WO2005116117A1 - Integrated dual-cure coating material system and use thereof for the internal and external coating of complex shaped three-dimensional substrates - Google Patents

Abstract

The invention relates to an integrated dual-cure coating material system, comprising two dual-cure multi-component systems (A) and (B), made from mostly or entirely the same components, each with two layered components separated from each other, whereby (I) one component comprises (i.1) isocyanate reactive functional groups, (i.2) reactive functional groups, containing at least one bond which may be activated by actinic radiation, (i.3) plasticising structural units, with a component of three-dimensional networks which lower the glass transition temperature Tg thereof and/or (i.4) hardening structural units, with a component of three-dimensional networks which increase the glass transition temperature Tg thereof and (II) a component comprising (ii.1) free isocyanate groups, (ii.2) reactive functional groups, containing at least one bond which may be activated by actinic radiation, (ii.3) plasticising structural units, with a component of three-dimensional networks which lower the glass transition temperature Tg thereof and/or (ii.4) hardening structural units, with a component of three-dimensional networks which increase the glass transition temperature Tg thereof and whereby the dual cure coating material system (B) has (a) a lower total content of reactive functional groups with bonds which may be activated by actinic radiation and/or (b) a lower total content of hardening structural units with a component of three-dimensional networks which increase the glass transition temperature Tg thereof, than the dual cure coating material system (A) and use thereof.

Description

Integrated dual-cure coating material system and its use for the inner and outer coating of complex shaped three-dimensional substrates

This application takes priority from DE 10 2004026423.6-43.

The present invention relates to a new integrated dual-cure coating material system. The present invention also relates to the use of the new integrated dual-cure coating material system for the interior and exterior coating of complexly shaped three-dimensional substrates. Furthermore, the present invention relates to a new method for the inner and outer coating of complex shaped three-dimensional substrates with dual-cure coating materials. Last but not least, the present invention relates to complex shaped three-dimensional substrates that have been coated inside and out using the new integrated dual-cure coating material system.

The high-quality coating or varnishing of complex three-dimensional substrates such as motor vehicle bodies, in particular car bodies, is naturally complex and poses numerous technical problems. Thus, the coloring and / or effect coating of motor vehicle bodies, in particular car bodies, nowadays preferably consist of several layers of paint that are applied one above the other and have different properties.

For example, an electrodeposited electrodeposition coating (ETL) as a primer, a primer filler or stone chip protection primer, a basecoat 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 of the surface and, due to its elasticity, ensures resistance to stone chips. If necessary, the filler coating 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 referred to collectively as topcoat. In addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 49 and 51, "Automotive paints" is referred to below. These multi-layer coatings are referred to as coloring and / or effect-giving multi-layer coatings.

Recently, clear coats in particular have been produced from clear coats that are thermally curable and with actinic radiation. Here and below, actinic radiation includes electromagnetic radiation, such as near infrared, visible light, UV radiation or X-rays or gamma radiation, in particular UV radiation, and corpuscular radiation, such as electron radiation, proton radiation, alpha radiation, beta radiation or neutron radiation, in particular 10 electron radiation understand. The combined hardening by heat and actinic radiation is also called dual-cure by experts.

Dual-cure coating materials, in particular dual-cure clearcoats, have the significant advantage that they are more complex in shape even in the shadow zones

15 three-dimensional substrates, such as car bodies, radiators or electrical winding goods, even without optimal, in particular complete, illumination of the shadow zones with actinic radiation to provide coatings whose application properties match that of the coatings outside the shadow zones. This will make those in the shadow zones

20 coatings are also no longer easily damaged by mechanical and / or chemical influences, which can occur, for example, in the line when installing further components of motor vehicles in the coated bodies.

On the other hand, curing with actinic radiation can compensate for incomplete thermal curing if, for example, the dual-cure coating materials, because of the temperature sensitivity of the coated substrates, must not be heated to the temperatures necessary for the rapid course of the thermal crosslinking reactions.

30 dual-cure coating materials and their use for producing high-quality color and / or effect multi-layer coatings are known, for example, from patent applications DE 42 15 070 A1, DE 198 18 735 A1, DE 199 08 018 A1, DE 199 30 665 A. 1, DE 199 30 067 A1, DE 199 30 664 A1, DE 199 24 674 A1, DE 199 20 799 A1, DE 199 58 726 A1, DE 199 61 926 A1, DE 100 42 152 A1 , DE 100 47

35 989 A1. DE 100 55 549 A1, DE 101 29 970 A1, DE 102 02 565 A1, DE 102 04 114 A1, EP 0 928 800 A1 or EP 0 952 170 A1 or the patent DE 101 29 660 C1 known. With all the advantages that the dual-cure coating materials undoubtedly offer, problems often arise in practice when coating or painting the very complex car bodies. Adequate radiation in the shadow areas, e.g. under the tailgate and the bonnet, as well as in the area of the door sills, the trunk and the inside of the door and the inside of the window, is often not as high as desired, even when doors, flaps and hoods are placed far away possible. A sufficient application-related property profile must therefore be set or forced in the shadow zones via thermal crosslinking, but this can lead to problems, especially if plastic body parts are to be painted, which must not be exposed to high temperatures. In other words, there is the problem that thermal crosslinking cannot compensate for the deficits of insufficient radiation curing to the required extent.

A conceivable solution to this problem is to use a special coating material for the interior (interior varnish) that is particularly reactive in terms of thermal crosslinking. Highly reactive coating materials of this type have been known for a long time and usually contain binders with isocyanate-reactive groups and polyisocyanates (two-component systems) as crosslinking agents. This could achieve that the application-related property profile of the coating in the shadow zones reaches the application-related property profile of the coating in the areas that have been thermally hardened with a sufficient dose of radiation.

However, it has been shown that in the areas of the bodies in which the interior paint and exterior paint, ie. H. the coating material for the outdoor area, overlap, serious paint defects occur. These are caused in particular by the incompatibility of the interior paint and exterior paint in wet-on-wet application. This incompatibility means that the spray mist of one lacquer is not absorbed by the wet film of the other lacquer.

The present invention was therefore based on the object of providing a new integrated dual-cure coating material system which no longer has the disadvantages of the prior art, but rather the coating of complexly shaped three-dimensional substrates, in particular motor vehicle bodies. especially car bodies, easily permitted inside and outside and supplies a coating that also has an application-related property profile in the interior, which at least matches the application-related property profile of the coating in the outside area, which could be cured with a sufficient radiation dose. In the areas in which the coating of the interior (interior painting) merges with that of the exterior (exterior painting), there should no longer be any defects in the coating (paint defects).

Accordingly, the new integrated dual-cure coating material system has been found which comprises at least two dual-cure multicomponent systems (A) and (B) which consist predominantly or entirely of the same constituents and each comprise at least two components which are stored separately from one another, whereby

(I) at least one component

(i.1) isocyanate-reactive functional groups and (i.2) reactive functional groups containing at least one bond which can be activated with actinic radiation, (i.3) flexibilizing structural units which, as components of three-dimensional networks, lower their glass transition temperature Tg, and / or (i .4) Hardening structural booklets which, as a component of three-dimensional networks, increase their glass transition temperature Tg, and

(II) at least one component (ii.1) free isocyanate groups, (ii.2) reactive functional groups containing at least one bond which can be activated with actinic radiation and (ii.3) flexibilizing structural units which, as components of three-dimensional networks, lower their glass transition temperature Tg, and / or (ii.4) hardening structural units which, as a component of three-dimensional networks, increase their glass transition temperature Tg, contains

and wherein the dual-cure coating material system (B)

(a) overall a lower content of reactive functional groups, containing at least one bond that can be activated with actinic radiation, and / or

(b) overall a higher content of hardening structural units which, as a component of three-dimensional networks, increase their glass transition temperature Tg,

than the dual-cure coating system (A).

The new integrated dual-cure coating material system is referred to below as the “system according to the invention”.

In addition, the new use of the system according to the invention for the interior and exterior coating of complexly shaped three-dimensional substrates has been found, which is referred to below as “use according to the invention”.

Furthermore, the new process for the inner and outer coating of complex shaped three-dimensional substrates was found, which comprises the use according to the invention and in which one

(1) at least one dual-cure coating material (A) and (B) each from at least one dual-cure multicomponent system (A) and (B) by mixing at least one component (I) and (II) and homogenizing the resulting mixture and

(2) the outside of the three-dimensional substrate is coated with the dual-cure coating material (A) and the inside of the three-dimensional substrate with the dual-cure coating material (B), after which

(3) the resulting coatings cure thermally and with actinic radiation, resulting in the interior and exterior coatings. In the following, the new process for the inner and outer coating of complex shaped three-dimensional substrates is referred to as the “process according to the invention”.

Further subjects of the invention are evident from the description.

In view of the prior art, it was surprising and unforeseeable for the person skilled in the art that the object on which the present invention was based could be achieved with the aid of the system according to the invention, the use according to the invention of the method according to the invention.

In particular, it was surprising that the system according to the invention no longer had the disadvantages of the prior art, but rather, within the scope of the use according to the invention, the coating of complexly shaped three-dimensional substrates, in particular motor vehicle bodies, especially passenger car bodies, in the interior and exterior using the method according to the invention easily permitted and delivered coatings that also had an application-related property profile in the interior, which at least matched the application-related property profile of the coatings in the outside area, which could be cured with a sufficient radiation dose. In the areas in which the coatings of the interior (interior painting) merged with those of the exterior (exterior painting), there were no more defects in the coatings (paint defects).

The system according to the invention comprises at least two, in particular two, dual-cure multicomponent systems (A) and (B), in particular dual-cure two-component systems (A) and (B).

The dual-cure multicomponent systems (A) and (B) consist predominantly or entirely of the same components. "Predominantly" means that the dual-cure multicomponent systems (A) and (B) differ from one another in at most three and preferably at most in two components, and in particular only in one component.

Each of the dual-cure multicomponent systems (A) and (B) comprises at least two, in particular two, components (I) and (II), which are used to produce the dual-cure Coating materials (A) and (B) are stored separately from one another in the context of the use according to the invention.

In each dual-cure multicomponent system (A) and (B), the at least one, in particular the one, component (I) contains isocyanate-reactive functional groups (i.1), which preferably consist of the group consisting of hydroxyl groups, thiol groups and primary and secondary amino groups, especially hydroxyl groups, can be selected.

It also contains reactive functional groups (i.2) which contain at least one, in particular one, bond which can be activated with actinic radiation. Examples of suitable bonds which can be activated with actinic radiation and reactive functional groups (i.2) which they contain are known from German patent application DE 101 29 970 A1, page 8, paragraphs [0059] to [0061]. In particular, acrylate groups (i.2) are used.

They also contain flexibilizing structural units (i.3), which lower the glass transition temperature Tg as components of three-dimensional networks. Examples of suitable flexibilizing structural units (i.3) are also known from German patent application DE 101 29 970 A1, page 8, paragraph [0064], to page 9, paragraph [0072].

Last but not least, they contain hardening structural units (i.4) which, as part of three-dimensional networks, increase their glass transition temperature Tg. Examples of suitable hardening structural units (i.4) are also from German patent application DE 101 29 970 A1, page 9, paragraph [0079], to page 10, paragraph [0085].

The »three-dimensional networks« exist in the thermoset solids of the coatings or coatings (A) and (B) made from the dual-cure multicomponent systems (A) and (B) and form the main component or the sole component of these coatings or coatings ( A) and (B). The glass transition temperature Tg of the coatings or coatings (A) and (B) is therefore largely determined by the material composition and structure of the three-dimensional networks. The material composition and the structure of the three-dimensional networks are in turn set by selecting the components of the dual-cure multicomponent systems (A) and (B). Component (I) preferably contains at least one polymeric and / or oligomeric binder; in particular, it contains two oligomeric and / or polymeric binders, part or all of the isocyanate-reactive functional groups (i.1) being contained in the binder or the binders.

The binders can contain reactive functional groups (i.2). However, they are preferably free of these.

The binder contains structural units (i.3) and (i.4) or consists of these. The structural units (i.3) and (i.4) are used in a ratio that the binders contribute to the setting of the desired glass transition temperature Tg after their incorporation into the three-dimensional networks.

Examples of suitable binders and the amounts in which they are preferably used in components (I) are known from German patent application DE 101 29 970 A1, page 3, paragraph [0018], to page 6, paragraph [0041] , In particular, (meth) acrylate copolymers are used. These preferably have a glass transition temperature of from - 50 ° C. to + 110, preferably - 30 to + 80, preferably - 15 to + 70, particularly preferably - 15 to + 50, very particularly preferably - 15 to + 40 and in particular - 15 to + 30 ° C. Their acid number depends primarily on whether they are to be used in aqueous coating materials according to the invention; the acid number is preferably 5 to 100 mg KOH / g. Likewise, their content of isocyanate-reactive groups, especially hydroxyl groups, can vary widely; their hydroxyl number is preferably 20 to 300, preferably 30 to 250, particularly preferably 40 to 200, very particularly preferably 60 to 190, in particular 80 to 180 mg KOH / g.

Component (I) preferably contains at least one, in particular one, low molecular weight and / or oligomeric constituent, the at least one reactive functional group (i.2) and preferably at least two, preferably at least three and in particular at least four reactive functional groups (i.2 ) contains. In addition, this constituent can also contain at least one, in particular one, isocyanate-reactive functional group (i.1). The majority or all of the reactive functional groups (i.2) of component (I) are preferably contained in this constituent. Examples of suitable constituents of this type and the amounts in which they are preferably used in components (I) are from the German patent application DE 101 29 970 A1, page 11, paragraphs [0101] to [0103].

In addition, component (I) can also contain customary and known paint additives, as described, for example, in German patent application DE 101 29 970 A1, page 12, paragraph [0123]. In particular, shear thinning Sag control agents (SCA) are used.

Component (I) may also contain customary and known pigments, as described, for example, in German patent application DE 101 29 970 A1, page 11, paragraph (0104] to page 12, paragraph [0121] In particular, nanoparticles are used.

The production of component (I) has no special features in terms of method, but instead takes place by mixing the components described above, mixing and homogenizing the resulting mixtures using customary and known mixing methods and devices such as stirred kettles, stirred mills, extruders, kneaders, Ultraturrax, in-line, Dissolvers, static mixers, gear rim dispersers, pressure relief nozzles and / or microfluidizers, preferably with the exclusion of actinic radiation.

In each dual-cure multicomponent system (A) and (B), the at least one, in particular one, component (II) contains free isocyanate groups (ii.1). In addition, it can to a lesser extent still contain blocked isocyanate groups, as described, for example, in German patent application DE 101 29 970 A1, the paragraph [0058] spanning pages 7 and 8.

Component (II) also contains reactive functional groups (ii.2) containing at least one bond which can be activated with actinic radiation. Examples of suitable reactive functional groups (ii.2) are the reactive functional groups (i.2) described above.

Component (II) also contains flexible structural units (ii.3) which, as a component of three-dimensional networks, lower their glass transition temperature Tg. Examples of suitable flexibilizing structural units (ii.3) are the structural units (i.3) described above. Last but not least, component (II) contains hardening structural units (ii.4) which, as part of three-dimensional networks, increase their glass transition temperature Tg. Examples of suitable hardening structural units (ii.4) are the structural units (i.4) described above.

Component (II) preferably contains at least one constituent which has features (ii.1) and (ii.2), or consists thereof.

Examples of suitable components (II) and suitable components of features (ii.1) and (ii.2), processes for their preparation and the amounts in which they are preferably used in the dual-cure multicomponent systems (A) and (B) can be known in detail from German patent application DE 101 29 970 A1, page 6, paragraph [0042], to page 11, paragraph [0100].

In addition, component (II) may contain the paint additives described above, provided that these do not react with the isocyanate groups (ii.1) under the conditions of production, storage and use of component (II).

The production of component (II) likewise does not require any special features in terms of method, but rather the devices and methods described above can be used.

It is essential for the system according to the invention that the dual-cure coating material system (B) overall has a lower content of reactive functional groups (i.2) + (ii.2) and / or overall a higher content of hardening structural units (i .4) + (ii.4) as the dual-cure coating system (A).

The system according to the invention serves for the inner and outer coating of complex shaped three-dimensional substrates. Examples of complexly shaped three-dimensional substrates are bodies of means of transportation, including means of transportation operated with motor power and / or muscle power, such as cars, commercial vehicles, buses, motorcycles, bicycles, rail vehicles, watercraft and aircraft, and parts thereof, structures and parts thereof, doors, windows, Furniture as well as mechanical, optical and electronic components. This is particularly useful System according to the invention of the inner and outer coating of motor vehicle bodies, especially car bodies.

In the context of the use according to the invention, the dual-cure coating materials (A) and (B) are made from the dual-cure coating material systems (A) and (B) by mixing the above-described components (I) and (II) and homogenizing the resulting Mixtures made.

The resulting dual-cure coating materials (A) and (B) are preferably conventional coating materials containing organic solvents, aqueous coating materials or essentially or completely solvent-free and water-free liquid coating materials (100% systems).

They can be used for the production of opaque coatings or paints such as filler paints, basecoats and solid-color paints. In particular, they are outstandingly suitable for the production of transparent, single- and multi-layer clear coats, as well as clear coatings of multi-layer, color and / or effect-giving, electrically conductive, magnetically shielding and / or fluorescent coatings, especially according to the wet-on-wet method a basecoat, in particular a waterborne basecoat, is applied to the surface of a substrate, after which the resulting basecoat film is dried without curing and covered with a clearcoat film. The two layers are then hardened together.

In terms of method, the application of the dual-cure coating materials (A) and (B) has no special features, but can be done using all the usual application methods, such as Spraying, knife coating, brushing, pouring, dipping, trickling or rolling. Spray application methods are preferably used. It is generally advisable to work with the exclusion of actinic radiation in order to avoid premature crosslinking of the coating materials, adhesives and sealing compounds according to the invention.

The method according to the invention is preferably used here. That is, the outside or areas of the outside of the three-dimensional substrate are coated with the dual-cure coating material (A) and the inside or areas of the inside of the three-dimensional substrate are coated with the dual-cure coating material (B). The resulting uncured coatings (A) are then and (B) if appropriate together with other existing uncured coatings, cured thermally and with actinic radiation, which results in the integrated internal and external coating or integrated internal / external coating (B / A)

The hardening itself has no special features in terms of method, but can instead be carried out using the methods and devices described in German patent application DE 102 02 565 A1, page 9, paragraph [0090] to page 10, paragraph [0107].

The resulting interior coating or interior coating (B) according to the invention is hard and scratch-resistant, so that it is no longer damaged, for example, during the further installation or fitting of motor vehicle parts. It has excellent optical properties and very high light, chemical, water, condensation, weather and etch resistance. Their ability to be repacked is excellent.

The resulting outer coating (A) according to the invention is highly scratch-resistant and hard, so that it meets all the requirements of the automobile manufacturers and their customers. In particular, their clearcoat produced from the dual-cure coating material (A) has a storage module E 'in the rubber-elastic range of at least 10 ⁷⁵ Pa and a loss factor tan δ at 20 ° C. of max. 0.1, the storage module E 'and the loss factor having been measured with the aid of dynamic mechanical thermal analysis (DMTA) on free films with a layer thickness of 40 + 10 μm (cf. German patent application DE 102 02 565 A 1). It also has excellent optical properties and a very high light, chemical, water, condensation, weather and etch resistance. Their ability to be repacked is excellent.

In addition, the integrated interior and exterior painting (B / A) according to the invention in the areas in which the interior painting (B) and exterior painting (A) overlap is free of paint defects, such as specks, craters, cookers or runners.

Examples

example 1

The manufacture of integrated dual-cure coating material systems The dual-cure two-component systems (A1) and (A2):

For the production of the integrated dual-cure coating material systems for the production of integrated interior and exterior paintwork (B / A) of car bodies, the dual-cure two-component systems (A1) and (A2) listed in Table 1 were first created by mixing the components their components (I) and (II) and homogenizing the resulting mixtures (I) and (II) with the exclusion of UV radiation. The respective components (I) and (II) were stored separately from one another until they were used.

Table 1: The material composition of the dual-cure two-component systems (A1) and (A2)

Component (A1) (A2)

Component (I):

Methacrylate copolymer (solids 65% by weight; hydroxyl number: 175 mg KOH / g; glass transition temperature: -21 ^β C) 39.9 39.9

Rheology aids (SCA) based on urea according to Preparation Example 3, page 11, lines 41 to 51 of DE 102 04 114 A1 (solids: 59% by weight) 17.1 17.1

Aerosil® paste (solids: 28.47% by weight) 3.3 3.3

Dipentaerythritol pentaacrylate (solids:

100% by weight) 22.8 22.8

Tinuvin® 292 (commercially available light stabilizer from Ciba Specialty Chemicals; solids:

100% by weight) 1.1 1.1 Tinuvin® 400 (commercially available light stabilizer from Ciba Specialty Chemicals; solids: 85% by weight) 1, 1 1, 1

5 Byk® 358 (commercially available paint additive from Byk Chemie; solids: 52% by weight) 0.9 0.9

Irgacure® 184 (commercially available photoinitiator from Ciba Specialty Chemicals; solids: 10 50% by weight) 2.2 2.2

Lucirin® TPO (commercial photoinitiator from BASF Aktiengesellschaft; solids: 10% by weight) 1.1 1.1

15 methoxypropanol 3 3

Butyl diglycol acetate 2 2

20 butyl acetate 5.5 5.5

Component (II):

Isocyanatoacrylate Roskydal ® UA VPLS 2337 25 from Bayer AG (basis: trimer hexamethylene diisocyanate; isocyanate equivalent weight: 329 g; solids: 100% by weight) 55.02 48.1 isocyanatoacrylate Roskydal ® UA VP FWO 30 3003-77 from the company Bayer AG based on the trimer of isophorone diisocyanate (solids: 70.5% by weight; isocyanate equivalent weight: 609 g) 13.77 22.3

35 polyisocyanate based on isophorone diisocyanate (Desmodur® N 3300 from Bayer AG) 9.79 12.8 Butyl acetate 98/100 21.42 16.8

The dual-cure two-component systems (B1) to (B5): For the production of the integrated dual-cure coating material systems for the production of integrated interior and exterior paintwork (B / A) of car bodies, the dual systems listed in Table 2 were first Cure two-component systems (B1) to (B5) by mixing the components of their components (I) and (II) and homogenizing the resulting mixtures (I) and (II) with the exclusion of UV radiation. The respective components (I) and (II) were stored separately from one another until they were used.

Table 2: The material composition of the dual-cure two-component systems (B1) to (B5)

Component (B1) (B2) (B3) (B4) (B5)

Component (I):

Methacrylate copolymer ^a > 58.7

Methacrylate copolymer ^b ) 39.9 39.9 38.7 38.7

Rheology Aid (SCA) ^c > 17.1 17.1 17.1 16.6 16.6

Aerosil® paste "> 3.3 3.3 3.3 3.2 3.2

Dipentaerythritol pentaacrylate ^e > 22.8 22.8 4.7 22.1 221

Tinuvin® 292 *> 1, 1 1, 1 1, 1 1, 1 1, 1

Tinuvin® 400 a> 1, 1 1, 1 1, 1 1, 1 1.1

Byk® 358 ^h > 0.9 0.9 0.9 0.9 0.9

Irgacure® 184 o 2.2 2.2 2.2 2.1 2.1

Lucirin® TPO »5.5 5.5 5.5 5.3 5.3

Methoxypropanol 2.9

Butyl diglycol acetate 1.9 8.9

Butyl acetate 1.1 1.1 0.4 4.1

Component (II):

Isocyanatoacrylate ^k »9.2 9.2 9.2 9.2 Isocyanatoacrylate '8.3 67.9 67.9 67.9 67.9

Polyisocyanate) 5.9 7.2 7.2 7.2 7.2

Isocyanatoacrylate ⁿ ) 73

Butyl acetate 98/100 12.8 15.7 15.7 15.7 15.7

a) solids: 65% by weight; Hydroxyl number: 175 mg KOH / g; Glass transition temperature: -21 ° C;

b) solids: 65% by weight; Hydroxyl number: 175 mg KOH / g; Glass transition temperature: + 11 ° C;

c) SCA based on urea according to production example 3, page 11, lines 41 to 51 of DE 102 04 114 A1 (solids: 59% by weight);

d) solids 28.47% by weight;

e) solid: 100% by weight;

f) commercial light stabilizers from Ciba Specialty Chemicals; Solids: 100% by weight;

g) commercially available light stabilizers from Ciba Specialty Chemicals; Solids: 85% by weight;

h) commercially available paint additive from Byk Chemie; Solids 52% by weight;

i) commercially available photoinitiator from Ciba Specialty Chemicals; Solid: 50% by weight;

j) commercially available photoinitiator from BASF Aktiengesellschaft; Solid: 10% by weight; k) Roskydal® UA VPLS 2337 from Bayer AG (based on: trimeric hexamethylene diisocyanate; content of isocyanate groups: 12% by weight; solid: 100% by weight;

I) Roskydal® UA VP FWO 3003-77 from Bayer AG based on the trimers of isophorone diisocyanate (solids: 70.5% by weight; content of isocyanate groups: 6.7% by weight;

m) polyisocyanate based on isophorone diisocyanate (Desmodur® N 3300 from Bayer AG;

n) isocyanato acrylate based on 4,4'-dicyclohexylmethane diisocyanate (Desmodur® W from Bayer AG) and 4-hydroxybutyl acrylate (solid: 70% by weight; isocyanate equivalent weight 724 g);

The integrated dual-cure coating material systems:

Each of the dual-cure multicomponent systems (A1) or (A2) described above could be integrated with any of the dual-cure multicomponent systems (B1), (B2), (B3), (B4) or (B5) described above to form an integrated dual - Cure coating system are combined, so that a total of 10 such systems resulted.

Example 2

The coating of car bodies with effect-giving multi-layer coatings with clear coats, which were produced using the integrated dual-cure coating material systems

General test instructions: For the interior painting of car bodies under the tailgate and the

Bonnet as well as in the area of the door sills, the trunk and the

The inside of the door and the inside of the window were made shortly before application from the dual-cure multicomponent systems (B1) to (B5) described above (cf.

Example 1, Table 2) by mixing the respective components (I) and (II) in the following mixing ratios (I) / (II) (% by weight) of the dual-cure coating materials

(B1) to (B5): (B1): 100/111; (B2): 100/111; (B3): 100/91; (B4): 100/89; (B5):

100/89. For the exterior painting of car bodies, shortly before application, the dual-cure two-component systems (A1) and (A2) described above (see Example 1, Table 1) were mixed in by mixing the respective components (I) and (II) 5 the following mixing ratios (I) / (H) (% by weight) produced the dual-cure coating materials (A1) and (A2): (A1): 100/67; can write (A2): 100/65.

Car bodies which had been coated with a customary and known electrodeposition coating and a conventional and known filler coating were coated with a commercially available water-based paint containing aluminum effect pigments. The waterborne basecoats were flashed off briefly at room temperature and dried at 80 ° C. for 10 minutes. The wet layer thicknesses were chosen so that layer thicknesses of 12 to 15 15 μm resulted after drying and curing.

The waterborne basecoat in the interior of five car bodies was coated wet-on-wet with one of each of the dual-cure coating materials (B1) to (B5), and the waterborne basecoat on the outside became wet-in-wet with the Dual-20 Cure coating material (A1) coated. The wet layer thicknesses of the clear lacquer layers were set so that layer thicknesses of 40 to 45 μm resulted after curing.

The waterborne basecoat in the interior of five car bodies was coated wet-in-wet with one of the dual-cure coating materials (B1) to (B5), and the waterborne basecoat on the outside was wet-in-wet with the dual Cure coating material (A2) coated. The wet layer thicknesses of the clear lacquer layers were set so that layer thicknesses of 40 to 45 μm resulted after curing. 30 The water-based lacquer layers and clear lacquer layers of the 10 car bodies were predried together for five minutes at room temperature and for 10 minutes at 80 ° C, irradiated with UV radiation at a dose of 1,500 mJ / cm2 and then cured at 140 ° C for 20 minutes.

35 The resulting interior paintwork (B) was hard and scratch-resistant, so that the other components of the cars could be installed without any problems. The resulting Exterior paints (A) were highly scratch-resistant and hard. Both paints had excellent optical properties and a very high light, chemical, water, condensation, weather and etch resistance. Their ability to be repacked was excellent. Above all, however, there were no more paint defects in the areas where the interior paints (B) and exterior paints (A) overlapped.

Claims

claims 1. Integrated dual-cure coating material system which comprises at least two dual-cure multicomponent systems (A) and (B) which consist predominantly or entirely of the same constituents and each comprise at least two components which are stored separately from one another, wherein (I) at least one component (i.1) isocyanate-reactive functional groups and (i.2) reactive functional groups containing at least one bond which can be activated with actinic radiation, (i.3) flexibilizing structural units which, as components of three-dimensional networks, lower their glass transition temperature Tg , and / or (i.4) hardening structural units which, as a component of three-dimensional networks, increase their glass transition temperature Tg, and (II) at least one component (ii.1) free isocyanate groups, (ii.2) reactive functional groups containing at least one bond which can be activated with actinic radiation and (ii.3) flexibilizing structural units which, as components of three-dimensional networks, lower their glass transition temperature Tg, and / or (ii. 4) hardening structural units which, as a component of three-dimensional networks, increase their glass transition temperature Tg, and the dual-cure coating material system (B) (a) overall a lower content of reactive functional groups, containing at least one bond that can be activated with actinic radiation, and / or (b) overall a higher content of hardening structural units, which increase the glass transition temperature Tg as a component of three-dimensional networks than the dual Cure coating material system (A). 2. Integrated dual-cure coating system according to claim 1, characterized in that it comprises two dual-cure multicomponent systems (A) and (B). 3. Integrated dual-cure coating system according to claim 1 or 2, characterized in that it comprises at least one dual-cure two-component system (A). 4. Integrated dual-cure coating system according to one of claims 1 to 3, characterized in that it comprises at least one dual-cure two-component system (B). 5. Integrated dual-cure coating system according to one of claims 1 to 4, characterized in that the dual-cure multicomponent systems (A) and (B) differ from one another in a maximum of two components. 6. Integrated dual-cure coating system according to one of claims 1 to 5, characterized in that the components (I) contain at least one oligomeric and / or polymeric binder with isocyanate-reactive functional groups (i.1). 7. Integrated dual-cure coating system according to one of claims 1 to 6, characterized in that the components (I) contain at least one low molecular weight and / or oligomeric constituent with at least one reactive functional group (i.2). 8. Integrated dual-cure coating system according to one of claims 1 to 7, characterized in that the components (II) contain at least one component which has the features (ii.1) and (ii.2). 9. Use of the integrated dual-cure coating system according to one of claims 1 to 8 for the inner and outer coating of complex shaped three-dimensional substrates. 10. Use according to claim 9, characterized in that the substrates are car bodies. 11. A method for the inner and outer coating of complex shaped three-dimensional substrates found using the integrated dual-cure coating system according to one of claims 1 to 8, characterized in that one (1) at least one dual-cure coating material (A) and (B) each from at least one dual-cure multicomponent system (A) and (B) by mixing at least one component (I) and (II) and homogenizing the resulting mixture and (2) ^' ' coated the outside of the three-dimensional substrate with the dual-cure coating material (A) and the inside of the three-dimensional substrate with the dual-cure coating material (B), after which (3) the resulting coatings (A) and (B) harden thermally and with actinic radiation, resulting in the integrated inner and outer coating (B / A).