molecule, copolymerizable with (a), (a2), (a4), (a5), (aß) and (a7) or a mixture of monomers of this type, (a4) optionally one or more vinylaromatic hydrocarbons, (a5) optionally at least one product of the reaction of acrylic acid and / or methacrylic acid with the glycidyl ester of a branched monocarboxylic acid alpha position with 5 to 18 carbon atoms per molecule (for example the glycidyl ester that can obt under the tradename Cardura®) or in the place of the reaction product, an equivalent amount of acrylic acid and / or methacrylic acid which reacts during or after the polymerization reaction with the glycidyl ester of a branched monocarboxylic acid in alpha position (for example the glycidyl ester obtainable commercially under the tradename Cardura®) with 5 to 18 carbon atoms per molecule, (aβ) at least one polysiloxane macromonomer to be used according to the present invention and described below with details as well as (a7) optionally an ethylenically unsaturated monomer, essentially free of acid groups, copolymerizable with (a), (a2), (a3), (a4), (a5) and (a6), different from (al), (a2), (a3), (a4), (a5) and (a6), or else a mixture of such monomers, so (a), (a2), (a3), (a4), (a5), (aß) and (a7) are selected in terms of type and amount such that the polyacrylate resin exhibits the desired OH number, the desired index and the desired molecular weight. For the preparation of the polyacrylate resins to be used according to the present invention, any ester of (meth) acrylic acid essentially free of acid groups copolymerizable with (a2), (a3), (a4), (a5), (aß) and (a7) or a mixture of such esters of (meth) acrylic acid. Examples are acrylates and alkyl methacrylates with up to 20 carbon atoms in the alkyl radical, such as, for example, methyl, ethyl, propyl, n-butyl acrylate or methacrylate, sec. butyl, tert.-butyl, hexyl, ethylhexyl, stearyl and lauryl esters or (meth) acrylic cycloaliphatic, such as (meth) acrylate ciciohexilo (meth) acrylate, (meth) acrylate and dicyclopentadienyl tert-butylcyclohexyl (meth) acrylate.

As monomers (al) can also be used (meth) acrylate ethyl triglycol (meth) acrylate methoxyoligoglycol with an average Mn of preferably 550 or other acid derivatives molecular weight (meth) acrylic ethoxylated hydroxyl groups and / or propoxylated . Monomers (a2) may be used ethylenically unsaturated monomers copolymerizable with (al), (a3), (a4), (a5), (SSA) and (a7) and different from (a5) carrying at least one hydroxyl group per molecule and essentially free of acid groups or a mixture of such monomers. Examples are hydroxyalkyl ester of acrylic acid, methacrylic acid or other alpha, beta-ethylenically unsaturated carboxylic acids. These esters can be derived from an alkylene glycol esterified with the acid or can be obtained by the reaction of the acid with an alkylene oxide. Monomers (a2) are preferably used hydroxyalkyl esters of acrylic acid or methacrylic acid wherein the hydroxyalkyl group contains up to 20 carbon atoms, reaction products from cyclic esters such as epsilon-caprolactone and hydroxyalkyl esters or mixtures of these hydroxyalkyl esters or modified hydroxyalkyl esters with epsilon-caprolactone. Examples of hydroxyalkyl esters of this type may be mentioned acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4 -hydroxybutyl, 4-hydroxybutyl methacrylate, methylpropanediol monoacrylate, methylpropanediol monomethacrylate, hydroxystearyl acrylate and hydroxystearyl methacrylate. Corresponding esters of other unsaturated acids such as for example ethacrylic acid, crotonic acid and similar acids with up to about 6 carbon atoms per molecule can also be used. In addition, olefinically unsaturated polyols can also be used as monomers (a2). Preferred polyacrylate resins are obtained when it is used as monomer (a2) at least partially trimethylolpropanmonalicylate ether. The portion of trimethylolpropane monosilicate ether usually ranges from 2 to 10% by weight relative to the overall weight of the monomers (al) to (a7) used for the preparation of the polyacrylate resin. Furthermore, it is also possible to use from 2 to 10% by weight of trimethylolpropane monosilicate ether, relative to the overall weight of the monomers used for the preparation of the polyacrylate resin in order to prepare the polyacrylate resin. The olefinically unsaturated polyols, such as especially trimethylolpropane monosilicate ether, can be used as monomers containing hydroxyl groups alone, especially, however, partially in combination with other monomers (a2) containing hydroxyl groups. As the monomer (a3), an ethylenically unsaturated monomer copolymerizable with (a) can be used in each case, (a2), (a4), (a5), (aβ) and (a7) carrying at least one acid group, preferably a carboxyl group per molecule, or a mixture of such monomers. As monomers (a3), acrylic acid and / or methacrylic acid are preferably used. However, it is also possible to use ethylenically unsaturated carboxylic acids with roughly 6 carbon atoms in the molecule. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. In addition, sulfonic acid or ethylenically unsaturated phosphonic acid or its partial esters can be used as monomers (a3). As monomers (a3), mono (meth) acryloyloxyethyl ester of maleic acid, mono (meth) acryloyloxyethyl ester of succinic acid and mono (meth) acryloyloxyethyl ester of phthalic acid can also be used. Optional optional monomers (a4) are vinylaromatic hydrocarbons, such as styrene, alpha-alkylstyrene and vinyl toluene. As optional monomers (a5), the product of the reaction of acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid having an alpha-branched position having 5 to 18 carbon atoms per molecule can be used. The reaction of acrylic acid or methacrylic acid with glycidyl ester of a carboxylic acid with a tertiary alpha carbon atom can be carried out before, during or after the polymerization reaction. As a monomer (a5), the product of the reaction of acrylic acid and / or methacrylic acid with the glycidyl ester of versatic acid is preferred. This glycidyl ester can be obtained commercially under the trade name "Cardura® ElO". It is especially preferred to use vinyl esters of saturated aliphatic monocarboxylic acids with 9 to 11 carbon atoms which are branched at the alpha carbon atom due to their good availability. For the present invention it is essential that the polyacrylate resins (A) contain at least one polymerized polysiloxane (aß) acromonomer. Polysiloxane macromonomers (aß) having an average molecular weight Mn of from 1,000 to 40,000, preferably from 2,000 to 20,000, especially from 2,500 to 10,000 and with special preference from 3,000 to 7,000 dalton and an average of from 0.5 to 2.5, are suitable. preference of 0.5 to 1.5 ethylenically unsaturated double bonds per molecule. Suitable for example are the polysiloxane macromonomers described in DE-A-38 07 571 on pages 5 to 7, the polysiloxane macromonomers described in DE-A 37 06 095 in columns 3 to 7, the macromonomers of polysiloxanes described in EP-B-0 358 153 on pages 3 to 6 and the polysiloxane macromonomers described in US Pat. No. 4,754,014 in columns 5 to 9. Other vinyl monomers are also suitable. they contain acryloxysilane with the molecular weights mentioned above and maintained in ethylenically unsaturated double bonds, for example compounds that can be made by the reaction of hydroxy-functional silanes with epichlorohydrin and then reaction of the reaction product with methacrylic acid and / or hydroxyalkyl esters of acid (meth) ) acrylic. The polysiloxane macromonomers presented in DE-A 44 21 823 are especially preferred as monomers (aß). Examples of suitable polysiloxane macromonomers as monomers (aβ) are also the compounds mentioned in the international patent application with publication number WO 92/22615 on page 12, row 18 to page 18, line 10. The polysiloxane macromonomers (aß) can be obtained commercially and are sold, for example, under the Marubeni® AK5 trademark of Toagosei. The amount used of the polysiloxane macromonomer (s) (aß) is from 0.1 to 20% by weight, preferably from 1 to 15% by weight, particularly preferably from 2 to 8% by weight, and very especially from 3 to 7% by weight relative to the overall weight of the monomers used for the preparation of the polyacrylate (a). As optional monomers (a7), all ethylenically unsaturated monomers which are essentially free of copolymerizable acid groups can be used with (a), (a2), (a3), (a4), (a5) and? aß) different from (a), (a2), (a3), (a4), (a5) and (aß) or mixtures of such monomers. As monomers (a7), one or more vinyl esters of alpha-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule can be used. The branched monocarboxylic acids can be obtained by the reaction of formic acid or carbon monoxide and water with olefins in the presence of a strongly acidic liquid catalyst; the olefins can be products of the decomposition of paraffinic hydrocarbons such as for example mineral oil fractions and can contain acyclic and / or cycloaliphatic branched or straight chain olefins. Through the reaction of such olefins with formic acid or carbon monoxide and water a mixture of carboxylic acids is obtained in which the carboxyl groups are mainly found in a quaternary carbon atom. Other olefinic starting products are, for example, propylene trimer, propylene tetramer and diisobutylene. The vinyl esters can also be prepared in a known manner from the acids, for example to the extent that the acids are reacted with acetylene. Especially preferred acrylate resins are obtained by copolymerization of (al) 5 to 80% by weight, preferably 10 to 70% by weight, of monomers (al) (a2) 3 to 45% by weight, preferably 15 to 35% by weight of monomers (a2), (a3) 0.1 to 15% by weight, preferably 0.5 to 5% by weight of monomers (a3), (a4) up to 50% by weight, preferably from 15 to 45% by weight of monomers (a4), (a5) up to 50% by weight, preferably from 15 to 35% by weight of monomers (a5), (aβ) from 0.1 to 20% by weight, preferably from 1 to 15% by weight of monomers (aß) and (a7) up to 30% by weight, preferably up to 25% by weight of monomers (aß), whereby the sum of the parts by weight of monomers (al) to (aß) is 100% by weight The preparation of the polyacrylate resins to be used according to the present invention is carried out in bulk or preferably in an organic solvent or solvent mixture and in the presence of at least one polymerization initiator and optionally a regulator. As organic solvents, polymerization initiators and regulators, customary solvents, regulators and polymerization initiators are used for the preparation of the polyacrylate resins. The solvents can participate in the reaction with the crosslinking agent and can even function as a reactive diluent. Examples of suitable solvents are butyl glycol, 2-methoxypropanol, n-butanol, methoxybutanol, n-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, trimethylolpropane, 2-hydroxypropionic acid ethyl ester and 3-methyl. -3-methoxybutanol as well as propylene glycol-based derivatives such as ethyletoxypropionate, isopropoxypropanol, methoxypropyl acetate, among others. Examples of suitable diluents and reagents are oligomeric polyols which are obtained from intermediate oligomeric products by metathesis reactions of acyclic monoolefins and cyclic monoolefins by hydroformylation and subsequently hydrogenation; examples of suitable cyclic monoolefins are cyclobutene, cyclopentene, cyclohexene, cyclooctene, cycloheptene, norbornene or 7-oxanorbornene; examples of suitable acyclic monoolefins are obtained in mixtures of hydrocarbons obtained through the treatment of petroleum by decomposition (Cs cut); Suitable examples of oligomeric polyols to be used according to the present invention have a hydroxyl number (OHZ) of 200 to 450, a number average molecular weight Mn of 400 to 1000 and a mass average molecular weight Mw of 600 to 1000. Further examples of suitable reactive diluents are cyclic and / or acyclic Cg-Cie alkanes, branched, which are functionalized with at least two hydroxyl groups, especially diethyl octanediols such as, for example, cyclohexanedimethanol, neopentyl glycol ester of hydro-pivalic acid, neopentyl glycol, trimethylolpropane or pentaerythritol. Further examples of suitable reactive diluents are dendrimers or hyperbranched compounds which are obtained from tetrolene as the compounds forming central groups, dicarboxylic acids and / or their anhydrides such as for example Versatic®-acid glycidylester. Examples of suitable polymerization initiators are initiators that form free radicals such as, for example, tert-butylperoxyethyl hexanoate, benzoyl peroxide, azobisisobutyronitrile and tert. -butylperbenzoate. The initiators are preferably used in an amount of 2 to 25% by weight, particularly preferably 4 to 10% by weight, based on the total weight of the monomers. Examples of suitable regulators are mercaptans, such as mercaptan-ethanol, thioglycolic acid ester and hydrogen chloride, among others. The regulators are preferably used in amounts of 0.1 to 15% by weight, particularly preferably 0.5 to 5% by weight, based on the total weight of the monomers. The polymerization is conveniently carried out at a temperature of 80 to 160 ° C, preferably 110 to 160 ° C. For this purpose, methods known and customary in the continuous or discontinuous copolymerization technique are used under normal pressure or over pressure in stirred vessels, autoclaves, tube reactors or Taylor reactors. Examples of suitable (Co) polymerization processes for the preparation of acrylate resins (A) are described in the patent documents DE-A-197 09 465, DE-C-197 09 476, DE-A-28 48 906, DE-A-195 24 182, EP-A-0 554 783, WO 95/27742 or WO 82/02387. Taylor reactors are preferred. Taylor reactors, which serve for the transformation of elements under Taylor current conditions are known. They essentially consist of two concentrically placed cylinders coaxially of which the outer cylinder is fixed and the inner cylinder rotates. The volume that is in the space between the cylinders is considered as the reaction space. With an increasing angular velocity of the internal cylinder, a series of different current forms are created which are characterized by a non-dimensional index, which is known as the Taylor Ta index. The Taylor index also depends on the angular velocity of the agitator and the kinematic viscosity v of the fluid in space and geometric parameters, the external radius of the internal cylinder ri, the internal radius of the external cylinder ra and the space d, the difference between the radii, according to the following formula: Ta = Ghrid v_1 (d / ri) 1/2 (I) with d = ra - r ^. In the case of a low angular velocity, a laminar Couette current is formed, a simple cutting current. With the increase in the speed of rotation of the internal cylinder, vortices that rotate in an opposite manner alternately (against rotation) with axes along the circumference are observed above a critical value. These Taylor vortices are symmetric in terms of rotation and have a diameter that is almost as large as the interval. Two neighboring vortices make up a pair of vortices or a vortex cell. This behavior is based on the fact that when rotating the internal cylinder with an immobile external cylinder, the fluid particles near the internal cylinder are subjected to a centrifugal force greater than the particles that are farthest from the internal cylinder. This difference of centrifugal forces pushes the fluid particles from the inner cylinder to the outer cylinder. The centrifugal force is opposed to the force of the viscosity since at the moment of the displacement of the fluid particles, the friction must be overcome. If the rotation speed increases, then the centrifugal force is increased. Taylor's vortex occurs when the centrifugal force is greater than the stabilizing force of the viscosity. In the case of the Taylor vortex with a small axial current the pairs of vortices move through the interval, so only a small exchange of material between pairs of neighboring vortices is observed. The mixing within such pairs of vortices is very important, unlike the axial mixing through pairs limits which is only small. A pair of vortices can therefore be considered as a vessel of agitation. The current system behaves like an ideal current tube in which the pairs of vortices move with a constant residence time as the ideal agitation vessel through the interval.

Preference is given to Taylor reactors with an external reactor wall and a concentrically or eccentrically placed rotor, a reactor bottom and a reactor cover which jointly define the ring-shaped reactor volume, at least one power supply device. educts as well as a device for product discharge, whereby the reactor wall and / or the rotor is determined geometrically in such a way that the conditions for the Taylor current are fulfilled over essentially the entire length of the reactor in the reactor. reactor volume, that is, that the ring widens in the direction of flow. Examples of crosslinking agents suitable for one component clearcoat (IC) are aminoplast resins, compounds or resins containing anhydride groups, compounds or resins containing epoxide, tris (alkoxycarbonylamino) triazine groups, compounds or resins containing siloxane groups, compounds or resins containing carbonate groups, blocked and / or unblocked polyisocyanates, beta-hydroxyalkylamide as well as compounds with on average at least two groups capable of esterification, for example reaction products of malonic acid diesters and polyisocyanates or esters and partial esters of lower alcohols of malonic acid with monoisocyanates, as described in European Patent Document EP-A-0 596 460. Such crosslinking agents are known to those skilled in the art and are offered by various companies as products for sale . Any suitable aminoplast resin can be used for clearcoat or clearcoat or a mixture of these aminoplast resins. Especially well-known and known aminoplast resins can be considered, whose methylol and / or methoxymethyl groups are partially defunctionalized by carbamate or allophanate groups. Crosslinking agents of this type are described in patent documents US-A-4 710 542 and EP-B-0 245 700 as well as in the article by B. Singh and colleagues "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, volume 13, pages 193 to 207. Examples of suitable polyepoxides are especially all aliphatic and / or cycloaliphatic and / or aromatic polyepoxides, for example based on Bisphenol-A or Bisphenol-F . Examples of suitable polyepoxides are those commercially available under the tradename Epikote® from Shell, Denacol® from Nagase Chemicals Ltd., Japan, polyepoxides obtainable, for example, Denacol EX-411 (pentaerythritol polyglycidylether) ), Denacol EX-321 (trimethylolpropane polyglycidyl ether), Denacol® EX-512 (polyglycerol-polyglycidyl ether) and Denacol® EX-521 (polyglycerol polyglycidyl ether). Suitable tris (alkoxycarbonylamino) triazines have the following formula: Examples of suitable tris (alkoxycarbonylamino) triazines are described in patent documents US-A-4, 939, 213, US-A-5,084,541 or EP-A-0 624 577. Especially tris (methoxy-, tris) are used. (butoxy- and / or tris (2-ethylhexyloxycarbonylamino) triazines) Mixed methyl-butyl esters, mixed butyl-2-ethylhexyl esters and butyl ether esters are advantageous, they have a better solubility in polymer melts and also have a lower solubility crystallization tendency compared to the pure methyl ester Examples of suitable siloxanes are siloxanes as at least one trialkyloxy group or a dialkoxysilane group such as for example trimethoxysilane One example of a suitable polyanhydride is polysuccinic acid anhydride. Suitable hydroxyalkylamides are N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N', N'-tetrakis (2-hydroxypropyl) adipamide Suitable examples of suitable crosslinking agents are: blocked polyisocyanates. Examples of suitable blocking agents are the blocking agents known from US-A-4,444,954: i) phenols such as for example phenol, cresol, xyleneol, nitrophenol, chlorophenol, ethylphenol, t-butylphenol, hydroxybenzoic acid. Esters of these acids or 2, 5-di-tert.-butyl-4-hydroxytoluol; ii) lactams, for example e-caprolactam, d-valerolacta a, β-butyrolactam or β-propiolactam; iii) methylene-active compounds, for example diethyl malonate, dimethyl malonate, ethyl or methyl ester of acetic acid or acetylacetone; iv) alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxymethanol, glycolic acid, glycolic acid ester, lactic acid, lactic acid ester, methylolurea, methylolmelamine, diacetone alcohol, ethylenechlorohydrin, ethylenebromhydrin, 1,3-dichloro-2-propanol , 1,4-cyclohexyldimethanol or acetocyanhydrin; v) mercaptans, such as, for example, butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol; vi) acidic amides such as, for example, acetoanilide, acetoanisidinamide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide; vii) imides such as succinimide, phthalimide or maleimide; viii) amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine; ix) imidazoles such as for example imidazole or 2-ethylimidazole; x) ureas such as, for example, urea, thiourea, ethyleneurea, ethylenethiourea or 1,3-diphenylurea; xi) carbamates such as, for example, phenyl ester of N-phenylcarbamide acid or 2-oxazolidone; xii) imines such as, for example, ethylene imine; xiii) oximes such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, diisobutylketoxime, diacetylmonoxime, benzophenone oxime or chlorohexanone oxime; xiv) sulfuric acid salts such as sodium bisulfite or potassium bisulfite; xv) hydroxamic acid esters such as, for example, benzylmethacrylohydroxamate (BMH) or allylmethacrylohydroxamate; or xvi) pyrazoles, ketoximes, imidazoles or substituted triazoles; as well as xvii) mixtures of these blocking agents, especially dimethylpyrazole and triazoles, malonic esters and acetic acid esters or dimethylpyrazole and succinimide. Suitable examples of organic blocking polyisocyanates are especially those known as lacquer polyisocyanates with aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanate groups attached. Polyisocyanates with 2 to 5 isocyanate groups per molecule and with viscosities between 100 and 10,000, preferably 100 and 5,000, are preferred. In addition, the polyisocyanates can be modified in a hydrophilic or hydrophobic manner in a conventional and known manner. Further examples of suitable blocking polyisocyanates are presented in "Methoden der organischen Chemie", [Methods of organic chemistry], Houben-Weyl, volume 14/2, 4th. edition, Georg Thieme Verlag, Stuttgart 1963, pages ßl to 70 and in W. Siefken, Liebigs Annalen der Chemie, Volume 562, pages 75 to 136. For example, polyurethane prepolymers containing isocyanate groups which can be prepared by reaction of polyols with an excess of polyisocyanates and preferably having a low viscosity. Further examples of suitable blocking polyisocyanates are polyisocyanates having isocyanurate, biuret, allophanate, iminooxadiazindone, urethane, urea and / or uretdione groups. Polyisocyanates having urethane groups are obtained, for example, by the reaction of a part of isocyanate groups with polyols such as, for example, trimethylolpropane and glycerin. Preferably, the aliphatic or cycloaliphatic polyisocyanates, especially hexamethylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, dimeric fatty acid diisocyanate, are derived. such as those sold by the company Henkel under the trade name DDI 1410 and such as are described in Patent Documents DO 97/49745 and WO 97/49747, especially 2-heptyl-3,4-bis (9-isocyanatononyl) -1 -pentyl-cyclohexane or 1,2-, 1,4- or 1,3-bis (isocyanatomethyl) cydohexane, 1,2-, 1,4- or 1,3-bis (2-isocyanatoet-1-) il) cyclohexane, 1,3-bis (3-isocyanatoprop-1-yl) cydohexane or 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-1-yl) cydohexane, 1, 8-diisocyanato-4-isocyanatomethyloctane, 1,7-diisocyanato-4-isocyanatomethyl-heptane or l-isocyanato-2- (3-isocyanatopropyl) cyclohexane or mixtures of these polyisocyanates. Especially preferred are mixtures of polyisocyanates having uretdione and / or isocyanurate groups and / or allophanate groups based on hexamethylene diisocyanate, as can be obtained from the catalytic oligomerization of hexamethylene diisocyanate using suitable catalysts. Examples of suitable crosslinking agents for two-component clearcoats (2C) or various components (3C, 4C) are the above-mentioned non-blocked polyisocyanates. Examples of suitable powder clearcoats are known, for example, from German Patent DE-A-42 22 194 or from the product information of the company BASF Lacke + Farben AG "Powdery Lacquer", 1990. The powder clearcoats contain as their essential constituents binders containing known epoxide groups and polycarboxylic acids as crosslinking agents and / or binders containing carboxylic acid groups and compounds or resins with at least two epoxide groups as crosslinking agents. Examples of binders containing suitable epoxide groups are polyacrylate resins containing epoxide groups which are obtained by copolymerization, especially in a Taylor reactor, of at least one ethylenically unsaturated monomer containing at least one epoxide group in the molecule, with at least one additional ethylenically unsaturated monomer containing no epoxide group in the molecule, wherein at least one of the monomers is an ester of acrylic acid or methacrylic acid. Such polyacrylate resins containing epoxide groups are described, for example, in patent documents EP-A-0 299 420, DE-B-22 14 650, DE-B-27 49 576, US-A-4,091,048 or US Pat. A-3, 781, 379. Examples of suitable monomers that do not contain epoxide groups in the molecule are alkyl esters of acrylic and methacrylic acid, especially methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-acrylate and butyl, n-butyl methacrylate, secondary butyl acrylate, tert acrylate. -butyl, tert-butyl methacrylate, neopentyl acrylate, neopentyl methacrylate, 2-ethylhexyl acrylate or 2-ethylhexyl methacrylate; amides of acrylic acid and methacrylic acid, especially acrylamide and methacrylic acid amide; vinyl aromatic compounds, especially styrene, methylstyrene or vinyl toluene; nitriles of acrylic acid and methacrylic acid, vinyl halide and vinylidene, especially vinyl chloride or vinylidene fluoride; vinyl esters, especially vinyl acetate and vinyl propionate; vinyl ethers, especially n-butyl vinyl ether; or monomers containing hydroxyl groups, especially hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate. Suitable examples according to the present invention of epoxy functional monomers to be used are glycidyl acrylate, glycidyl methacrylate or eterallylglycidyl. The polyacrylate resin containing epoxide groups conventionally has an epoxide equivalent weight of 400 to 2500, preferably 420 to 700, a number-average molecular weight Mn (determined in accordance with gel permeation chromatography using a polystyrene standard) from 2000 to 20,000, preferably from 3,000 to 10,000, and a glass transition temperature Tg from 30 to 80, preferably from 40 to 70, more preferably from 40 to 60 and especially from 48 to 52 ° C (measured with the aid of differential scanning calorimetry (DSC)). Examples of suitable crosslinking agents for these polyacrylate resins containing epoxide groups are straight chain aliphatic polycarboxylic acids, dicarboxylic acids, preferably saturated with 3 to 20 carbon atoms in the molecule. Polyesters having carboxy functionality can also be used instead or in addition to them. Dodecane-1,2-dicarboxylic acid is very particularly preferred. Examples of binders containing carboxylic groups suitable for this clear powder coating are the binders containing carboxyl groups described above. Examples of crosslinking agents containing suitable epoxide groups for this binder are the binders containing epoxide groups described above or low molecular weight compounds containing at least two glycidyl groups, especially pentaerythritol tetraglycidyl ether or triglycidyl isocyanurate. Furthermore, the powder clearcoats can contain the crosslinking agents described above, especially tris (alkoxycarbonylamino) triazines. Examples of suitable clearcoats in powder paste are mentioned, for example, in US Pat. No. 4,282,842 and in German Patent Applications DE-A-195 18 392.4 and DE-A-196 13 547. or they are described in the Non-Prepublished German Patent Application DE-A-198 14 471.7. The powder clearcoat clearcoats are known as clear powder coatings dispersed in an aqueous medium. UV curable transparent lacquers are described, for example, in patent documents EP-A-0 540 884, EP-A-0 568 967 or US-A-4, 675, 234. They contain oligomeric compounds as is known. and / or low molecular weight polymers curable with actinic light and / or electron beams, preferably radiation-hardenable binders, especially based on ethylenically unsaturated prepolymers and / or ethylenically unsaturated oligomers, optionally one or more reactive diluents as well as optionally one or more photoinitiators. Examples of radiation-hardenable binders are (meth) acrylic (meth) acrylic copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxyacrylates, urethane acrylates, amino acrylates, melamine acrylates, silicon acrylates and the corresponding methacrylates. The use of free binders of aromatic structures is preferred. Reactive, radiation-hardenable reactive diluents are low molecular weight polyfunctional ethylenically unsaturated compounds. Suitable compounds of this type are esters of acrylic acid with polyols, such as, for example, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate or pentaerythritol tetraacrylate.; or products of the reaction of hydroxyalkyl acrylates with polyisocyanates, especially aliphatic polyisocyanates. The constituents described above of the clearcoats can be combined with each other, in such a way that the result is one component clearcoats (ÍC), two components (2C) or several components (3C), (4C), transparent powder lacquers and clear lacquers in powder paste which are thermally hardenable and / or actinic radiation. In addition, the clearcoats can contain conventional and known additives. Examples of suitable additives are UV absorbers; radical scavengers, rheology agents; Silicic acids; hydroxides of colloidal metals which have blocked isocyanate groups as described, for example, in EP-A-0 872 500; slip additives; polymerization inhibitors; foam removers; dispersing agents; biosides; flame protection agents or film forming aids such as cellulose derivatives. It is essential that these additives do not negatively affect the transparency and other particularly useful properties of the clearcoat layers, but that they modify them and improve them in a beneficial manner. Additional examples of suitable additives are disclosed in patent document US-A-5, 605, 695. The preparation of the coating materials according to the present invention or of the clearcoats according to the present invention from their The constituents do not present any particularity but are carried out in a customary and known manner by mixtures of constituents in mixed aggregates suitable as solvents. The additional essential constituent of the lacquering in several layers of the present invention is the base lacquer layer (A). The base lacquer layer (A) is made from a coating material (A), preferably an aqueous coating material (A), especially an aqueous base lacquer (A), and is the part that provides color and / or effects to the lacquering of several layers according to the present invention. The water-based lacquer used with particular preference in accordance with the present invention (A) contains the following essential components dispersed in water: (Al) at least one stabilized anionic and / or non-ionic polyurethane and (A2) at least one pigment that provides color and / or effect. Examples of pigments (A2) which provide suitable color and / or effect are metallic flake pigments such as for example commercially available bronze aluminum, chromed bronze aluminum in accordance with DE-A-36 3ß 183, as well as bronze stainless steel available in the trade as well as pigments of non-metallic effects such as, for example, interference pigments or pearl gloss. Examples of suitable inorganic coloring pigments (A2) are titanium dioxide, iron oxide, transamarillo and carbon black. Examples of pigments (A2) suitable organic dyes are indanthrene blue, chromophthalum red, orange, irgazin and heliogenic green. Furthermore, the coating material according to the present invention may contain organic and inorganic fillers (A3) in known and effective amounts. Examples of suitable fillers are gis, calcium sulfate, barium sulfate, silicates such as talc or kaolin, salicylic acid, oxide such as for example aluminum hydroxide or magnesium hydroxide, nanoparticles or organic fillers such as textile fibers, fibers of cellulose, polyethylene fibers or wood flour. The coating material according to the present invention also contains lacquer additives (A4) in effective, customary and known amounts. Suitable additives (A4) are those mentioned above. Additional examples of suitable additives (A4) are additives that control rheology such as those known from the patent documents WO 94/22968, EP-A-0 276 501, EP-A-0 249 201 or WO 97 / 12945; cross-linked polymeric microparticles are provided, for example, in EP-A-0 008 127; inorganic layer silicates such as aluminum-magnesium silicates, sodium-magnesium layer silicates and sodium-magnesium-fluorine-lithium layer silicates of the montmorillonite type; Salicylic acid such as aerosils; or synthetic polymers with ionic and / or associative active groups such as for example polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone, copolymers of styrene-maleic anhydride or ethylene-maleic anhydride and their derivatives or ethoxylated urethanes hydrophobically modified or polyacrylates. Preferred as rheology control additives (A4) are polyurethanes and / or layer silicates. In addition, the water-based lacquer (A), when it must be hardened not only by physical drying, may contain at least one cross-linking agent (A5) in effective amounts. Examples of suitable crosslinking agents (A5) are the crosslinking agents described above which are suitable for use in one component clearcoats (IC). If the water-based lacquer (A) is applied as a two-component clear lacquer (2C) or several components (3C, 4C), said lacquer contains the polyepoxides described above and / or the unblocked polyisocyanates described above. Numerous examples of suitable anionic and / or nonionic (Al) stabilized polyurethanes as well as numerous examples of suitable formulations of aqueous basecoats (A) are disclosed in EP-A-0 089 497, EP-A-0 256 540, EP-A-0 260 447, EP-A-0 297 576, WO 96/12747, EP-A-0 523 610, EP-A-0 228 003, EP-A-0 397 806, EP- A-0 574 417, EP-A-0 531 510, EP-A-0 581 211, EP-A-0 708 788, EP-A-0 593 454, DE-A-43 28 092, EP-A- 0 299 148, EP-A-0 394 737, EP-A-0 590 484, EP-A-0 234 362, EP-A-0 234 361, EP-A-0 543 817, WO 95/14721, EP -A-0 521 928, EP-A-0 522 420, EP-A-0 522 419, EP-AO 649 865, EP-A-0 536 712, EP-A-0 596 460, EP-A-0 596 461, EP-A-0 584 818, EP-A-0 669 356, EP-A-0 634 431, EP-A-0 678 536, EP-A-0 354 261, EP-A-0 424 705 , WO 97/49745, WO 97/49747 or EP-A-0 401 565. From a methodological perspective, the preparation of the water-based lacquer (A) has no particularities but is carried out in accordance with usual and known methods through me zllas of the components in mixture aggregates suitable as solvents. The lacquering in several layers according to the present invention can be carried out according to various methods. It is advantageous to make them in accordance with the process of the present invention. The process according to the present invention depends on the substrate to be coated. The substrate may consist of metal, wood, plastic, glass or paper or contain these materials as compounds. Preferably they are automobile body parts or industrial parts including metal containers. The substrate may have a preparation treatment. In the case of plastics, this is what is known as a hardened hydropreparation prior to the application of the base lacquer (A), especially the water-based lacquer (A). In the case of metals, especially parts of automobile bodies, these are conventional and known hardened electrodeposition lacquers on which a filler is applied and baked In the process according to the present invention, the lacquer base (A) is applied in a process step (I) on the surface of the substrate and partially dried (process step II), however it does not harden.In a process step (III), on the surface of the A first clearcoat (B) is applied to the basecoat layer, which will then form the intermediate layer.In process step (IV), layers (A) and (B) are hardened together (wet-on-wet process) In this way, the layer (B) according to its shape is hardened with thermal and / or actinic radiation.With regard to thermal hardening, the baking temperature depends above all on whether the coating materials (A) and (B) they are one-component systems ( ÍC) or two components (2C) or several components (3C, 4C). In the case of systems with one component (ÍC), baking temperatures higher than 120 ° C are generally used. In the case of two-component systems (2C) or several components (3C, 4C), the baking temperature is usually set below 100 ° C, especially below 80 ° C. In accordance with the present invention, on the surface of the transparent lacquer layer (B) the transparent lacquer layer (C) in process step (V) and hardened in process step (VI). For hardening, the methods described above are used according to the transparent lacquer used (C). This variant of the process according to the present invention is especially contemplated in the case of vehicle preparation lacquering. A grinding of the clear lacquer layer (B) to improve intercoat adhesion is no longer required. Alternatively to this variant of the process according to the present invention, the transparent lacquer layer (B) applied in the process step (III) is only partially dried in the process step (IV). Subsequently, in the process step (V), the transparent lacquer layer (C) is applied wet-wet condition, so then the lacquer layers (A), (B) and (C) are hardened together . In the process according to the present invention, the coating materials (A), (B) and (C) can be applied to the substrate by customary application methods such as spraying, brushing, pouring, dipping or rolling. For the hardening of the individual layers, known and customary methods such as heating in an air circulation oven, radiations with IR lamps and possibly UV lamps can be used.

Within the lacquering of several layers according to the present invention, the thickness of the individual layers (A), (B) and (C) can vary within wide ranges. According to the present invention, however, it is an advantage that the base lacquer layer (A) has a thickness of 5 to 25 μm, especially of 7 to 15 μm, and that the two layers of clear lacquer (B) and (C) together have a thickness of 15 to 120 μm, preferably 40 to 80 μm and especially 60 to 70 μm. The proportion of the layer thicknesses varies within wide ranges, however, also due to economic reasons, it is advantageous that the clearcoat layer (B) is the thickest of both layers. This transparent lacquer layer (B) can provide, so to speak, the basic properties of the multilayer transparent lacquer layer, unlike the clear lacquer layer (C) with its different conformation, optionally specially selected in proportion to the specific technical properties desired. The lacquering of several layers in accordance with the present invention exhibits exceptional optical, mechanical and chemical properties. Thus, it is free of superficial disorders such as shrinkage (wrinkle formation). It is exceptionally transparent and resistant to scratches. No delamination is observed due to unsatisfactory adhesion between layers. The stability to chemical attacks is excellent. The very special advantage of multi-layer lacquering in accordance with the present invention is that the profile of its surface properties can vary greatly and therefore can be adapted to the varied requirements in a precise and simple manner. Examples and comparison experiments Preparation examples 1 to 6 1. Preparation of a polyacrylate In a laboratory reactor with a useful volume of 4 1 equipped with a stirrer, two dropping funnels for the monomer mixture or initiator solution, Nitrogen inlet, thermometer and reflux cooler, 640.6 g of a fraction of aromatic hydrocarbons with a boiling point between 158 and 172 ° C was introduced. The solvent was heated to a temperature of 140 ° C. After reaching the temperature at 140 ° C, a monomer mixture consisting of 597 g of ethylhexyl acrylate, 173.2 g of hydroxyethyl methacrylate was introduced., 128.4 g of styrene and 385.2 g of 4-hydroxybutyl acrylate within a period of 4 hours and an initiator solution of 25.6 g of t-butylperethyl hexanoate in 50 g of the aromatic solvent described within a period of 4.5 hours regularly in the reactor. The addition of mixtures of monomers and initiator solution was started at the same time. After the completion of the addition of initiator, the reaction mixture was kept for a further 2 hours at a temperature of 140 ° C and then cooled. The resulting polymer solution had a solids content of 65% as determined in an air stream oven 1 hour at 130 ° C. 2. Fabrication of a polyacrylate as a friction resin In a laboratory reactor with a useful volume of 4 1, equipped with a stirrer, two dropping funnels for the mixture of monomers or initiator solution, nitrogen inlet tube, thermometer and reflux cooler, were introduced 720 g of a fraction of aromatic hydrocarbons with a boiling point comprised between 158 and 172 ° C. The solvent was heated to a temperature of 140 ° C. After reaching the temperature of 140 ° C, a monomer mixture consisting of 450 g of 2-ethylhexyl methacrylate, 180 g was introduced. of n-butyl methacrylate, 210 g of styrene, 180 g of hydroxyethyl acrylate, 450 g of 4-hydroxybutyl acrylate and 30 g of acrylic acid within a period of 4 hours and an initiator solution of 150 g of hexanoate of t-butylperethyl in 90 g of the aromatic solvent described within a period of 4.5 hours regularly in the reactor. The addition of mixtures of monomers and initiator solution was started at the same time. After the completion of the addition of initiator, the reaction mixture was kept for a further 2 hours at a temperature of 140 ° C and then cooled. The resulting polymer solution had a solids content of 65% as determined in an air stream oven 1 hour at 130 ° C, an acid number of 15 and a viscosity of 3 dPas (measured in a 60% strength solution). polymer solution in the aromatic solvent described using an ICI plate-ball viscometer at a temperature of 23 ° C). 3. Preparation of a thixotropic paste In a laboratory stirring mill of the Vollrath company, 800 g of flour was introduced, which consisted of 323.2 g of polyacrylate according to preparation example 2, 187.2 g of butanol, 200.8 g of xylol and 88.8 g of Aerosil® 812 (Degussa AG, Hanau), together with 1100 g of quartz sand (size: 0.7 - 1 mm) and ground with cooling with water for 30 minutes. 4. Preparation of a crosslinking agent In a 4 1 stainless steel reactor with stirrer, reflux cooler, thermometer, oil heating and a flow container for the blocking agent, 41.76 parts by weight of Vestanat® 1890 was introduced ( isocyanurate based on isophorone diisocyanate from Creanova) and 20.76 parts by weight of Solventnaphta and heated to a temperature of 50 ° C. Within a 4 hour period, 23.49 parts by weight of diethyl malonate, 5.81 parts were added. by weight of acetic acid ethyl ester and 0.14 parts by weight of catalyst solution (sodium methyl hexanoate) regularly. After the completion of the addition, 0.14 parts by weight of catalyst solution was further added. The temperature was then raised to 80 ° C. Upon reaching an isocyanate equivalent weight of 5900 to 6800, 0.9 part by weight of 1,4-cyclohexyldimethanol was added for 30 minutes at a temperature of 80 ° C under stirring. After reaching an equivalent weight in isocyanate >; 13,000, 5 parts by weight of n-butanol was added. The temperature was lowered to 50 ° C and the resulting blocked polyisocyanate was dissolved with 2 parts by weight of n-butanol until a theoretical solids content of 68% by weight was obtained. The blocked polyisocyanate obtained in this way had a solids content of 74.5% by weight (1 hour, 130 ° C) and an original viscosity of 41.6 dPas. 5. Preparation of an additional standard polyacrylate In a laboratory reactor with a useful volume of 4 1, equipped with an agitator, two dropping funnels for the monomer mixture or initiator solution, nitrogen introduction tube, thermometer and cooler After refluxing, 720 g of a fraction of aromatic hydrocarbons with a boiling point of 158-172 ° C were introduced. The solvent was heated to a temperature of 140 ° C. After reaching the temperature of 140 ° C, it was introduced to the reactor a monomer mixture consisting of 427.5 g of n-butyl acrylate, 180 g of n-butyl methacrylate, 450 g of styrene, 255 g of hydroxyethyl acrylate, 165 g of 4-hydroxybutyl acrylate and 22.5 g of Acrylic acid within 4 hours, and an initiator solution of 120 g of t-butylperethyl hexanoate in 90 g of the aromatic solvent described within a period of 4.5 hours steadily. The addition of the monomer mixture and the initiator solution started at the same time. After finishing the addition of initiators, the reaction mixture was maintained for an additional two hours at a temperature of 140 ° C and then cooled. The resulting polymer solution had a solids content of 60%, as determined in a 1 hour air clation oven at 130 ° C, an acid number of 13 mg KOH / g, an OH number of 116 mg KOH / g, a glass transition temperature Tg of 3.23 ° C and a viscosity of 9 dPas (measured in a 60% polymer solution in the aromatic solvent described using an ICI plate-ball viscometer at a temperature of 23p C). 6. Preparation of a tricyclodecanedimethanol solution 312 g of tricyclodecanedimethanol were mixed with 83 g of butyl diglycol acetate and stirred under heating until a homogeneous solution was obtained. The concentration of the solution was 79% by weight.

Example 1 and comparative experiment VI Production of a clear lacquer of a component according to the present invention (example 1) and production of a clear lacquer of a non-component according to the present invention (comparative experiment VI) A transparent lacquer was prepared of a component according to the present invention (example 1) and a transparent coating of a usual component (comparative experiment VI) from the constituents presented in Table 1, by means of mixtures. Table 1: Conformation of a transparent lacquer of a component according to the present invention (example 1) and clear lacquer of a usual component (comparative experiment VI) Constituents Experiment Example 1 Comparative VI (parts by weight) Polyacrylate of conformity 43.4 43.4 with the manufacturing example 4 Cross-linking agent of 9.0 9.0 according to the manufacturing example 5 Melamine-formaldehyde resin 16.0 16.0 heteronylated with commercially available butanol (60% in butanol / xylol) Setalux® C91756 (agent of 13.5 13.5 thixotropization available in the market of the company Akzo) Hydroxyphenyltriazine substituted 0.6 0.6 (65% in xylol) (Cyagard® 1164L) -2,2,6,6-tetramethylpiperidinyl-0.8 0.8 ester modified with amino ether (Tinuvin® 123 from Ciba) Byk® 390 (Byk Chemie) 0.05 0.05 Byk® 310 (Byk Chemie) 0.15 0.15 Tego® LAG 502 0.2 0.2 Butanol 11.4 11.4 Solventnaphtha® 2.5 2.5 Xilol 0.9 0.9 Butyl diglycol acetate 1.5 1.5 Tricyclodecanedimethanol in accordance with preparation example 6 - 6.0 SUM 100 106 The clear lacquer from comparative experiment VI presented a flow time of 46 s in a container according to DIN 4 at a temperature of 21 ° C. For the application, the flow time was adjusted to 28 s with the addition of 8 parts by weight of a solvent (organic solvent mixture). The transparent lacquer of the example had a flow time of 51.5 s in a container according to DIN 4 at a temperature of 21 ° C. For the application, the flow time was adjusted to 28 s with the addition of 10 parts by weight of a solvent (mixture of organic solvent). EXAMPLE 2 AND COMPARATIVE EXPERIMENT V2 Preparation of a lacquering of several layers according to the present invention ML (example 2) and of a lacquering of several layers not in accordance with the present invention (comparative experiment V2) For the production of a multilayer lacquer according to the present invention KL of Example 2 and of a multilayer lacquer not according to the present invention of comparative experiment V2, a transparent coating lacquer was first produced by mixing the constituents presented in Table 2. Table 2: Conformation of the clear coating lacquer Constituents (parts by weight) Polyacrylate binder in accordance with the 50.0 manufacturing example 1 Thixotropic paste in accordance with 3.0 with the manufacturing example 3 Crosslinking agent TACT 26.6 Additional constituents Hydroxyphenylbenzotriazole substituted 1.0 (95% in xylene) (Tinuvin® 123 from Ciba) 2 , 2.6, 6-tetramethylpiperidinylester 1.2 modified with amino ether (Tinuvin® 400 from Ciba) Market-available solution of 1.4 a polydimethylsiloxane modified with polyether (5% in xylene) Byk® 310 (Byk Chemie) Butyl diglycol acetate 5.5 Butylglycol acetate 5.5 Solvesso® 150 5.8 SUMA 100 TACT = tris (alkoxycarbonylamino) triazine commercially available from CYTEC Transparent coating lacquer presented in a container in accordance with DIN 4 at a temperature of 21 ° C a run-off time of 28 s For the preparation of the experiment tables, an electro-immersion lacquer (dry layer thickness: 22 um) and an aqueous filler (FU63-9400 from BASF Coatings AG) was applied, and baked (dry layer thickness: 30 μm). Electro-immersion lacquer It was baked for 20 minutes at a temperature of 170 ° C and the filler was baked for 20 minutes at a temperature of 160 ° C. A blue water-based lacquer was then applied (Wasser-Percolor-Basislack FW 05-513P from the company BASF Coatings AG) with a layer thickness of 15-18 μm and ventilated for 10 minutes at a temperature of 80 ° C. Then in the case of example 2 the clear lacquer of a component of example 1 was applied and for the comparative experiment V2, the transparent lacquer of a component of comparative experiment VI (see Table 1) wet-dampened and baked for 30 minutes at a temperature of 135 ° C in such a way that dry film thicknesses of 35 μm were obtained. The experiment tables obtained in this way were coated with the clear coating lacquer without grinding (see Table 2). The resulting clearcoat layers were baked for 20 minutes at a temperature of 140 ° C such that dry layer thicknesses of 20 μm were obtained. The adhesion of the multilayer lacquer according to the present invention ML of Example 2 was determined after storage for 24 hours at room temperature after the grid cut test according to DIN 53151 (2 mm) [rating: 0 to 5] . No detachment was observed: GTO rating. On the contrary, in the case of the lacquering of several layers not in accordance with the present invention of comparative experiment V2, a clear lacquering was observed: rating GT4. In addition, the adhesion properties of the multilayer lacquering according to the present invention ML of Example 2 and the multilayer lacquering not in accordance with the present invention of comparative experiment V2 were provided through the test of grid cuts after attack with condensation water. The results are found in Table 3. Again, the superior adhesion of the multilayer lacquer according to the present invention is emphasized again ML. Table 3: Condensation water test - constant climate (KK test) and adhesion properties of the multilayer lacquer according to the present invention ML of example 2 and the lacquering of several layers of the comparative experiment 2 Example 2 Comparative experiment 2 Adhesion in accordance with the grid cut test b) GTI GT5 a) usual procedure to determine the stability of lacquer materials in relation to an attack with constant humidity (240 hours, 100% relative humidity, 40 ° C, details in the guidelines MKK0001A of BASF Coatings AG, edition AA / 14.05.1996). The evaluation was carried out one hour after the end of the attack with condensation water. b) grid cut in accordance with DIN 53151 (2 mm) after 240 SKK hours and 24 hours of regeneration; Rating from 0 to 5: 0 = best value, 5 = worst value.

Claims (10)

1. CLAIMS 1. The use of tricyclodecanedimethanol for the production of multilayer lacquers.
2. 2. The use according to claim 1, characterized in that tricyclodecanedimethanol is used for the formation of multilayer transparent lacquers.
3. 3. The use of tricyclodecanedimethanol as a binding agent in multilayer lacquers.
4. 4. Coating material, especially clear lacquer, containing at least one binder and at least one crosslinking agent as well as tricyclodecanedimethanol. 5. The coating material, especially transparent lacquer, according to claim 4, characterized in that tricyclodecanedimethanol is used in an amount of 0.2 to 20% by weight, preferably 1.0 to 7.0% by weight and especially 2.0 to
5. 5.0% by weight each time in relation to the coating material.
6. 6. A process for improving intercoat adhesion in multilayer transparent lacquers, characterized in that tricyclodecandimetol is combined with at least one of the layer-forming agents used for the production of the multilayer transparent lacquers. The process according to claim 6, characterized in that tricyclodecanedimethanol is used in an amount of 0.2 to 20% by weight, preferably 1.0 to
7. 7.0% by weight and especially 2.0 to 5.0% by weight each time relation to the coating material.
8. 8. Lacquering of several layers in a possibly prepared substrate, which contains in the following order: (A) a layer of base lacquer, (B) a first layer of clear lacquer as intermediate layer and (C) a second layer of lacquer transparent as upper layer, characterized in that at least one of the coating materials used (B) and (C) for the production of the clearcoat layers (B) and (C) contains effective amounts of tricyclodecanedimethanol.
9. 9. The lacquering of several layers according to claim 8, characterized in that the transparent lacquer layers (B) and (C) are different among themselves in terms of their constituents.
10. 10. A process for the production of a multilayer lacquering that covers at least the following process steps: (I) application of a base lacquer (A) on a possibly prepared substrate, (II) partial drying of the lacquer applied base (A), (III) application of a first clear lacquer (B), (IV) joint hardening of layers (A) and (B) applied in process steps (I) and (III) (moist wet process), (V) ) application of a second layer of clear lacquer (C) different in its components of the first layer of clear lacquer (B) on the layer of clear lacquer (B) hardened in process step (IV) Y (VI) hardening of the transparent lacquer layer (C) applied in process step (B) or, alternatively: (I) application of a base lacquer (A) on a possibly prepared substrate, (II) partial drying of the lacquer applied base (A), (III) application of a first clear lacquer (B), (IV) partial drying of the applied clear lacquer (B), (V) application of a second layer of clear lacquer (C) on the transparent lacquer layer (B) partially dried in process step (IV) and (VI) joint hardening of lacquer layers (A), (B) and (C) (wet wet process), characterized in that at least one of the coating materials used (B) and (C) for the preparation of the clearcoat layers (B) and (C) ) contains effective amounts of tricyclodecanedimethanol.