WO2001091920A2

WO2001091920A2 - Method for producing multilayer clearcoats and color- and/or effect-imparting multilayer coats

Info

Publication number: WO2001091920A2
Application number: PCT/EP2001/006228
Authority: WO
Inventors: Thomas Farwick; Andrea Zumbrink; Ulrike RÖCKRATH; Annette Roters; Hubert Baumgart
Original assignee: Basf Coatings Ag
Priority date: 2000-06-02
Filing date: 2001-06-01
Publication date: 2001-12-06
Also published as: WO2001091920A3; DE10027268A1; AU2001272444A1

Abstract

The invention relates to a method for producing a multilayer clearcoat, especially used in color- and/or effect-imparting multilayer coats, by applying a first clearcoat, drying the resulting first clearcoat layer without curing it, or, alternatively, curing the first clearcoat layer, applying a second clearcoat that differs in terms of composition from the first clearcoat and curing the first and the second clearcoat layer together, or, alternatively, curing the second clearcoat layer separately. The second clearcoat contains (A) as a binder a siloxane-group free (meth)acrylate copolymer that contains, based on the siloxane-group free (meth)acrylate copolymer, up to 90 wt.- % of hydroxy-group containing monomers polymerized into it. 10 to 90 wt.- % of these monomers are 4-hydroxybutyl(meth)acrylate and/or 2-alkyl-propane-1,3-diol-mono(meth)acrylate and 0 to 45 wt.- % or other hydroxyl-group containing monomers. The second clearcoat further contains (B) tris(alkoxycarbonylamino)triazine as the cross-linking agent, and the first and second clearcoats do not contain tricyclodecane dimethanol (TCD).

Description

Process for the production of multi-layer clear coats and color and / or effect multi-layer coats

The present invention relates to the production of multi-layer clearcoats, in particular in the context of coloring and / or effect-giving multi-layer coatings. The present invention further relates to new multilayer clearcoats.

Coloring and / or effect-giving paintwork of motor vehicle bodies, in particular car bodies, today preferably consist of several layers of paint which are applied one above the other and have different properties.

For example, an electrically deposited electrodeposition coating (ETL) as a primer, a filler coating, stone chip protection primer or functional layer, a base coat and a clear coat are applied to a substrate. Here, the ETL serves in particular to protect the sheet against corrosion. It is often referred to by experts as a primer. The filler coating serves to cover unevenness in the surface and, due to its elasticity, ensures resistance to stone chips. If necessary, the filler coating or functional layer can also serve to increase the hiding power and to deepen the color tone of the coating. The base coat contributes the colors and / or the optical effects. The clear coat serves to enhance the optical effects and to protect the paint from mechanical and chemical damage. Basecoat and clearcoat are often collectively referred to as topcoat. In addition, reference is also made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 49 and 51, "Automobillacke". It is an important goal of modern automotive painting to further improve the scratch resistance of the clearcoats without the other essential advantageous properties such as excellent transparency and DOI (Distinctiveness of the reflected image), high hardness, very good chemical resistance, weather resistance and resistance to bird droppings and tree resin , very good flow without affecting surface defects and excellent intermediate adhesion.

So-called sol-gel clearcoats based on siloxane-containing paint formulations, which are obtained by hydrolysis and condensation of silane compounds, have recently been developed. These clearcoats, which are used for the production of coatings for plastics, are described, for example, in German patents DE 43 03 570 A1, DE 3407 087 A1, DE 40 11 045 A1, DE 40 25 215 A1, DE 38 28 098 A 1, DE 40 20 316 A 1 or DE 41 22743 A 1.

Sol-gel clear coats give plastic substrates such as glasses or motorcycle helmet visors very good scratch resistance. However, the replacement of the clearcoats usually used in automotive painting by sol-gel clearcoats is not readily possible because the clearcoats produced from them are too brittle or often have poor optical properties (appearance). Above all, the sol-gel clearcoats are too expensive. The economically more favorable use of a sol-gel clearcoat as an additional clearcoat or so-called sealer over the previously used clearcoats results in adhesion problems between the clearcoat and the sol-gel clearcoat, which occur particularly after stone chips and when exposed to condensation.

It would therefore be highly desirable to have a process for scratch-proofing conventional and known clearcoats to have that works without the use of sol-gel clearcoats as a sealer.

Attempts have been made to improve the property profile of clearcoats and clearcoats produced from them by using thermally curable reactive thinners.

The use of polyhydroxy-functionalized cyclic and / or acyclic alkanes with 9 to 16 carbon atoms in the molecule, such as the positionally isomeric diethyloctanediols, as thermally curable reactive thinners in thermally or thermally and with actinic radiation-clearcoats, has already been described in German patent application DE 198 09 643 A1.

The use of hyperbranched compounds with a tefrafunctional central group as thermally curable reactive diluents in thermally or thermally and with actinic radiation clearcoats has already been described in German patent application DE 198 40 405 A1.

The use of hydroformylated and hydrogenated oligomers, obtainable by metathesis of acyclic monoolefins and cyclic monoolefins, hydroformylation of the resulting oligomers and subsequent hydrogenation, as thermally curable reactive diluents in thermally or thermally and with actinic radiation clearcoats, is already described in German patent application DE 198 05 421 A 1 described.

The corresponding clear coats provide clear coats with good scratch resistance, good hardness and good reflow behavior. The use of the known clearcoats as sealers in the context of multi-layer clearcoats is neither described nor suggested in patent applications DE 198 09 643 A1, DE 198 40 405 A1 or DE 198 05 421 A1. Thermally curable clear lacquers based on binders and crosslinking agents containing hydroxyl groups and containing functional groups reactive with hydroxyl groups are known from German published patent application DE 197 09 465 A1. After curing, they have a memory module E 'in the rubber-elastic range of at least 10 ^ .5 p _a and a loss factor tan δ at 20 ° C of a maximum of 0.10, the memory module E' and the loss factor using the dynamic mechanical thermal Analysis of free films with a layer thickness of 40 + 10 μm were measured. Inter alia (meth) acrylate polymers which contain 4-hydroxybutyl methacrylate in copolymerized form are used as binders. The clearcoats produced from the known clearcoats are scratch-resistant and chemical-stable. However, the level of scratch resistance that has already been achieved must be further improved for particularly demanding uses, for example in the series and refinishing of particularly high-quality automobiles of the upper class. In addition, the known coatings should be easier to polish. Furthermore, the height of the storage module E 'necessarily limits the selection of the constituents of the coating materials. The use of the known clearcoats as a sealer in the context of multi-layer clearcoats is neither described nor suggested in German patent DE 197 09 467 C 2 or German patent application DE 197 09 465 A1.

German patent application DE 198 50 210 A1 describes the use of 2-methyl-propane-1,3-diol-mono (meth) acrylate for the production of (meth) acrylate copolymers. The concerned

(Meth) acrylate copolymers are used for the production of clear lacquers. The clear coats deliver scratch-resistant and chemical-resistant clear coats. The use of the known clearcoats as a sealer in the context of Multi-layer clear coats are neither described nor suggested in German patent application DE 198 50 210 A1.

The German patent application DE 196 52 886 A 1 describes clear lacquers, the hydroxy-functional binders and

Tris (alkoxycarbonylamino) triazines contain as crosslinking agents. The scratch resistance of the clearcoats produced from these known clearcoats does not meet the requirements placed on a sealer. Accordingly, the use of the known clearcoats as sealers in the context of multi-layer clearcoats is neither described nor suggested in German patent application DE 196 52 886 A1.

In the unpublished German patent application DE 198 50 243 describes (meth) acrylate copolymers which are prepared by radical copolymerization of olefinically unsaturated monomers in liquid, thermally crosslinkable reactive diluents. The (meth) acrylate copolymers or their liquid mixtures with the said reactive diluents can be used in clearcoats. The resulting clear coats are thermostable, weather-resistant, scratch-resistant and light-resistant. The use of the clearcoats as a sealer in the context of multilayer clearcoats is not described in the unpublished German patent application DE 198 50 243.

German patent application DE 198 50 254 A1 describes sealers for multilayer clearcoats which are produced from clearcoats which contain at least one hydroxyl-containing polyacrylate which contains at least one polymerized polysiloxane macromonomer as binder and at least emTris (alkoxycarbonylamino) triazine as crosslinking agent. The use of thermally curable hydroxyl-containing reactive diluents is described in German patent application DE 198 50 254 A1 not described. A disadvantage of the known sealers is that they tend to cloud, in some cases have insufficient transparency and often do not allow the nameplate to be glued anymore.

The non-prepublished German patent application DE 199 38 759 also describes sealers for multilayer clearcoats which are produced from clearcoats which, as binders, contain at least one hydroxyl-containing polyacrylate which contains a polysiloxane macromonomer, containing a statistical average of at least 3.0 double bonds per molecule , and as a crosslinking agent

Tris (alkoxycarbonylamino) triazine included.

The non-prepublished German patent application DE 100 04 750.5 also describes sealers for multilayer clearcoats which are produced from clearcoats which contain tricyclodecanedimethanol (TCD) as an additive and TAGT as a crosslinking agent.

The object of the present invention is to find a new process for producing multilayer clearcoat, in particular in the context of coloring and / or effect-giving multicoat paint systems, on primed or unprimed substrates, which no longer has the disadvantages of the prior art, but rather without the use of Sol-gel clearcoats, without intermediate sanding, without the addition of special additives such as TCD to the clearcoats and without the use of (meth) acrylate copolymers which contain polymerized polysiloxane macromonomers, and which provides multilayered, high-scratch-resistant clearcoats which also have a high hardness, flexibility, Weather stability and chemical resistance, an excellent flow, a very good intermediate adhesion, an excellent overall optical impression and a very good polishability. Accordingly, the new process for producing a multi-layer clear coat on a primed or unprimed substrate was carried out

(I) application of at least a first clearcoat to the primed or unprimed substrate,

(II) drying the resulting first clear coat layer (s) without curing it, or - alternatively - curing the first clear coat layer (s),

(III) application of at least a second clear coat which is different from the first clear coat and

(IN) curing the first and second clear coat layers together or - alternatively - curing the second clear coat layer (s) on their own,

found the second clearcoats as a binder

(A) at least one siloxane group-free (Mefh) acrylate copolymer which, based on the siloxane group-free (meth) acrylate copolymer (A), contains up to 90% by weight of hydroxyl-containing olefinically unsaturated

Polymerized monomers (a) contains, of which

(al) 10 to 90 wt .-%, based on the siloxane group-free (meth) acrylate copolymer (A), 4-hydroxybutyl (meth) acrylate and / or 2-alkyl-propane-l, 3-diol-mono (meth) acrylate and

(a2) 0 to 45% by weight, based on the siloxane-free (meth) acrylate copolymer (A), represent other hydroxyl-containing olefinically unsaturated monomers; and as a wetting agent

(B) at least one tris (alkoxycarbonylamino) triazine

included, the first and the second clearcoats containing no tricyclodecanedimethanol (TCD).

In addition, the new Ner process for producing a color and or effect-giving multi-layer coating on a primed or unprimed substrate was carried out

(I) application of at least one coloring and / or effect paint to the primed or unprimed substrate,

(II) drying the resulting color and / or effect paint layer without curing it, or - alternatively - hardening the color and / or effect paint layer, resulting in the color and / or effect paint,

(III) application of at least a first clear lacquer to the coloring and / or effect lacquer layer or lacquer,

(TV) drying the first clear lacquer layer (s) without hardening it, or - alternatively - hardening the first clear lacquer layer (s) on its own or together with the coloring and / or effect lacquer layer,

(N) application of at least a second clear lacquer materially different from the first clear lacquer to the first clear lacquer layer or the first clear lacquer and (NI) curing of the second clear coat layer (s) on its own, together with the first clear coat layer (s) or together with the color and / or effect coating layer and with the first one or more

Clear coat layer (s), which results in the coloring and / or effect-giving multi-layer coating,

found the second clearcoats as a binder

(A) at least one siloxane group-free (meth) acrylate copolymer which, based on the siloxane group-free (meth) acrylate copolymer (A), contains up to 90% by weight of hydroxyl-containing olefinically unsaturated monomers (a) in copolymerized form, of which

(al) 10 to 90% by weight, based on the siloxane group-free (Mefh) acrylate copolymer (A), 4-hydroxybutyl (meth) acrylate and / or 2-alkyl-propane-1,3-diol-mono (meth) acrylate and

(a2) 0 to 45% by weight, based on the siloxane-free (meth) acrylate copolymer (A), represent other hydroxyl-containing olefinically unsaturated monomers;

and as a wetting agent

(B) at least one tris (alkoxycarbonylamino) triazine

The following are the new ner process for producing a multilayer clear coat on a primed or unprimed substrate and the new one Ner process for producing a color and / or effect multi-layer coating on a primed or unprimed substrate collectively referred to as "ner process according to the invention".

5 Further objects according to the invention result from the description.

In the context of the present invention, the term “physical hardening” means the hardening of a layer of a coating material by filming by solvent release from the coating material, the

10 Linking within the coating via loop formation of the polymer molecules of the binders (for the term cf. Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders", pages 73 and 74). Or the filming takes place via the coalescence of binder particles (cf. Römpp Lexikon Lacke and

15 printing colors, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 and 275). Usually no crosslinking agents are necessary. If necessary, the physical hardening can be supported by atmospheric oxygen, heat or by exposure to actinic radiation.

In the context of the present invention, the term "self-crosslinking" denotes the property of a binder to undergo crosslinking reactions with itself. A prerequisite for this is that the binders already contain both types of complementary reactive functional groups which are necessary for crosslinking. As external crosslinking become such

25 coating materials, adhesives and sealants referred to, wherein one type of complementary reactive functional groups in the binder, and the other type in a hardener or crosslinking agent. In addition, Römpp Lexikon Lacke und Druckfarben, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 to 276, especially page

30 275, below. In the context of the present invention, actinic radiation means electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation or X-rays, in particular UV radiation, and corpuscular radiation such as electron beams.

If thermal and curing with actinic light are used together, this is also called "dual cure".

The method according to the invention is used primarily in automotive painting, painting of buildings indoors and outdoors, painting furniture, doors and windows and industrial painting, including coil coating and container coating and the impregnation of electrotechnical components.

The method according to the invention is therefore based on primed or unprimed substrates made of metal, plastic, glass, wood, textile, leather, natural and artificial stone, concrete, cement or composites of these materials, as are usually used in the technical fields mentioned above, where the electrically conductive substrates are preferred.

In the case of electrically conductive substrates, in particular based on iron, primers can be used which are produced in a customary and known manner from electrocoat materials (ETL). Both anodic (ATL) and cathodic (KTL) electrodeposition coatings, but especially KTL, come into consideration for this.

The hardened electro-dip coating or the not or only partially hardened

Electrocoating layer can be covered with a filler, either alone or together with the electrocoating layer is cured (wet-on-wet process). The overlay with a filler takes place in particular in areas that are exposed to strong mechanical stress, such as stone chips.

Examples of suitable cathodic electrocoating materials and, if appropriate, wet-on-wet processes are described in Japanese Patent Application 1975-142501 (Japanese Patent Application Laid-Open JP 52-065534 A 2, Chemical Abstracts Section No. 87: 137427) or in the patent specifications and applications US 4,375,498 A 1, US 4,537,926 A 1, US 4,761,212 A 1, EP 0 529 335 A 1, DE 41 25 459 A 1, EP 0 595 186 A 1, EP 0 074 634 A 1, EP 0 505 445 A 1, DE 42 35 778 A 1, EP 0 646 420 A 1, EP 0 639 660 A 1, EP 0 817 648 A 1, DE 195 12017 C 1, EP 0 192 113 A 2, DE 41 26 476 A 1 or WO 98/07794 described.

Likewise, suitable fillers, in particular aqueous fillers, which are also referred to as stone chip protection primers or functional layers, from the patents and applications US 4,537,926 A1, EP 0 529 335 A1, EP 0 595 186 A1, EP 0 639 660 A1, DE 44 38 504 A1, DE 43 37 961 A1, WO 89/10387, US 4,450,200 A1, US 4,614,683 A1 or WO 490/26827 are known.

In the context of the method according to the invention, the filler layers applied to the electrodeposition coating can also be cured together with at least one further coating layer located thereon.

In the case of electrically conductive substrates based on aluminum, an aluminum oxide layer produced by anodic oxidation is preferably used as the primer.

In the process according to the invention, the clearcoats described below are applied directly to the substrates described above and hardened, the following process steps being carried out according to the invention:

(IV) joint curing of the first and second clear lacquer layer (s) or - alternatively - hardening of the second clear lacquer layer (s) on their own,

which results in the multilayer clearcoats.

According to the invention, it is advantageous to produce the multilayer clearcoats as part of the production of color and / or effect multi-layer coatings, the following process steps being carried out according to the invention:

(II) drying the resulting coloring and / or effect coating layer without curing it, or - alternatively - curing the coloring and / or effect coating layer, which results in the coloring and / or effect coating, (III) application of at least a first clear lacquer to the coloring and / or effect lacquer layer or lacquer,

(IN) drying the first clear lacquer layer (s) without hardening it, or - alternatively - hardening the first clear lacquer layer (s) on its own or together with the coloring and / or effect lacquer layer,

(N) application of at least a second clear lacquer materially different from the first clear lacquer to the first clear lacquer layer or the first clear lacquer and

(NI) curing of the second clear coat layer (s) on its own, together with the first clear coat layer (s) or together with the color and / or effect coat layer and with the first clear coat layer (s), whereby the colored and / or effect

Multi-layer painting results.

In the vast majority of cases, the desired technical effect can already be achieved by a first clear coat and a second clear coat in the ner driving according to the invention.

In the ner driving according to the invention, the outermost surface of the first clear coat can be treated physically and / or chemically before the second clear coat is applied. The physical treatment may include exposure to actinic radiation, treatment with ultrasound and or heat and or mechanical treatment, for example by grinding or polishing, and chemical treatment may include etching with suitable chemicals such as acids or bases and / or flame treatment. The physical and / or chemical treatment is used in particular when the first and second clearcoat layers and / or clearcoats contain no or only a very small number of reactive functional groups which match the complementary reactive functional groups in the other clearcoat layer (s). or clearcoat (s) can enter into reactions and / or contain none of the organic compounds (C) described below.

In terms of method, the application of the coating materials to be used in the process according to the invention has no special features, but can be carried out by all customary and known application methods suitable for the respective coating material, such as e.g. Electro dipping, spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling. Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot air - hot spraying, unless it is ETL or powder coatings.

In the physical hardening of the applied lacquer layers, no special measures need to be taken per se; however, physical hardening can be supported by atmospheric oxygen (oxidative hardening), heat or by exposure to actinic radiation.

The coating materials used in the process according to the invention are generally cured after a certain resting time or flash-off time. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 45 min. The rest period is used, for example, for the course and degassing of the lacquer layers and for the evaporation of volatile constituents such as any solvent and / or water still present. The ventilation can be caused by an increased temperature, which leads to hardening not sufficient, and / or accelerated by reduced humidity.

In the context of the present process, this process measure is also used for the purpose of drying the applied lacquer layers.

If coating materials curable with actmic radiation are used in the process according to the invention, the application, flashing off and drying are carried out with the exclusion of actinic radiation.

The thermal curing takes place, for example, with the aid of a gaseous, liquid and / or solid, hot medium, such as hot air, heated oil or heated rollers, or by microwave radiation, infrared light and / or near infrared light (NIR). The heating is preferably carried out in a forced air oven or by irradiation with IR and / or NIR lamps. As with curing with actmic radiation, thermal curing can also be carried out in stages. The thermal curing advantageously takes place at temperatures from room temperature to 200.degree.

When curing with actinic radiation, a dose of 1,000 to 3,000, preferably 1,100 to 2,900, particularly preferably 1,200 to 2,800, very particularly preferably 1,300 to 2,700 and in particular 1,400 to 2,600 mJ / cm ^{2 is} preferably used. If necessary, this hardening can be supplemented with actinic radiation from other radiation sources. In the case of electron beams, work is preferably carried out under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the powder slurry layer. In the case of curing with UV radiation, it is also possible to work under inert gas in order to avoid the formation of ozone. The usual and known radiation sources and optical auxiliary measures are used for curing with actmic radiation. Examples of suitable radiation sources are flash lamps from VISIT, high-pressure or low-pressure mercury vapor lamps, which may be doped with lead in order to open a radiation window up to 405 nm, or electron radiation sources. Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters. In the case of workpieces of complex shape, such as those intended for automobile bodies, the areas which are not directly accessible to radiation (shadow areas), such as ceilings, folds and other undercuts due to construction, can be combined with point, small area or all-round emitters, combined with an automatic movement device for irradiating cavities or Edges to be (partially) cured.

The facilities and conditions of these hardening methods are described, for example, in R. Holmes, UN. and E.B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984.

The curing can take place in stages, i. H. by multiple exposure or exposure to actinic radiation. This can also take place alternately, i. that is, curing alternately with UN radiation and electron radiation.

With Dual Cure, thermal curing and curing with actinic radiation can be used simultaneously or in succession. If the two curing methods are used in succession, thermal curing can be started, for example, and curing with actinic radiation can be ended. In other cases, it may prove advantageous to start and end the curing with actinic radiation. Basically, all customary and known color and / or effect paints are suitable for the process according to the invention. These are curable physically, thermally or thermally and with actinic radiation. They are conventional basecoats, waterborne basecoats, essentially solvent-free and water-free liquid basecoats (100% systems), essentially solvent-free and water-free solid basecoats (pigmented powder coatings) or essentially solvent-free pigmented powder coating dispersions (powder slurry basecoats). If they are thermally or dual-cure curable, they are self-curing or cross-linked.

10

For the purposes of the present invention, essentially solvent-free means that the coating material in question has a residual volatile solvent content of <2.0% by weight, preferably <1.5% by weight and particularly preferably <1.0% by weight , It is of particular advantage if the residual content 15 is below the gas chromatographic detection limit.

In the process according to the invention, water-based paints such as those from patent applications EP 0 089497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 are particularly preferably used

20 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A1, EP 0 593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590 484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95/14721, EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649 865 A1, EP 0 536 712 A1, EP 0 596

25 460 A 1, EP 0 596461 A 1, EP 0 584 818 A 1, EP 0 669 356 A 1, EP 0 634431 A 1, EP 0 678 536 A 1, EP 0 354 261 A 1, EP 0 424 705 A 1, WO 97/49745, WO 97/49747, EP 0 401 565 A1 or EP 0 817 684, column 5, lines 31 to 45, are known. The color and / or effect coatings described above can be used not only to produce color and / or effect base coats, but also of color and / or effect combination effect layers. In the context of the present invention, this is to be understood as a coating which fulfills at least two functions in a coloring and / or effect-giving multi-layer coating. Functions of this type are in particular protection against corrosion, the imparting of adhesion, the absorption of mechanical energy and the coloring and / or effect. Above all, the combination effect layer serves to absorb mechanical energy as well as color and / or effect at the same time; it therefore fulfills the functions of a filler paint or stone chip protection primer and a base coat. The combination effect layer preferably also has a corrosion protection effect and / or an adhesion-promoting effect.

All customary and known clearcoats are suitable as the first clearcoats. These are liquid solventborne clearcoats, liquid aqueous clearcoats, essentially solvent-free and water-free liquid clearcoats (100% systems), essentially solvent-free solid clearcoats (powder clearcoats) or essentially solvent-free powder clearcoat dispersions (powder slurry clearcoats). In particular, the powder clearcoats, the 100% systems and the powder slurry clearcoats are one-component systems. The conventional and the aqueous clear coats are one-component systems or multi-component systems. They are curable thermally and / or with actinic radiation. If they can be cross-linked thermally or dual-cure, they are cross-linking themselves or externally. In addition, they do not contain tricyclodecanedimethanol (TCD).

The first clear coats can be at least one of those described below

Compounds (C) which have reactive groups which react with the complementary reactive groups of the binders or of the crosslinking agents in the second clear coat layer (s) or clear coat (s), in which Contained quantities described below. If the second clearcoats do not contain any of the compounds (C) described below, at least one compound (C) in the amounts described below is mandatory in the first clearcoats. The compounds (C) here surprisingly act as adhesion promoters.

Suitable first clear coats are from the patent applications, patent specifications and publications DE 42 04 518 A1, EP 0 594 068 A1, EP 0 594 071 A1, EP 0 594 142 A1, EP 0 604 992 A1, EP 0 596 460 A 1, WO 94/10211, WO

10 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615, US 5,474,811 A 1, US 5,356,669 A 1 or US 5,605,965 A 1, DE 42 22 194 A 1, product information from BASF Lacke + Farben AG, "Powder Coatings", 1990, company lettering from BASF Coatings AG "Powder Coatings, Powder Coatings for Industrial Applications", January 2000, US 4,268,542 A1, DE 195 40 977 A1, DE 195 18

15 392 A1, DE 196 17 086 A1, DE-A-196 13 547, DE 196 52 813 A1, DE-A-198 14 471 A1, EP 0 928 800 A1, EP 0 636 669 A1 , EP 0 410 242 A1, EP 0 783 534 A1, EP 0 650 978 A1, EP 0 650 979 A1, EP 0 650 985 A1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1, EP 0 002 866 A1, DE 197 09 467 A1, DE 42 03 278 A1, DE 33 16 593 A1, DE 38 36 370 A1, DE 24 36 186 A1, DE

20 20 03 579 B 1, WO 97/46549, WO 99/14254, US 5,824,373 A 1, US 4,675,234 A 1, US 4,634,602 A 1, US 4,424,252 A 1, US 4,208,313 A 1, US 4,163,810 A 1, US 4,129,488 AI , US 4,064,161 A1, US 3,974,303 A1, EP 0 844 286 A1, DE 43 03 570 AI, DE 34 07 087 A1, DE 40 11 045 A1, DE 40 25 215 A1, DE 38 28 098 A. 1, DE 40 20 316 A 1 or DE 41 22 743 A 1.

25

The second clearcoats are different in material from the first clearcoats. Otherwise, they are also liquid solvent-based clearcoats, liquid aqueous clearcoats, essentially solvent-free and water-free liquid clearcoats (100% systems), essentially solvent-free solid clearcoats (powder clearcoats) or

30 essentially solvent-free powder clear coat dispersions (powder slurry Clearcoats). In particular the powder clearcoats, the 100% systems and the powder slurry clearcoats are one-component systems. The conventional and the aqueous clear coats are one-component systems or multi-component systems. They are thermally or thermally curable with actinic radiation. Conventional one-component systems are preferably used. In addition, they do not contain tricyclodecanedimethanol (TCD).

The first essential constituent of the second clearcoats to be used according to the invention are the binders (A). This is at least one special (meth) acrylate copolymer (A) free of siloxane groups.

The (meth) acrylate copolymer (A) to be used according to the invention preferably has

an OH number of 130 to 200, preferably 135 to 190, preferably 140 to 185 and in particular 145 to 180 mg KOH / g,

a glass transition temperature of -35 to +60, in particular -20 to + 40 ° C,

a number average molecular weight of 1,000 to 5,000 daltons, in particular 2,000 to 4,500 daltons, and

a mass average molecular weight of 2,000 to 20,000 daltons, in particular 4,000 to 16,000 daltons.

The (meth) acrylate copolymer (A) contains, based in each case on (A), up to 90, preferably up to 88, preferably up to 86, particularly preferably up to 84, very particularly preferably up to 82 and in particular up to 80% by weight. -% on copolymerized olefin-unsaturated monomers (a) containing hydroxyl groups, of which

(al) 10 to 90, preferably 12 to 80, preferably 20 to 70 and in particular 30 to 60% by weight, in each case based on the (meth) acrylate copolymer

(A), 4-hydroxybutyl (meth) acrylate and / or 2-alkyl-propane-l, 3-diol mono (meth) acrylate and

(a2) 0 to 45, preferably 5 to 40 and in particular 15 to 37% by weight, based in each case on the (meth) acrylate copolymer (A), are other hydroxyl-containing olefinically unsaturated monomers.

Examples of suitable 2-alkyl-propane-1,3-diol-mono (meth) acrylates (al) are 2-methyl, 2-ethyl, 2-propyl, 2-isopropyl or 2-n-butyl-propane -1,3-diol-mono (meth) acrylate, of which 2-methyl-propane-1,3-diol-mono (meth) acrylate is particularly advantageous and is preferably used according to the invention.

Examples of suitable other hydroxyl-containing olefinically unsaturated monomers (a2) are hydroxyalkyl esters of acrylic acid, methacrylate or another alpha, beta-ethylenically unsaturated carboxylic acid which (i) are derived from an alkylene glycol which is esterified with the acid, or (ii) by reaction the acid can be obtained with an alkylene oxide such as ethylene oxide or propylene oxide, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, crotonic acid or ethacrylic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 3-hydroxypropyl, 3-hydroxybutylmefhacrylate, ethacrylate or crotonate; 1,4-

Bis (hydroxymethyl) cyclohexane or octahydro-4,7-methano-1H-indenedimethanol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate; or reaction products from cyclic esters, such as, for example, epsilon-caprolactone and these hydroxyalkyl esters; or olefinically unsaturated alcohols such as allyl alcohol; or polyols such as trimethylolpropane mono- or diallyl ether or pentaeiythritol mono-, di- or triallyl ether. These higher functional

Monomers (a2) are generally only used in minor amounts. In the context of the present invention, minor amounts of higher-functional monomers (a2) are to be understood as amounts which do not lead to the crosslinking or gelling of the (meth) acrylate copolymers (A), unless they should be in the form of crosslinked microgel particles ,

Furthermore, ethoxylated and / or propoxylated AUyl alcohol, which is sold by Arco Chemicals, or 2-hydroxyalkylallyl ether, in particular 2-hydroxyethylallyl ether, are suitable as monomers (a2). If used, they are preferably not used as sole monomers (a2), but in an amount of 0.1 to 10% by weight, based on the (meth) acrylate copolymer (A).

In addition, there are reaction products of acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, or an equivalent amount of acrylic and / or methacrylic acid instead of the reaction products which then during or after the polymerization reaction with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule branched in the alpha position, in particular one Versatic® acid (cf.Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, »Versatic® acids«, pages 605 and 606).

In addition, the (meth) acrylate copolymers (A) contain further olefinically unsaturated monomers (a3), the proportion of (A) of which is at least 10, preferably at least 12, preferably at least 14, particularly preferably at least 16, is very particularly preferably at least 18 and in particular at least 20% by weight.

Examples of suitable monomers (a3) are

Monomers (a31):

Essentially acid group-free (meth) acrylic acid esters such as (meth) acrylic or alkyl cycloalkyl esters with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert.-butyl , Hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; cycloaliphatic (meth) acrylic acid esters, especially cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene methanol or tert-butylcyclohexyl (meth) acrylate; (Meth) acrylic acid oxaalkyl esters or oxacycloalkyl esters such as ethyl triglycol (meth) acrylate and methoxy oligoglycol (meth) acrylate with a molecular weight Mn of preferably 550 daltons or other ethoxylated and / or propoxylated hydroxyl group-free (meth) acrylic acid derivatives (further examples of suitable monomers (a2) of this type are from the published patent application DE 196 25 773 A1, column 3, line 65, to column 4, line 20, is known). These can be used in minor amounts of higher functional (meth) acrylic or alkyl cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-diol, hexane-1,6-diol, octahydro- 4,7-methano-1H-indene-dimethanol or cyclohexane-1,2-, 1,3- or -1,4-diol-di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol di-, tri- or tetra (meth) acrylate. With regard to the amounts of higher functional monomers (a31), what has been said above with regard to the monomers (a2) applies.

Monomers (a32): At least one acid group, preferably a carboxyl group, per molecule carrying ethylenically unsaturated monomers or a mixture of such monomers. Acrylic acid and / or methacrylic acid are particularly preferably used as component (a32). However, other ethylenically unsaturated carboxylic acids with up to 6 carbon atoms in the molecule can also be used. Examples of such acids are Efhacrylic acid, Crόtonsäure, maleic acid, fumaric acid and itaconic acid. Furthermore, ethylenically unsaturated sulfonic or phosphonic acids or their partial esters can be used as component (a32). Monomers (a32) are furthermore maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester as well as vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or

Vinylbenzenesulfonic acid (all isomers). Further examples of monomers containing acid groups (a32) are known from published patent application DE 196 25 773 A1, column 2, line 58 to column 3, line 8, or from international patent application WO 98/49205, page 3, lines 23 to 34 ,

Monomers (a33):

Vinyl esters of monocarboxylic acids with 5 to 18 carbon atoms in the molecule, branched in the alpha position. The branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins. When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom. Other olefinic starting materials are, for example, propylene frimer, propylene tetramer and diisobutylene. However, the vinyl esters can also be prepared from the acids in a manner known per se, for example, by allowing the acid to react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used.

Monomers (a34):

N, N-diethylamino-alpha-methylstyrene (all isomers), N, N-diethylaminostyrene (all isomers), allylamine, crotylamine, 2-amino- or 2-N-methyl-, 2-N, N-dimethyl-, 2 -N-ethyl, 2-N, N-diethyl, 2-N-propyl, 2-N, N-dipropyl, 2-N-butyl, 2-N, N-dibutyl, 2-N -Cyclohexyl- or 2-N, N-cyclohexyl-methyl-amino- or 2-N, N, N, N-teframethylammonium- or 2-N, N-dimethyl-N, N-diethylammonium-, 2-tetramethylphosphonium- or 2-triethylsulfonium ethyl acrylate, ethyl methacrylate, propyl acrylate or propyl methacrylate or 3-amino or 3-N-methyl, 3-N, N-dimethyl, 3-N-ethyl, 3-N, N-diethyl -, 3-N-Propyl-, 3-N, N-dipropyl-, 3-N-butyl-, 3-N, N-dibutyl-, 3-N-cyclohexyl- or 3-N, N-cyclohexyl-methyl -amino- or 3-N, N, N, N-tetramethylammomum- or 3- N, N-dimethyl-N, N-diethylammomum-, 3-tetramethylphosphomum- or 3-triethylsulfonium propyl acrylate or propyl methacrylate.

Monomers (a35):

Diarylethylenes, in particular those of the general formula I:

J ^ R ^ CR (I),

wherein the radicals R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R ¹ , R ² , R ³ and R ^{4 are} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl residues. Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert. -Butyl, amyl, hexyl or 2-ethylhexyl. Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl. Examples of suitable alkylcycloalkyl radicals are methylene cyclohexane, ethylene cyclohexane or propane-1,3-diylcyclohexane. Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylcyclohex-1-yl. Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl, preferably phenyl and naphthyl and in particular phenyl. Examples of suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diyl-benzene. Examples of suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-l-yl. Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylphen-1-yl. Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-l-yl. The aryl radicals R ¹ , R ² , R ³ and / or R ⁴ are preferably phenyl or naphthyl radicals, in particular phenyl radicals. The substituents optionally present in the radicals R ¹ , R ² , R ³ and / or R ⁴ are electron-withdrawing or electron-donating atoms or organic radicals, in particular halogen atoms, nitrile, nitro, partially or completely halogenated alkyl, cycloalkyl, alkylcycloalkyl , Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; Aryloxy, alkyloxy and cycloalkyloxy radicals; Arylthio, alkylthio and cycloalkylthio residues and / or primary, secondary and / or tertiary amino groups. Diphenylethylene, dinaphthaleneethylene, eis or frans stilbene, vinylidene-bis (4-N, N-dimethylaminobenzene), vmylidene-bis (4-aminobenzene) or vinylidene-bis (4-nifrobenzene), in particular diphenylethylene (DPE), are particularly advantageous which is why they are preferred. In the context of the present invention, the monomers (a35) are used in order to regulate the copolymerization advantageously in such a way that a free-radical copolymerization in batch mode is also possible. Monomers (a36):

Cyclic and / or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene.

Monomers (a37:

Monido-containing monomers such as (meth) acrylic acid amide such as (meth) acrylic acid amide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-diρroρyl, N -Butyl-, N, N-dibutyl-, N-cyclohexyl-, N, N- cyclohexy 1-methyl- and / or N-methylol-, N, N-dimethylol-, N-methoxymefethyl-, N, N-Di (methoxymethyl) -, N-ethoxymethyl-xmd or N, N-di (ethoxyethyl) - (meth) acrylic acid amide; monomers containing carbamate groups such as

(Meth) acryloyloxyethyl carbamate or (meth) acryloyloxypropyl carbamate; or urea group-containing monomers such as ureido acrylate or methacrylate.

Monomers (a38):

Monomers containing epoxy groups, such as the glycidyl ester of acrylic acid,

Methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or

Itaconic acid.

Monomers (a39):

Vinylaromatic hydrocarbons such as styrene, vinyltoluene, diphenylethylene or alpha-alkylstyrenes, especially alpha-methylstyrene.

Monomers (A310):

Nitriles such as acrylonitrile and / or methacrylonitrile.

Monomers (A311):

Vinyl compounds, especially vinyl and / or vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N- Vinylamides such as vinyl-N-methylformamide, N-vinylcaprolactam or N-vinylpyrrolidone; 1-Vmylimidazol; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinyl cyclohexyl ether; xmd / or vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid.

Monomers (a312):

Allyl compounds, especially allyl ether xmd esters such as allylmethyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.

The monomers (al) and (a3) and optionally (a2) are selected so that the OH numbers and glass transition temperatures given above result. In addition, the monomers (a3) which contain reactive functional groups are selected according to their type and amount such that they do not inhibit or completely prevent the crosslinking reactions of the hydroxyl groups with the crosslinking agents (B) described below.

The person skilled in the art can select the monomers (a) to adjust the glass transition temperatures with the aid of the following formula from Fox, with which the glass transition temperatures of poly (meth) acrylates can be approximately calculated:

n = x

n = l

Tg = glass transition temperature of the poly (meth) acrylate; W _n = weight fraction of the nth monomer; Tg _n = glass transition temperature of the homopolymer from the nth

Monomer and x = number of different monomers.

The production of the (meth) acrylate copolymers (A) to be used according to the invention also has no special procedural features, but takes place with the aid of the methods known and known in the plastics field of continuous or discontinuous radical-initiated copolymerization in bulk, solution, emulsion, miniemulsion or microemulsion Normal pressure or overpressure in stirred tanks, autoclaves, tubular reactors, loop reactors or Taylor reactors at temperatures from 50 to 200 ° C.

Examples of suitable copolymerization processes are described in patent applications DE 197 09 465 A1, DE 197 09 476 A1, DE 28 48 906 A1, DE 195 24 182 A1, DE 198 28 742 A1, DE 196 28 143 A1, DE 19628 142 A1, EP 0 554 783 A1, WO 95/27742, WO 82/02387 or WO 98/02466. The copolymerization can, however, also be carried out in the polyols (C) described below as the reaction medium, as is described, for example, in the unpublished patent application DE 198 50 243.

Examples of suitable free-radical initiators are dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; peroxodicarbonates; Potassium, sodium or

ammonium peroxodisulfate; Azo initiators, for example azo dinitriles such as azobisisobutyronitrile; CC-cleaving initiators such as benzpinacol silyl ether; or a combination of a non-oxidizing initiator with hydrogen peroxide. It Combinations of the initiators described above can also be used.

Further examples of suitable initiators are described in German patent application DE 196 28 142 A1, page 3, line 49, to page 4, line 6.

Comparatively large amounts of free-radical initiator are preferably added, the proportion of the initiator in the reaction mixture, based in each case on the total amount of the monomers (a) and the initiator, particularly preferably 0.2 to 20% by weight, very particularly preferably 0.5 is up to 15 wt .-% and in particular 1.0 to 10 wt .-%.

Furthermore, thiocarbonylthio compounds or mercaptans such as dodecyl mercaptan can be used as chain transfer agents or molecular weight regulators.

The (meth) acrylic copolymers (A) are preferably selected according to their type and quantity so that the coating materials, adhesives and sealants according to the invention, after they have hardened, have a storage module E 'in the rubber-elastic range of at least 10 ^, p _a and a loss factor tan δ at 20 ° C of a maximum of 0.10, the storage module E 'and the loss factor having been measured with dynamic mechanical thermal analysis on free films with a layer thickness of 40 + 10 μm (cf. the German patent DE 197 09 467 C 2).

In addition to the hydroxyl groups, the (meth) acrylate copolymers (A) of the second dual-cure clearcoats contain, on average, at least one, preferably at least two, group (s) with at least one bond (s) which can be activated with actinic radiation per molecule. In the context of the present invention, a bond which can be activated with actinic radiation is understood to mean a bond which becomes reactive when irradiated with actinic radiation and which undergoes polymerization reactions and / or crosslinking reactions with other activated bonds of its kind which take place according to radical and / or ionic mechanisms. Examples of suitable bonds are single carbon-hydrogen bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds. Of these, the carbon-carbon double bonds are particularly advantageous and are therefore used with very particular preference according to the invention. For the sake of brevity, they are referred to below as "double bonds".

Accordingly, the group preferred according to the invention contains one double bond or two, three or four double bonds. If more than one double bond is used, the double bonds can be conjugated. According to the invention, however, it is advantageous if the double bonds are isolated, in particular each individually in the group in question here. According to the invention, it is particularly advantageous to use two, in particular one, double bond.

On a statistical average, the dual-cure binder (A) contains at least one of the groups described above which can be activated with actinic radiation. This means that the functionality of the binder in this regard is an integer, that is, for example, two, three, four, five or more, or is not an integer, that is, for example, 2.1 to 10.5 or more. If, on average, more than one group that can be activated with actinic radiation is used per molecule, the groups are structurally different from one another or of the same structure.

If they are structurally different from one another, this means within the scope of the present invention that two, three, four or more, but in particular two, groups which can be activated with actinic radiation and which differ from two, three, four or more, in particular two, are used. Derive monomer classes.

Examples of suitable groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, but especially acrylate groups.

The groups are preferably bonded to the respective basic structures of the binders via urethane, urea, allophanate, ester, ether xmd / or amide groups, but in particular via ester groups. This is usually done by customary and known polymer-analogous reactions, such as the reaction of pendant glycidyl groups with the above-described olefinically unsaturated monomers which contain an acid group, of pendant hydroxyl groups with the halides of these monomers, of isocyanates containing hydroxyl groups with double bonds, such as vinyl isocyanate, methacryloyl isocyanate and / or l- (l-isocyanato-l-methylethyl) - 3- (l-methylethenyl) benzene (TMI® from CYTEC) or of isocanate groups with the above-described monomers containing hydroxyl groups. However, mixtures of purely thermally curable (meth) acrylate copolymers (A) and binders curable purely with actinic radiation can also be used in the second dual-cure clearcoats.

The content of the (meth) acrylate copolymer (A) described above in the second clearcoats to be used according to the invention can vary widely. The content depends in particular on the functionality of the binders on the one hand and the functionality of the crosslinking agents (B) described below on the other. The content is preferably 5.0 to 90, preferably 6.0 to 85, particularly preferably 7.0 to 80, very particularly preferably 8.0 to 75 and in particular 9.0 to 70% by weight, in each case based on the Solid of the second clear coats.

The second essential component of the second clearcoat is at least one tris (alkoxycarbonylannno) triazine (TAGT) of the general formula II,

(II)

0

which serves as a crosslinking agent (B).

Examples of suitable tris (alkoxycarbonylarnino) triazines (B) are described in US Pat. Nos. 4,939,213 A1 or 5,084,541 A1 or US Pat Patent applications EP 0 624 577 A1 or EP 0 604 922 A1 described. In particular, the tris (methoxy-, tris (butoxy- and / or tris (2-ethymexoxycarbonylamino) triazines are used.

The methyl-butyl mixed esters, the butyl-2-ethylhexyl mixed esters and the butyl esters are advantageous. Compared to the pure methyl ester, these have the advantage of better solubility in polymer melts and also have less tendency to crystallize out.

TACT is or are in the second clear lacquers preferably in an amount of 1.0 to 60, preferably 2.0 to 55, particularly preferably 3.0 to 50, very particularly preferably 4.0 to 50 and in particular 5.0 to 45% by weight .-%, each based on the solids of the second clearcoat.

The first and / or the second clearcoats can have at least one of the compounds (C) described below which have reactive groups which react with the complementary reactive groups of the binders or the crosslinking agents in the respective other clearcoat layer (s) or clearcoat (s) , contained in the amounts described below.

Examples of suitable complementary reactive functional groups for the compounds (C) and the binders and crosslinking agents are compiled in the following overview. In the overview, the variable R ^{5 stands} for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R ⁶ and R ⁷ represent the same or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring. Overview: Examples of complementary functional groups

Agents and crosslinking agents or crosslinking agents and binders

-SH -C (O) -OH

-NH ₂ -C (O) -OC (O) -

-OH -NH-C (O) -OR ⁵

-O- (CO) -NH- (CO) -NH ₂ -CH ₂ -OH

-O- (CO) -NH ₂ -CH ₂ -OR ⁵

> NH -NH-CH ₂ -OR ⁵

-NH-CH ₂ -OH

NCO

-N (-CH ₂ -OR ⁵ ) ₂

-NH-C (O) -CH (-C (O) -OR ⁵ ) ₂

-NH-C (O) -CH (-C (O) -OR ⁵ ) (- C (O) -R ⁵ )

O / \

-CH-CH ₂

-N = ON

-C (O) -N (CH ₂ -CH ₂ -OH) ₂

The selection of the respective complementary groups depends on the one hand on the fact that they do not undergo any undesirable reactions, in particular no premature crosslinking, during the production, storage and application of first and / or second clearcoats, and / or, if appropriate, curing with actinic radiation must not disturb or inhibit, and on the other hand in which temperature range the crosslinking should take place.

Preferably, the thermally or thermally and with actinic

Radiation curable first and / or second clearcoats crosslinking temperatures of 60 to 180 ° C applied. It is therefore preferred to use thio, hydroxyl, N-methylolamino, N-alkoxymemylamino, imino, carbamate, AUophanat- and or carboxyl groups, preferably hydroxyl groups, on the one hand and preferably anhydride, carboxyl, epoxy, blocked isocyanate, urethane or Ajj oxycarbonylamino groups (see general formula II), methylol, methylol ether, carbonate, amino, Hydroxy and / or beta-hydroxyalkylamide groups, preferably urethane or alkoxycarbonylamino groups, used on the other hand.

The above-described complementary functional groups can be contained in the binders (A) in addition to the hydroxyl groups and in the crosslinking agents (B) in addition to the alkoxycarbonylamino groups.

Basically, all organic compounds that meet the requirements described above and carry at least two of the reactive functional groups described above are suitable as compounds (C).

Examples of suitable compounds (C) are polythiols, polyols, polyaniines, polythiol polyols, PolytMol polyamines, polyamine polyols, polytool polyamine polyols, polycarbamates, polyurethanes or poly (alkoxycarbonylamino) frazines or pyrimidines, polyallophanates or polycarboxylic acids.

Particular advantages result if the hydroxyl groups in polyols (C) and the alkoxycarbonylamino groups are present in at least one of the tris (alkoxycarbonylamino) triazines (B) described above.

Examples of suitable polyols (C) are the cyclic and or acyclic C ₉ -C ₁₆ alkanes which are functionalized with at least two hydroxyl groups (“functionalized alkanes”), such as the positionally isomeric diethyloctanediols, as described in German patent application DE 198 09 643 A 1 are described. Advantageous functionalized alkanes (C) are derived from branched acyclic alkanes with 9 to 16 carbon atoms, which each form the basic structure.

Examples of suitable alkanes with 9 carbon atoms are 2-methyloctane, 4-methyloctane, 2,3-dimethyl-heptane, 3,4-dimethyl-heptane, 2,6-dimethyl-heptane, 3,5-dimethyl-heptane, 2-methyl -4-ethyl hexane or isopropyl cyclohexane.

Examples of suitable alkanes with 10 carbon atoms are 4-ethyloctane, 2,3,4,5-tetramethyl-hexane, 2,3-diethyl-hexane or 1-methyl-2-n-propyl-cyclohexane.

Examples of suitable alkanes with 11 carbon atoms are 2,4,5,6-tetramethyl-heptane or 3-methyl-6-ethyl-octane.

Examples of suitable alkanes with 12 carbon atoms are 4-methyl-7-ethyl-nonane, 4,5-diethyl-octane, 1'-ethyl-butyl-cyclohexane, 3,5-diethyl-octane or 2,4-diethyl-octane.

Examples of suitable alkanes with 13 carbon atoms are 3,4-dimethyl-5-ethyl-nonane or 4,6-dimethyl-5-ethyl-nonane.

An example of a suitable alkane with 14 carbon atoms is 3,4-dimethyl-7-ethyl-decane.

Examples of suitable alkanes with 15 carbon atoms are 3,6-diethyl-undecane or 3,6-dimethyl-9-ethyl-xxndecane.

Examples of suitable alkanes with 16 carbon atoms are 3,7-diethyl-dodecane or 4-ethyl-6-isopropyl-undecane. Of these basic structures, the alkanes with 10 to 14 and in particular 12 carbon atoms are particularly advantageous and are therefore used with preference. Of these, the octane derivatives are particularly advantageous.

It is advantageous for the present invention that the functionalized alkanes (C), which are derived from these branched, cyclic or acyclic alkanes as basic structures, are liquid at room temperature. Either single liquid functionalized alkanes (C) or liquid mixtures of these compounds can thus be used. This is particularly the case when functionalized alkanes (C) are used which, because of their high number of carbon atoms in the alkane backbone, are solid as individual compounds. The person skilled in the art can therefore select the corresponding functionalized alkanes (C) in a simple manner.

It is also essential for the invention that the functionalized alkanes (C) have a boiling point above 200, preferably 220 and in particular 240 ° C. In addition, they should have a low evaporation rate.

According to the invention, it is also advantageous if the functionalized alkanes (C) are acyclic.

The functionalized alkanes (C) have primary and / or secondary hydroxyl groups. According to the invention, it is advantageous if primary and secondary groups of this type are present in a functionalized alkane (C).

The functionalized alkanes (C) can be used individually or together as mixtures. There are particular advantages if the polyols (B2) Diols and / or triols, but especially diols. They are therefore used with particular preference.

Diols (C) which are particularly advantageous are the positionally isomeric dialkyloctanediols, in particular diethyloctanediols. Of these, 2,4-diethyl-octanediol-1,5 is particularly noteworthy.

The polyols (C) described above are compounds known per se and can be prepared using customary and known synthesis methods in organic chemistry, such as base-catalyzed aldol condensation, or they are obtained as by-products of large-scale chemical syntheses, such as the preparation of 2-ethylhexanol.

Further examples of suitable polyols (C) are hyperbranched compounds with a tefrafunctional central group, as are described, for example, in German patent application DE 198 40 405 A1.

Particularly suitable are polyols (C) are hyperbranched compounds with a tefrafunctional central group, derived from ditrimethylolpropane, diglycerol and / or ditrimethylolethane, or a tefrafunctional zenfral group of the general formula III,

C [-A _q -X-] _m [-A _r -X-] _n [-A _s -X-] ₀ [-A _t -X-] _p (III),

where the indices and the variables have the following meaning:

m + n + o + p = 4; with m = an integer from 1 to 3 and n, o and p = 0 or an integer from 1 to 3; q, r, s and t = an integer from 1 to 5, where q> r, s, t, in particular q> r, s, t;

X = -O-, -S- or -NH-;

A = -C (R ⁸ ) ₂ -; With

R ⁸ = -H, -F, -CL -Br, -CN, -NO ₂ , C ₁ -C ₃ alkyl- or -

Haloalkyl or C Cs alkoxy or - for q, r, s and or t = at least 2 - R = a C ₂ -C - alkanediyl and / or -Oxaalkandiylrest, which 2 to

5 carbon atoms and / or an oxygen atom -O-, which bridges 3 to 5 carbon atoms of the radical -A-.

The term “derived” is to be understood here as the conceptual abstraction of the hydrogen atoms from the hydroxyl groups of the tetrols.

According to the invention, the central groups III are advantageous and are therefore used with particular preference.

In the general formula III, the indices q, r, s and t denote integers from 1 to 5. Here, the index q can be equal to the indices r, s and t. Under this framework, symmetrical central groups III result.

Examples of suitable symmetrical central groups III to be used according to the invention are derived from symmetrical tetrols such as pentaeryxfrit, tefrakis (2-hydroxyethyl) methane or tetrakis (3-hydroxypropyl) methane.

According to the invention, Zenfralgruppen III, in which the index q is larger than the indices r, s and t and therefore has a value of at least 2, are advantageous and are therefore used with particular preference. Under this framework, asymmetrical Zenfral groups III result.

In the general formula III, the indices m, n, o and p add up to 4. The index m is always greater than 0 and stands for an integer from 1 to 3, in particular for 1.

The indices n, o and p have the value 0 in consideration of the above boundary condition or stand for an integer from 1 to 3. This means that not each of these indices can assume the value 0.

According to the invention, the following value combinations of the indices are advantageous:

m = 1 and n, o, p = 1; m = 1, n = 2, o, p = 1; m = 1, n = 2, o = 1 and p = 0; m = 1, n = 3, o, p = 0;

m = 2, = 1, o = 1 and p = 0; m = 2, n = 2 and o, p = 0;

m = 3, n = 1 and o, p = 0.

Of these, the number combinations in which m = 1 are particularly advantageous.

The following number combinations of the indices are advantageous according to the invention:

q = 2, r, s and / or t = 1; q = 3, r, s and / or t = 1 and / or 2; q = 4, r, s and / or t = 1, 2 and / or 3; q = 5, r, s and / or t = 1, 2, 3 and / or 4.

The variable -X- in the general formula III denotes double-bonded oxygen atoms -O- or sulfur atoms -S- or a secondary amino group - NH-. According to the invention, it is advantageous if -X- stands for -O-.

The variable -A- in formula III means a double-bond radical -C (R) ₂ -.

The radical R ⁷ here stands for hydrogen atoms -H, fluorine atoms -F, chlorine atoms - Cl, bromine atoms -Br, nitrile groups -CN, nitro groups -NO ₂ , CrCralkyl or - haloalkyl groups or -C-C ₃ alkoxy groups. Examples of suitable groups of this type are methyl, ethyl, propyl, trifluoromethyl, trichloromethyl, perfluoroethyl, perfluoropropyl, methoxy, ethoxy or propoxy groups.

According to the invention, hydrogen atoms or methyl groups are advantageous, which are therefore used with preference. In particular, hydrogen atoms are used. The variables -A- which are particularly preferred according to the invention are accordingly methylene groups.

If in the general formula III at least one of the indices q, r, s and / or t is at least the number 2, the radical R can also be a C ₂ -C -alkanediyl and / or oxaalkanediyl radical which has 2 to 5 carbon atoms of the Rest - A cyclically bridged. The radical -R ⁸ - can, however, also represent an oxygen atom - O-, which cyclically bridges 3 to 5 carbon atoms of the radical -A-. As a result, cyclopentane-1, 2- or -1,3-diyl groups, tefrahydrofuran-2,3-, -2,4-, -2,5- or -3,4-diyl groups, cyclohexane-1, 2-, -1,3- or -1,4-diyl groups or tetrahydropyran-2,3-, 2,4-, 2,5- or 2,6-diyl groups, but no epoxy groups. Examples of central groups III which are particularly advantageous according to the invention are derived from the tefrols of the general formula IIIA described below:

C [-A _q -XH] _m [-A _r -XH] _n [-A _S -XH] ₀ [-A _t -XH] _P (IIIA),

In the general formula Va, the indices and the variables have the same meaning as given above for the general formula III. According to the invention, it is particularly advantageous if the variable X represents an oxygen atom -O-.

Accordingly, the tefroles of the general formula IIIA are of particular advantage for the preparation of the zenfral group III or of the compounds to be used according to the invention and are therefore used with particular preference. For the sake of brevity, they are referred to below as "Tefrole IIIA".

Examples of very particularly suitable tefrole IIIA to be used according to the invention are the symmetrical tefrole pentaeiythritol, tetrakis (2-hydroxyethyl) methane or tetrakis (3-hydroxypropyl) methane or the asymmetrical tefrole (IIIA1) to (IIIA10):

HO - (- CH ₂ -) ₂ -C (-CH ₂ -OH) ₃ , (IIIA1)

HO - (- CH ₂ -) ₃ -C (-CH ₂ -OH) ₃ , (IIIA2)

HO - (- CH ₂ -) ₄ -C (-CH ₂ -OH) ₃ , (IHA3) HO - (- CH ₂ -) ₅ -C (-CH ₂ -OH) ₃ , (IIIA4)

[HO - (- CH ₂ -) ₂ -] ₂ C (CH ₂ -OH) ₂ , (IIIA5)

[HO - (- CH ₂ -) ₂ -] ₃ C-CH ₂ -OH, (HIA6)

HO - (- CH ₂ -) ₃ -C [- (- CH ₂ -) ₂ -OH] ₃ , (IIIA7)

HO - (- CH ₂ -) ₃ -C [- (- CH ₂ -) ₂ -OH] ₂ (-CH ₂ -OH), (IIIA8)

HO - (- CH ₂ -) ₄ -C (-CH ₂ -OH) [- (- CH ₂ -) ₂ -OH] [- (- CH ₂ -) ₃ -OH] or (IIIA9)

HO - (- CH ₂ -) ₅ -C (-CH ₂ -OH) [- (- CH ₂ -) ₄ -OH] 2 (IIIAIO).

Of these, the tefrol (IIIA1) (2,2-bis-hydroxymethyl-butanediol- (1,4); homopentaerythritol) is particularly noteworthy because it has very particularly advantageous properties. It is therefore used with very particular preference.

The most preferred polyols (IIIA) are those described above

Variables -X- linked to a hydroxyl group via spacer groups. This applies mutatis mutandis to the Zenfralgruppen, which are derived from the tefrolene ditrimethylolpropane, diglycerol or ditiimethylolethane, their Oxygen atoms correspond to the variable -X-. The following description of the spacer groups therefore also applies to these Zenfral groups, which differ from central groups III.

All double-bonded organic residues are suitable as spacer groups.

Examples of highly suitable double-bonded organic radicals are those which are derived from the following compounds:

(i) an alkane, alkene, cycloalkane, cycloalkene, alkylcycloalkane, alkylcycloalkene, alkenylcycloalkane, or alkenylcycloalkene, aromatics and heteroamates as well as an alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcycloalkyl, alkylcycloalkenyl, alkenyl or alkenyl alkenyl or alkenyl alkenyl or alkenyl alkenyl or alkenyl Aromatics or heteroaromatics; or from

(i) an abovementioned radical which contains at least one heteroatom in the chain and / or in the radical; or from

(iii) a radical mentioned under (i) or (ii), the chain and / or ring of which is substituted.

Examples of suitable substituents for the double-bonded organic radicals to be used according to the invention are all organic radicals which are essentially inert, ie that they do not undergo any reactions with the compounds which are used for the construction of the particularly preferred polyols (C), in particular halogen atoms, Nifro groups, nitrile groups or alkoxy groups. The spacer groups are connected in particular via carbonyl groups to the zenfral groups III or the central groups which are derived from the other tefrols mentioned.

Examples of organic compounds which are particularly suitable for the preparation of these spacer groups are epsilon-caprolactone, hexahydrophthalic acid, hexahydrophthalic anhydride, phthalic acid,

Phthalic anhydride, hexahydroterephthalic acid, terephthalic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, oxalic acid, malonic acid, malonic acid anhydride, succinic acid, succinic acid anhydride, peanutic acid, adipic acid, adipic acid, adipic acid, adipic acid, adipic anhydride Of these, epsilon-caprolactone, maleic acid or maleic anhydride and hexahydrophthalic anhydride are particularly suitable and are therefore used with particular preference.

In the production of the particularly preferred polyols (C) to be used according to the invention, the tefrole IIIA or the other tefrolene mentioned are reacted with the above-mentioned functional compounds to form an intermediate product into which the hydroxyl groups can be introduced.

All organic compounds which can react with the intermediates to form a hydroxyl group or to obtain a hydroxyl group are suitable for this purpose. According to the invention, it is advantageous to use a compound which reacts with the intermediates to form a hydroxyl group.

Examples of highly suitable organic compounds / of this type are compounds containing epoxy groups, in particular those containing glycidyl groups. Examples of highly suitable epoxy group-containing, in particular glycidyl group-containing, compounds are ethylene oxide, propylene oxide, EpicMorhydrin, glycidol, glycidyl ether, in particular aryl and alkyl glycidyl ether, or glycidyl esters, in particular the glycidyl esters of tertiary, highly branched, saturated monocarboxylic acids, which are sold under the trade name Versatic® are distributed by Deutsche Shell Chemie. Of these, the Versatic ^® acid glycidyl esters are particularly advantageous and are therefore used with very particular preference.

It is advantageous for the present invention that the polyols (C) described above are liquid at room temperature. Either single liquid hyperbranched compounds (C) or liquid mixtures of these compounds (C) can thus be used. This is particularly the case when hyperbranched compounds (C) are used which are solid as individual compounds because of their high molecular weight and / or their symmetry. The person skilled in the art can therefore select the corresponding hyperbranched compounds (C) in a simple manner.

The particularly preferred polyols (C) can be prepared by the customary and known methods of producing hyperbranched and dendrimeric compounds. Suitable synthetic methods are described, for example, in patent applications WO 93/17060 or WO 96/12754 or in the book by GR Newkome, CN Moorefield and F. Vögtle, "Dendritic Molecules, Concepts, Syntheses, Perspectives", VCH, Weinheim, New York, 1996 , described.

Further examples of suitable polyols (C) are hydroformylated and hydrogenated

Oligomers, obtainable by metathesis of acyclic monoolefins and cyclic monoolefins, hydroformylation of the resulting oligomers and subsequent hydrogenation, as described in German patent application DE 198 05 421 A1.

The polyols (C) of the type mentioned are obtained by oligomers of the formula TV,

wherein R - (-CH ₂ -) _W -, where the index w is an integer from 1 to 6, or

where W = -CH ₂ - or an oxygen atom;

R ¹⁰ , R ^π , R ¹² and R ¹³ independently of one another are hydrogen atoms or alkyl; and

Index v is an integer from 1 to 15;

hydroformylated and the resulting products containing aldehyde groups IN are reduced to the polyols IN (C), which are optionally partially or completely hydrogenated.

The index v in the formula IN stands for the number of divalent radicals R which are included in those of cyclic olefins such as, for example, cyclopropene, Cyclopentene, cyclobutene, cyclohexene, cycloheptene, norbornene, 7-oxanorbone or cyclooctene-derived oligomers NI were carried out by ring-opening metathesis reaction. The oligomer mixtures IV preferably have the largest possible proportion, such as, for example, at least 40% by weight (determined by the area integration of the gas chromatograms; device: Hewlett Packard; detector: flame ionization detector; column; DB 5.30 mx 0.32 mm, Assignment lμ; temperature program: 60 ° C 5 min, isothermal, heating rate 10 ° C / min max: 300 ° C), a value of v> 1. The value v and thus the degree of ring-opening metathesis can be influenced by the activity of the metathesis catalyst used.

The radicals R ¹⁰ , R ¹¹ , R ¹² and R ¹³ independently of one another represent hydrogen or alkyl, the term “alkyi” encompassing straight-chain and branched alkyl groups.

These are preferably straight-chain or branched C1-C15-alkyl, preferably Ci-do-alkyl, particularly preferably Ci-Cs-alkyl groups. Examples of alkyl groups are in particular methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl. n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-2-dimethylρroρyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, l-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylpropyl, 1,2,2-trimethylpropyl. 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl, etc.

The degree of branching xmd the number of carbon atoms in the terminal

Alkyl residues R ¹⁰ , R ¹¹ , R ¹² xmd R ¹³ depend on the structure of the acyclic

Monoolefins of the hydrocarbon mixture used and the activity of the catalyst, which determines the degree of cross-metathesis (self-metathesis) of the acyclic olefins influenced with the formation of structurally new olefins, into which cyclopentene is then formally inserted in the sense of a ring-opening metathesis polymerization.

Oligomer mixtures are usually used which have an increased proportion of oligomers with only one terminal double bond. The oligomer is preferably produced by mixing a hydrocarbon mixture from petroleum processing by cracking (C ₅ -clinitt) in a homogeneous or heterogeneous metathesis reaction implemented.

The metathesis reaction includes formal

a) the disproportionation of the acyclic monoolefins of the hydrocarbon mixture by cross metathesis,

b) the oligomerization of the cyclic monoelefin by ring-opening metathesis,

c) chain termination by reacting the oligomers from b) with an acyclic olefin of the hydrocarbon mixture or a product from a),

wherein steps a) and / or b) and / or c) can be carried out several times alone or in combination.

Step a) The cross metathesis of acyclic monoolefins will be explained using the example of the metathesis of 1-pentene and 2-pentene:

CH ₂ = CH-C ₃ H ₇

Propene + 1-butene + 2-hexene + 3 heptene

CH ₃ -CH = CH-C ₂ H ₅

By combining cross metathesis of different and self-methathesis of the same acyclic olefins, e.g. the self-metathesis of 1-pentene to give ethene and 4-octene and by running this reaction several times, a large number of monoolefins with different structures and number of carbon atoms are obtained, which form the end groups of the oligomers IV. The double bond fraction of the oligomers is also influenced by the proportion of cross-metathesis products, which increases with increasing activity of the catalyst used. For example, in the previously described self-methathesis of 1-pentene, ethene is released, which can optionally escape in gaseous form, a double bond equivalent being removed from the reaction. At the same time, the proportion of oligomers without terminal double bonds increases. So in the above example e.g. an oligomer without terminal double bonds is formed by insertion of cyclic monoolefins in 4-octene.

Step b)

The average number of insertions of the cyclic monoolefin into the growing chain in the sense of a ring-opening metathesis polymerization determines the average molecular weight of the oligomer mixture IN formed. Most preferably, the invention Nerfahr oligomer mixtures JN with an average molecular weight of at least 274 g per mole formed, which corresponds to an average number of three units of a cyclic monoolefin per oligomer.

Step c)

The chain termination takes place by reacting oligomers which still have an active chain end in the form of a catalyst complex (alkylidene complex) with an acyclic olefin, ideally recovering an active catalyst complex. The acyclic olefin can originate unchanged from the hydrocarbon mixture originally used for the reaction or can have been modified beforehand in a cross-metathesis according to stage a).

The process is generally suitable for the production of oligomers IV from hydrocarbon mixtures which contain acyclic and cyclic monoolefins. Mono-olefins such as Cyclobutene, cyclopentene, cyclohexene, cycloheptene, Νorbonen or 7-oxanorbonen, in particular cyclopentene. Variants of this method are described, for example, in the article by M. Schuster and S. Bleckert in Angewandte Chemie, 1997, volume 109, pages 2124 to 2144.

A hydrocarbon mixture obtained on a large industrial scale in petroleum processing is preferably used, which, if desired, can be subjected to a catalytic partial hydrogenation beforehand to remove dienes. For example, a mixture enriched in saturated and unsaturated Cs hydrocarbons (Cs cut) is particularly suitable for use in the present process. To obtain the Cs cut, pyrolysis gasoline obtained during steam cracking of Νaphtha can first be subjected to a selective hydrogenation in order to selectively convert the dienes and acetylenes contained into the corresponding ones To convert alkanes and alkenes xmd are then subjected to a fractional distillation, the C ₆ -C _{8 cut} , which contains the aromatic hydrocarbons, which is important for further chemical syntheses, and the C _{5 cut} used for the process according to the invention.

The C ₅ slurry generally has a total olefin content of at least 30% by weight, preferably at least 40% by weight, in particular at least 50% by weight.

Cs-hydrocarbon mixtures with a total cyclopentene content of at least 5% by weight, preferably at least 10% by weight, in particular at least 12% by weight, and generally not more than 30% by weight, preferably not more than 20, are suitable wt .-%.

In addition, suitable Cs-hydrocarbon mixtures have a pentene isomer content of the acycyclic monoolefins of at least 70% by weight, preferably at least 80% by weight, in particular at least 90% by weight.

The manufacturing process can also be a large-scale Cs cut with a total olefin content of e.g. 50 to 60% by weight, a cyclopentene content of e.g. 10 to 20% by weight and a proportion of pentene isomers of e.g. 33 to 43% by weight are carried out, the weight percentages adding up to 100% by weight.

According to a special embodiment, a hydrocarbon mixture is used in the production process, which comprises the Cs cut and a petroleum fraction (raffinate-2) containing acyclic C ₄ olefins. According to another special embodiment of the production process, a hydrocarbon mixture is used which comprises the Cs cut and ethene. This gives TV oligomer mixtures with an increased double bond content. This is achieved on the one hand by efhenolysis of the acyclic n- and iso-pentenes contained in the C ₅ -clinitt to shorter-chain α-olefins, such as propene and 1-butene, which, with cyclopentene in a ring-opening metathesis reaction with the formation of oligomers IN with one each terminal double bond react. In the presence of ethene, the self-metathesis of the acyclic olefins is also suppressed to form further efenes, such as the self-metathesis of 1-pentene to give ethene and 4-octene, which leads to products without terminal double bonds as a chain termination reagent. On the other hand, the double bond content is further increased by the ethenolysis of cyclopentene with ethene to 1,6-heptadiene. This results in oligomer sequences, each of which has two tenninal double bonds. When the oligomer mixtures IN thus obtained with an increased double bond content are used for functionalization, oligomer mixtures IN with an increased density of functionality normally result.

Suitable catalysts for metathesis are known in the prior art and include homogeneous and heterogeneous catalyst systems. In general, the catalysts suitable for the production process are based on a transition metal of the 6th, 7th or 8th subgroup of the periodic table, preference being given to using catalysts based on Mo, W, Re and Ru.

Suitable homogeneous catalyst systems are described, for example, by RH Grubbs in Comprehensive Organometallic Chemistry, Pergamon Press, Ltd., New York, Volume 8, page 499 ff. (1982), by RR Schrock in Accounts of Chemical Research, Volume 23, page 158 ff. ( 1990), in Angewandte Chemie, volume 107, pages 2179 ff. (1995), in Journal of the American Chemical Society, volume 118, Page 100 ff. (1996) and in Journal of the Chemical Society, Chemical Communications, page 1127 ff. (1995).

Suitable heterogeneous catalyst systems generally comprise a transition metal compound on an inert support which is capable of without

Cocatalyst, a catalytic active by reaction with the olefin ducts

To form alkylidene complex. Re ₂ O ₇ and CH ₃ ReO ₃ are preferably used.

Suitable inorganic carriers are the oxides customary for this, in particular silicon and aluminum oxides, aluminosilicates, zeolites, carbides, nitrides, etc. xmd their mixtures. Al ₂ O ₃ , SiO ₂ and mixtures thereof, optionally in combination with B ₂ O ₃ and Fe ₂ O ₃ , are preferably used as carriers.

The reaction temperature of the metathesis is from -20 to 200 ° C, preferably 0 to 100 ° C, in particular 20 to 80 ° C.

The metathesis can be carried out at an increased pressure of up to 20 bar, preferably up to 10 bar, or in particular at ambient pressure.

The process engineering execution of the manufacturing process can take place both continuously and discontinuously. Suitable reaction apparatuses are known to the person skilled in the art and are e.g. in Ullmann's Encyclopedia of Industrial Chemistry, Volume 1, page 743 ff. (1951). For discontinuous driving, these include e.g. Mixing kettle xmd for continuous ner driving e.g. Tubular reactors.

The metathesis mixture is broken up according to normal ner methods. This includes e.g. fractional distillation, if appropriate with reduced

Pressure, or separation at elevated temperatures and normal pressure in a falling film evaporator. Low-boiling fractions that are not yet contain converted olefins, if desired, be returned to the reaction apparatus. Disadvantageously, a further conversion of the olefins contained in the Cs cut to oligomers NI is achieved in the manufacturing process, so that the separated low boilers comprise a C ₅ hydrocarbon mixture with predominantly saturated cyclic and acyclic compounds.

Preferably, the iodine number of the oligomers is at least 250 g I _2/100 g NI oligomers, preferably at least 300 g I _2/100 g NI oligomers.

The average molecular weight of these oligomers IN derived from cyclic monoolefins, in particular cyclopentene, is at least 274 g / mol, which corresponds to an average conversion of three cyclopentene units per oligomer NI, in this case chain termination by an acyclic pentene (and not by a Cross metathesis product) is assumed.

To prepare the polyols IN (C), the oligomers IN described above in detail are hydroformylated in a customary and known manner. In general, the oligomers IN are reacted in the presence of suitable transition metal-containing catalysts with hydrogen and carbon monoxide under normal pressure or under elevated pressure at temperatures from 50 to 150 ° C. to products IN containing aldehyde groups.

An example of a suitable transition metal is rhodium.

The polyaldehydes IN thus obtained are isolated and in the usual and known

Reduced way to the reactive diluents to be used according to the invention.

All reducing agents with which aldehyde groups can be reduced to hydroxyl groups are suitable for this. Examples of more suitable Reducing agents are borohydrides such as sodium tefrahydroboranate or hydrogen in the presence of hydrogenation catalysts.

Examples of suitable hydroformylation and reduction processes are described in European patent application EP 0 502 839 A1.

The polyols IN (C) can be partially or completely hydrogenated in a customary and known manner. This includes the above-mentioned reducing agents.

The particularly advantageous polyols IN (C) have a hydroxyl number (OHZ) of 200 to 650, in particular 250 to 450. The number average molecular weight M _n determined with the aid of gel permeation chromatography with polystyrene as the internal standard is in the range from 400 to 1,000, in particular 400 to 600. The average molecular weight M _w determined with the aid of gel permeation chromatography and polystyrene as the internal standard is in the range from 600 to 2,000 , in particular 600 to 1,100. The inconsistency M _n M _w is 1.4 to 3, in particular 1.7 to 1.9.

Also suitable as polyols (C) are linear aliphatic polyester diols which have primary hydroxyl end groups. Polyester polols, in particular diols, they are known compounds and are sold, for example, by the King Industries company under the K-Flex® brand (e.g. K-Flex® 148 or 188).

Surprisingly, the above-described compounds (C) have an excellent effect as an adhesion promoter in the process according to the invention. The content of the above-described polyols (C) in the second clearcoats and / or the first clearcoats can vary very widely. The content depends in particular on the functionality of the polyols (C) on the one hand and on the amount and functionality of the binders (A) and the crosslinking agents (B) on the other. The content is preferably 1.0 to 70, preferably 2.0 to 60, particularly preferably 3.0 to 50, very particularly preferably 4.0 to 40 and in particular 5.0 to 30% by weight, in each case based on the Solids of the second and / or first clearcoats.

The first and / or the second clearcoats can also contain customary and known additives (D) in effective amounts. It is essential that they do not inhibit or completely prevent the crosslinking reactions and or reduce or eliminate the transparency of the clearcoats.

Examples of suitable additives (D) are organic and inorganic, transparent fillers, nanoparticles, reactive thinners curable with actinic radiation, low-boiling organic solvents and high-boiling organic solvents (“long solvents”), water, UV absorbers, light stabilizers, free radical scavengers, thermolabile free-radical initiators , Photoinitiators and initiators, other additional binders, additional crosslinking agents, such as those used in one-component or multicomponent systems, catalysts for thermal crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents and diperging agents, coupling agents, sealants, film-forming aids, Sag confrol agents (SCA), rheology control additives (thickeners), flame retardants, siccatives, drying agents,

Release agents, corrosion inhibitors, waxes, matting agents or precursors of organically modified ceramic materials. Examples of suitable organic and inorganic fillers (D) are those described in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 250 ff, "Füllstoffe", if they meet the above-mentioned conditions of use in clear lacquers.

Examples of suitable reactive thinners (D) curable with actinic radiation are those described in Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the keyword “reactive thinners”.

Examples of suitable low-boiling organic solvents (D) and high-boiling organic solvents (D) (“long solvents”) are ketones such as methyl ethyl ketone or methyl isobutyl ketone, esters such as ethyl acetate or butyl acetate, ethers such as dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Butylene glycol or

Dibutylene glycol dimethyl, diethyl or dibutyl ether, N-methylpyrrolidone or xylenes or mixtures of aromatic hydrocarbons such as Solventnaphtha® or Solvesso®.

Examples of suitable thermolabile free radical initiators (D) are organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.

Examples of suitable catalysts (D) for crosslinking are dibutyltin dilaurate, lithium decanoate or zinc octoate.

Examples of suitable photoinitiators and coinitiators (D) are described in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446. Examples of suitable other additional binders (D) which can also contribute complementary reactive functional groups (cf. the overview) are oligomeric and polymeric, linear and / or branched and / or block-like, comb-like and / or curable with amine radiation. or statistically constructed (co) polymers of ethylenically unsaturated monomers, or polyaddition resins xmd / or polycondensation resins, as described in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457: "Polyaddition" and "Polyadditionharze (polyadducts ) «, Pages 463 and 464:» polycondensates «,» polycondensation «and» polycondensation resins «, as well as pages 73 and 74:» binders «. Further examples of suitable other additional binders (D) are the poly (meth) acrylates or acrylate copolymers described in the patent DE 197 36 535 A1, polyesters, in particular those described in the patents DE 40 09 858 A1 or DE 44 37 535 A1 , Alkyds, acrylated polyesters, polylactones, polycarbonates, polyethers, epoxy amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters, polyurethanes and acrylated polyurethanes, such as those in the patents EP 0 521 928 A 1, EP 0 522420 A 1 , EP 0 522 419 A1, EP 0 730 613 A1 or DE 44 37 535 A1, or polyureas.

Examples of suitable additional crosslinking agents (D) which can also contribute complementary reactive functional groups (see the overview) are amino resins, as described, for example, in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29, "Aminoharze", the Textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff, the book "Paints, Coatings and Solvente", second completely revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A1 or EP-B-0 245 700 A1 as well as in the article by B. Singh and employees "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry", described in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207, compounds or resins containing carboxyl groups, as described, for example, in the patent specification DE 196 52 813 A 1, epoxy group-containing compounds or resins, as are described, for example, in the patents EP 0 299 420 A 1, DE 22 14 650 B1, DE 27 49 576 B1, US 4,091,048 A1 or US 3,781,379 A1, blocked polyisocyanates, as described, for example, in the patents US 4,444,954 A1, DE 196 17 086 A1, DE 196 31 269 A1, EP 0 004 571 A1 or EP 0 582 051 A1, and / or unblocked polyisocyanates such as they are described, for example, in the literature references cited above for waterborne basecoats.

Examples of suitable venting agents (D) are diazadicycloundecane or benzoin.

Examples of suitable emulsifiers (D) are nonionic emulsifiers, such as alkoxylated alkanols, polyols, phenols and alkylphenols, or anionic emulsifiers, such as alkali metal salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids and sulfonic acids of alkoxylated alkanols, polyols, phenols and alkylphenols.

Examples of suitable wetting agents (D) are siloxanes, fluorine-containing compounds, carboxylic acid half-esters, phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes.

Examples of suitable film-forming auxiliaries (D) are cellulose derivatives, such as cellulose acetobutyrate (CAB). Examples of suitable sag confrol agents (D) are ureas, modified ureas and / or silicas, as described, for example, in references EP 0 192 304 A1, DE 23 59 923 A1, DE 18 05 693 A1, WO 94/22968, DE 27 51 761 C 1, WO 97/12945 or "färbe + lack", 11/1992, pages 829 ff.

Examples of suitable rheology control additives (D) are those known from the patent specifications WO 94/22968, EP 0 276 501 A1, EP 0 249 201 A1 or WO 97/12945; crosslinked polymeric microparticles, as disclosed, for example, in EP 0 008 127 A1; inorganic layered silicates such as aluminum-magnesium-silicates, sodium-magnesium and

Montmorillonite-type sodium-magnesium-fluor-lithixime layered silicates; Silicas such as aerosils; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates;

An example of a suitable matting agent (D) is magnesium stearate.

Examples of suitable precursors (D) for organically modified ceramic materials are hydrolyzable organometallic compounds, in particular of silicon and aluminum.

Further examples of the additives (D) listed above and examples of suitable UV absorbers, radical scavengers, leveling agents,

Flame retardants, desiccants, drying agents, flame retardants, corrosion inhibitors and waxes (D) are described in detail in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998. The production of the second clearcoats to be used according to the invention has no special features, but is carried out in a customary and known manner by mixing the components described above in suitable mixing units such as stirred kettles, dissolvers, agitator mills or extruders.

For the process according to the invention it is particularly advantageous if the first and the second clearcoats, clearcoat layers and / or clearcoats contain reactive functional groups which can react with the complementary reactive functional groups in the other clearcoat layers or clearcoats.

According to the invention, this can be implemented in various preferred variants.

In a first particularly preferred variant of the process according to the invention, the first clearcoats, clearcoat layers and / or clearcoats and / or the second clearcoats, clearcoat layers and / or clearcoats contain at least one binder (A), at least one other additional binder (D), at least one crosslinking agent (B) and / or at least one other additional crosslinking agent (D) which have reactive functional groups which have complementary reactive functional groups of at least one binder (A), at least one other additional binder (D), at least one crosslinking agent (B) and / or at least one other additional crosslinking agent (D) of the second clearcoats, clearcoat layers and / or clearcoats can react.

Contained in a second particularly preferred variant of the method according to the invention (i) the first clearcoats, clearcoat layers and / or clearcoats have a stoichiometric excess of reactive functional groups of the binders (A) over the complementary reactive functional groups of the crosslinking agents (B), so that excess reactive functional groups of the first clearcoats, clearcoat layers and / or

Clearcoats can react with complementary reactive functional groups of the crosslinking agents (B) of the second clearcoats, clearcoat layers and / or clearcoats;

or included

(ii) the first clearcoats, clearcoat layers and / or clearcoats have a stoichiometric excess of reactive functional groups of the crosslinking agents (B) over the complementary reactive functional groups of the binders (A), so that excess reactive functional parts

Groups of the first clearcoats, clearcoat layers and / or clearcoats can react with complementary reactive functional groups of the crosslinking agents (B) of the second clearcoats, clearcoat layers and / or clearcoats.

In a third particularly preferred variant of the process according to the invention, the first and / or the second clearcoats contain at least one compound (C), with the exception of tricyclodecanedimethanol (TCD), which has reactive functional groups which react with the complementary reactive functional groups of the binders or of the crosslinking agents in the other clearcoat layers or clearcoats can react. The individual lacquers within the multi-layer clearcoats and color and or effect multi-layer lacquers produced according to the inventive method preferably have the following dry layer thicknesses:

Electro-dip coating: 5 to 40, preferably 10 to 35, particularly preferably 12 to 30 and in particular 15 to 25 μm,

Filler paint, stone chip protection primer or functional paint: 10 to 60, preferably 11 to 55, particularly preferably 12 to 50 and in particular 13 to 45,

Basecoat: 5 to 50, preferably 5 to 40, particularly preferably 5 to 30 and in particular 10 to 25 μm,

Combination effect layer: 10 to 100, preferably 15 to 90, particularly preferably 20 to 80, very particularly preferably 25 to 70 and in particular 30 to 60 μm,

- First and second clear coat in total: 10 to 100, preferably 15 to

80, particularly preferably 20 to 75 and in particular 25 to 70 μm, the layer thickness 2 of the second clearcoat preferably at least 5, preferably at least 10, particularly preferably at least 15, very particularly preferably at least 20 and in particular at least 25% of the total layer thickness 1 + 2 of the first and second clear coat.

In the multilayer coating according to the invention, the functional coating preferably has only a layer thickness of 20 to 50% of the total layer thickness of the functional coating and basecoat. The multi-layer clearcoats and color and / or effect multi-layer coatings according to the invention produced in the procedure according to the invention are highly scratch-resistant and very easy to polish. They also have a high level of hardness, flexibility, weather stability and chemical resistance, an excellent flow without surface defects, a very good interlayer stitching and an excellent overall optical impression.

Examples

Production Examples 1 to 7

1. The preparation of a methacrylate copolymer (A) for the second clear coat

In a laboratory reactor with a useful volume of 4 1, equipped with a stirrer, two dropping funnels for the monomer mixture resp. Initiator solution, nitrogen inlet tube, thermometer and reflux condenser, 640.6 g of a fraction of aromatic hydrocarbons with a boiling range of 158-172 ° C were weighed out. The solvent was heated to 140 ° C. After reaching 140 ° C., a monomer mixture of 597 g of ethyl hexyl acrylate, 173.2 g of hydroxyethyl methacrylate (corresponding to 13.5% by weight, based on (A)), 128.4 g of styrene and 385.2 g of 4-hydroxybutyl acrylate ( corresponding to 30 wt .-%, based on (A)) within 4 hours and an initiator solution of 25.6 g of t-butyl perethylhexanoate in 50 g of the aromatic solvent described evenly metered into the reactor within 4.5 hours. The metering of the monomer mixture and the initiator solution was started simultaneously. After the initiator metering had ended, the reaction mixture was kept at 140 ° C. for a further two hours and then cooled. The resulting one Polymer solution had a solids content of 65%, determined in a forced air oven at 130 ° C. for 1 h.

2. The production of a methacrylate copolymer (A) as a rubbing resin

5

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 tube, thermometer and reflux condenser were 720 g of a fraction of aromatic hydrocarbons with a boiling range of 158-172

Weighed in at 10 ° C. The solvent was heated to 140 ° C. After 140 ° C. had been reached, a monomer mixture of 450 g of 2-ethyl-hexyl methacrylate, 180 g of n-butyl methacrylate, 210 g of styrene, 180 g of hydroxyethyl acrylate (corresponding to 12% by weight, based on (A)), 450 g of 4- Hydroxybutyl acrylate (corresponding to 30% by weight, based on (A)) and 30 g of acrylic acid within 4 hours and one

15 mitiator solution of 150 g of t-butyl perethyl hexanoate in 90 g of the aromatic solvent described evenly metered into the reactor within 4.5 hours. The metering of the monomer mixture and the initiator solution was started simultaneously. After the initiator had ended, the reaction mixture was kept at 140 ° C. for two more hours and then

20 cooled. The resulting polymer solution had a solids content of 65%, determined in a forced air oven at 130 ° C. for 1 h, an acid number of 15 and a viscosity of 3 dPas (measured on a 60% solution of the polymer solution in the aromatic solvent described using an ICI Plate-cone viscometers at 23 ° C).

25

The production of a thixotropic paste

In a laboratory agitator mill from Vollrath, 800 g of regrind consisting of 323.2 g of the polyacrylate according to Preparation Example 2, 187.2 g of butanol,

30 200.8 g xylene and 88.8 g Aerosil® 812 (Degussa AG, Hanau), together with Weighed in 1100 g quartz sand (grain size 0.7 - 1 mm) and rubbed under water cooling for 30 minutes.

4. The preparation of a crosslinking agent

41.76 parts by weight of Vestanat ^R 1890 (isocyanurate based on isophorone diisocyanate from Creanova) and 20.76 parts by weight of solvent naphtha were weighed into a 41 stainless steel reactor with stirrer, reflux condenser, thermometer, oil heater and an inlet vessel for the blocking agent and weighed at 50 ° C. heated. In the course of four hours, 23.49 parts by weight of diethyl malonate, 5.81 parts by weight of ethyl acetoacetate and 0.14 part by weight of catalyst solution (natriximethylhexanoate) were metered in uniformly. After the feed had ended, a further 0.14 parts by weight of catalyst solution were added. The temperature was then raised to 80 ° C. When an isocyanate equivalent weight of 5900 to 6800 was reached, 0.9 part by weight of 1,4-cyclohexanedimethanol was added over 30 minutes at 80 ° C. with stirring. After an isocyanate equivalent weight of> 13,000 was reached, 5 parts by weight of n-butanol were added. The temperature was lowered to 50 ° C., and the resulting blocked polyisocyanate was dissolved with 2 parts by weight of n-butanol to a theoretical solids content of 68% by weight. The blocked polyisocyanate thus obtained had a solids content of 74.5% by weight (one hour; 130 ° C.) and an original viscosity of 41.6 dPas.

5. The preparation of a methacrylate copolymer (A) for the first clear coat

In a laboratory reactor with a useful volume of 4 1, equipped with a stirrer, two dropping funnels for the monomer mixture resp. Initiator solution Nitrogen inlet tube, thermometer and reflux condenser, 720 g of a fraction of aromatic hydrocarbons with a boiling range of 158-172 ° C were weighed out. The solvent was heated to 140 ° C. After reaching 140 ° C., a monomer mixture of 427.5 g of n-butyl acrylate, 180 g of n-butyl methacrylate, 450 g of styrene, 255 g of hydroxyethyl acrylate (corresponding to 17% by weight, based on (A)), 165 g of 4- Hydroxybutyl acrylate (corresponding to 11% by weight, based on (A)) and 22.5 g of acrylic acid within 4 hours and an initiator solution of 120 g of t-butyl perethylhexanoate in 90 g of the aromatic solvent described within 4.5 hours evenly in the Reactor metered. The metering of the monomer mixture and the initiator solution was started simultaneously. After the initiator metering had ended, the reaction mixture was kept at 140 ° C. for two more hours and then cooled. The resulting polymer solution had a solids content of 60%, determined in a forced air oven for 1 h 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 on the 60% polymer solution in the aromatic solvent described using an ICI plate-cone viscometer at 23 ° C.).

6. The production of a first one-component clear coat

A first one-component clearcoat was prepared from the components listed in Table 1 by mixing.

Table 1: Composition of the first one-component clearcoat

Ingredients parts by weight

Copolymer according to Preparation Example 5 43.4

Crosslinking agent 9.0 according to preparation example 4

Commercial butanol-16.0 etherified melamine-formaldehyde resin (60% in

Butanol / xylene)

Setalux® C91756 13.5

(Commercial

Akzo thixotope)

Substituted hydroxy-0.6 phenyltriazine (65% in xylene)

(Cyagard® 1164 L)

Amino ether modified 0.8

-2,2,6,6-tetramethylpiperydinyl ester (Tinuvin® 123 from Ciba)

Byk® 390 (Byk Chemie) 0.05

Byk® 310 (Byk Chemie) 0.15

Tego® LAG 502 0.2

Butanol 11.4 Solventnaphtha® 2.5

Xylene 0.9

Butyl diglycol acetate 1.5

K-Flex® 188 from the company

King Industries 6.0

TOTAL 106

The first clear coat had a run-out time of 51.5 s in the DIN4 cup at 21 ° C. For the application, it was set to an outflow time of 28 s with 10 parts by weight of a thinner (organic solvent mixture).

7. The production of a second clear coat

The second clear coat was prepared by mixing the ingredients shown in Table 2.

Table 2: Composition of the second clear coat

Ingredients parts by weight

Binder copolymer according to

Preparation Example 1 50.0

Thixotropy aste according to preparation example 3 3.0 crosslinking agent

TACT 26.6

Other ingredients Substit. Hydroxyphenyl-1.0 benzotriazole (95% in

Xylene) (Tinuvin® 292 from the company

Ciba)

A ether-modified 1,2 -2,2,6,6-tetramethylpiperydinyl ester (Tinuvin® 400 from Ciba)

Commercial solution of a 1.4 polyether modified polydimethylsiloxane (5% in xylene)

Byk® 310 (Byk Chemie)

Butyl diglycol acetate 5.5

Butyl glycol acetate 5.5

Solvesso® 150 5.8

TOTAL 100

TACT = commercial tris (alkoxycarbonylamino) triazine from the company

CYTEC

The clear coat of coating had a spill time of 28 s in the DIN4 cup at 21 ° C.

example 1 The production of a color and effect-giving multi-layer coating in the procedure according to the invention

To produce the test panels, an electro dip coating (dry layer thickness 22 μm) and a water filler (FU63-9400 from BASF Coatings AG) were applied and baked in (dry layer thickness 30 μm). The electrodeposition paint was baked at 170 ° C. for 20 minutes and the filler at 160 ° C. for 20 minutes. A blue waterborne basecoat (water percolor basecoat FW 05-513P from BASF Coatings AG was then applied with a layer thickness of 15-18 μm and flashed off at 80 ° C. for 10 minutes.

The first clearcoat material from Preparation Example 6 (see Table 1) was then applied wet-on-wet and baked at 135 ° C. for 30 minutes, so that dry film thicknesses of 35 μm resulted.

The test panels thus obtained were overcoated without intermediate sanding with the second clearcoat of Preparation 7 (see Table 2). The resulting clear lacquer layers were baked at 140 ° C. for 20 minutes, so that dry layer thicknesses of 20 μm resulted.

The resulting multi-layer coating showed a very high scratch resistance, very good polishability, an excellent overall optical impression, a very good flow, a very high gloss, a high level of hardness and flexibility, even without intermediate sanding, a very good intermediate adhesion and no whitening after exposure in a constant condensation water climate , a very good stability against chemicals, bird droppings and tree resin and a high weather stability.

Claims

claims

1. Process for the production of a multilayer clearcoat on a primed or unprimed substrate

(III) application of at least a second, and different Klaiiacks material material from the first clear coat

(IV) joint curing of the first and second clear coat (s) or - alternatively - curing of the second clear coat (s) on its own

characterized in that the second clearcoats as binders

(A) at least one siloxane group-free (meth) acrylate copolymer which, based on the siloxane group free

(Meth) acrylate copolymer (A), up to 90% by weight of hydroxyl-containing olefinically unsaturated monomers (a), in copolymerized form, of which (al) 10 to 90% by weight, based on the (meth) acrylate copolymer (A) free of siloxane groups, 4-

Hydroxybutyl (meth) acrylate xmd / or 2-alkyl-propane-l, 3-diol-mono (meth) acrylate and

(a2) 0 to 45% by weight, based on the siloxane group-free (Mefh) acrylate copolymer (A), are other hydroxyl-containing olefinically unsaturated monomers;

and as a crosslinking agent

(B) at least one tris (alkoxycarbonylamino) triazine

included, the first and the second clearcoats none

Tricyclodecanedimethanol (TCD) included.

2. Process for producing a color and / or effect multi-layer coating on a primed or unprimed subsfrat

(I) application of at least one color and / or effect paint to the primed or unprimed subsfrat,

(II) drying of the resulting coloring and / or effect

Lacquer layer without hardening it, or - alternatively - hardening of the color and / or effect lacquer layer, which results in the color and or effect lacquer coating, (III) application of at least a first clear lacquer to the color and / or effect lacquer layer or coating,

(IV) drying the first clear lacquer layer (s) without hardening it, or - alternatively - hardening the first clear lacquer layer (s) alone or together with the coloring and / or effect-imparting lacquer layer,

(V) application of at least a second clear lacquer materially different from the first clear lacquer to the first clear lacquer layer or the first clear lacquer and

(VI) Hardening of the second clear coat layer (s) on its own, together with the first clear coat layer (s) or together with the coloring and / or effect coat layer and with the first clear coat layer (s), whereby the color and / or effect-giving multi-layer coating resulted,

characterized in that the second clearcoats as binders

(Meth) acrylate copolymer (A), up to 90% by weight of hydroxyl-containing olefinically unsaturated monomers (a), in copolymerized form, of which

(al) 10 to 90% by weight, based on the (meth) acrylate copolymer (A) free of siloxane groups, 4-

Hydroxybutyl (meth) acrylate xmd / or 2-alkyl-propane-l, 3-diol-mono (meth) acrylate and (a2) 0 to 45% by weight, based on the siloxane-free (meth) acrylate copolymer (A), represent other hydroxyl-containing olefinically unsaturated monomers;

and as a crosslinking agent

(B) at least one tris (alkoxycarbonylamino) triazine

3. The method according to claim 1 or 2, characterized in that the first and the second clearcoats, clearcoat layers and / or clearcoats contain reactive functional groups which can react with the complementary reactive functional groups in the other clearcoat layers or clearcoats.

4. The method according to claim 3, characterized in that the first clearcoats, clearcoat layers and / or clearcoats and or the second clearcoats, clearcoat layers and / or clearcoats at least one binder (A), at least one other additional binder (D), at least one crosslinking agent (B) and / or at least one other additional crosslinking agent (D) which have reactive functional groups which have complementary reactive functional groups of at least one binder (A), at least one other additional binder (D), at least one crosslinking agent (B) and / or at least one other additional crosslinking agent (D) of the second clearcoats, clearcoat layers and / or clearcoats can react.

5. The method according to claim 3, characterized in that

(i) the first clearcoats, clearcoat layers and / or clearcoats have a stoichiometric excess of reactive functional groups of the binders (A) over the complementary reactive functional groups of the crosslinking agents (B), so that excess reactive functional groups of the first

Clearcoats, clearcoat layers and / or clearcoats can react with complementary reactive functional groups of the crosslinking agents (B) of the second clearcoats, clearcoat layers and / or clearcoats; or

(ii) the first clearcoats, clearcoat layers and / or clearcoats have a stoichiometric excess of reactive functional groups of the crosslinking agents (B) over the complementary reactive functional groups of the binders (A), so that excess reactive functional groups of the first

Clearcoats, clearcoat layers and / or clearcoats can react with complementary reactive functional groups of the crosslinking agents (B) of the second clearcoats, clearcoat layers and or clearcoats.

6. The method according to any one of claims 1 to 5, characterized in that the first and / or the second clearcoats

(C) contain at least one compound, except tricyclodecanedimethanol (TCD), that is reactive has functional groups which react with the complementary reactive functional groups of the binders or the crosslinking agents in the respective other clearcoat layers or clearcoats.

7. The method according to any one of claims 1 to 6, characterized in that the outermost surface of the first clear coat (s) is treated physically and / or chemically before the application of the second clear coat.

8. The method according to claim 7, characterized in that the physical treatment comprises irradiation with actinic Sfrahlxmg, treatment with ultrasound and / or heat and / or mechanical treatment and chemical treatment, the etching with suitable chemicals and / or flame treatment.

9. The method according to any one of claims 1 to 8, characterized in that the first clearcoat is curable physically or thermally and / or with actinic radiation and that the second clearcoat is curable thermally or thermally and with actinic radiation (dual cure).

10. The method according to any one of claims 2 to 9, characterized in that the coloring and / or effect coating is a basecoat or a combination effect layer.

11. The method according to any one of claims 1 to 10, characterized in that the primer is produced by applying an electrocoat on the subsfrate and the resulting electrocoat layer on its own or together with at least one other existing lacquer layer hardens, which results in the electrophoretic coating.

12. The method according to claim 11, characterized in that a filler is applied to the electrocoat or the electrocoat and the resulting filler layer on its own, together with the electrocoat, together with at least one further paint layer thereon or together with the electrocoat and at least one another layer of lacquer thereon hardens, causing the filler coating, the

Stone chip protection primer or the functional layer results.

13. The method according to any one of claims 1 to 12, characterized in that as substrates motor vehicle bodies or parts thereof, buildings in the interior and exterior, doors, windows, furniture and industrial

Components, including coils, containers and electrical components, are used.

14. The method according to any one of claims 1 to 13, characterized in that hydroxyl groups are used as reactive functional groups and alkoxycarbonylamino groups (-NH-C (O) -OR) as complementary reactive functional groups.

15. The method according to claim 14, characterized in that the hydroxyl groups in at least one polylol (C) and the

Alkoxycarbonylamino groups in at least one

Present tris (alkoxycarbonylamino) triazine (B).

16. The method according to claim 15, characterized in that as polyols (C) hyperbranched compounds with a tefrafunctional zenfral group, derived from ditrimethylolpropane, diglycerol and / or ditrimethylolethane, or a tefrafunctional central group of the general formula III,

C [-A _q -X-] _m [-A _r -X-] _n [-A _s -X-] ₀ [-A _t -X-] _p (III),

where the indices and the variables have the following meaning:

m + n + o + p = 4; with m = an integer from 1 to 3 and n, o and p = 0 or an integer from 1 to 3;

q, r, s and t = an integer from 1 to 5, where q> r, s, t, in particular q> r, s, t;

X = -O-, -S- or -NH-;

A = -C (R ⁸ ) ₂ -; with R ⁸ = -H, -F, -Cl, -Br, -CN, -NO ₂ , Ci-CrAlkyl- or -

Haloalkyl or CrCralkoxy radical or - for q, r, s and / or t = at least 2 - R ⁸ = C ₂ -C ₄ alkanediyl and / or oxaalkanediyl radical which has 2 to 5 carbon atoms and / or an oxygen atom -O- , which bridges 3 to 5 carbon atoms of the radical -A-;

cyclic and / or acyclic Cg-Ci _δ alkanes which are functionalized with at least two hydroxyl groups; Polyols obtainable by using oligomers of the formula IN,

wherein

R ⁹ = - (- CH ₂ -) _W -, where the index w is an integer from 1 to

6 means or

wherein W = -CH ₂ - or an oxygen atom;

R ¹⁰ , R ⁿ , R ¹² and

R ¹³ independently of one another = hydrogen atoms or alkyl; and

Index v = an integer from 1 to 15;

hydroformylated and the resulting products are hydrogenated; and or

linear alphatic polyester polyols with primary hydroxyl end groups

be used.

17. Use of hyperbranched compounds with a tefrafunctional zenfral group, derived from ditrimethylolpropane, diglycerol and / or ditrimethylolethane, or a tefrafunctional zenfral group of the general formula III,

C [-Aq-X-lm lA _r -X-] n [-A _s -X-] ₀ [-A _t -X-] _p (III),

where the indices and the variables have the following meaning:

X = -O-, -S- or -NH-;

A = -C (R ⁸ ) ₂ -; with R ⁸ = -H, -F, -Cl, -Br, -CN, -NO ₂ , Q-Ca-alkyl- or -

Haloalkyl or Ci-CrAlkoxy radical or - for q, r, s and / or t = at least 2 - R ⁸ = C ₂ -C ₄ alkanediyl and / or oxaalkanediyl, which has 2 to 5 carbon atoms and or an oxygen atom -O -, which bridges 3 to 5 carbon atoms of the radical -A-;

cyclic and / or acyclic C ₉ -C ₁₆ alkanes which are functionalized with at least two hydroxyl groups; Polyols obtainable by using oligomers of the formula IN,

R ^U R ¹⁰ C = [= CH-R ⁹ -CH =] _V = CR ¹³ R ¹² (IN),

wherein

R ^y - (- CH ₂ -) _W -, in which the index w is an integer from 1 to 6, or

wherein W = -CH ₂ - or an oxygen atom;

R ¹⁰ , R ^π , R ¹² and R ¹³ independently of one another ^: hydrogen atoms or alkyl; and

Index v = an integer from 1 to 15;

hydroformylated and the resulting products are hydrogenated; and / or from

linear alphatic polyester polyols with primary hydroxyl end groups

as an adhesion promoter in multi-layer clear coats, especially in the context of color and / or effect multi-coat coats.

18. Use according to claim 17, characterized in that the clearcoats can be produced by the method according to one of claims 1 to 16.

19.Multi-layer clearcoat containing at least one first clearcoat and at least one second clearcoat different in terms of material, can be produced by applying at least one second clearcoat to the first clearcoat layer (s) or the first clearcoat (s) and the resulting one ^) second (s) clear coat layer (s) with the first clear coat layer (s) and with at least one possibly underlying underlying coat coat or the second clear coat layer (s) cures on its own, characterized that the second clear coats as binders

(A) at least one siloxane group-free (Mefh) acrylate copolymer which, based on the siloxane group-free

(Meth) acrylate copolymer (A), containing up to 90% by weight of hydroxyl-containing olefinically unsaturated monomers (a) in copolymerized form, of which

Hydroxybutyl (meth) acrylate and / or 2-alkyl-propane-l, 3-diol-mono (meth) acrylate and

(a2) 0 to 45% by weight, based on the siloxane-free (meth) acrylate copolymer (A), represent other hydroxyl-containing olefinically unsaturated monomers; and as a crosslinking agent

(B) at least one tris (alkoxycarbonylamino) triazine

contain, the clearcoats, clearcoat layers and clearcoats contain no tricyclodecanedimethanol (TCD).

20. Multi-layer clear coat according to claim 19, characterized in that it can be produced by the method according to one of claims 1 to 16.