WO2022037950A1 - Systems of coating agents, consisting of a base coat and a top coat, and semi-finished product based thereon and production of same - Google Patents

Abstract

The present invention relates to a layer structure comprising at least one of the following directly successive layers that are adhesively bonded to each other in the order cover layer - adhesion-promoting layer - thermoplastic polymer layer, to a kit-of-parts, to a method for producing the layer structure according to the invention, to a film-insert molding process for producing a molding, to products comprising the layer structure according to the invention, and to the use of the layer structure according to the invention.

Description

Coating agent systems consisting of base coat and top coat, and based thereon

Semi-finished product and production of the same

The present invention relates to a layer structure comprising at least the following directly consecutive layers that are adhesively bonded to one another in the sequence cover layer-adhesion promoter layer-thermoplastic polymer layer, a kit-of-parts, a method for producing the layer structure according to the invention, a film insert molding method for the production of a molded part, products comprising the layer structure according to the invention, and the use of the layer structure according to the invention.

Film insert molding technology has become established for the production of plastic parts using injection molding. It provides that the front surface of a part is first prefabricated in two or three dimensions from a coated film and then filled or back-injected with a plastic melt from the rear.

It is often desirable that the front side is adequately protected against chemical and mechanical influences. In the prior art, this is often achieved by a corresponding coating or painting of the surface. In order to avoid wet coating of the finished three-dimensional parts, it is advantageous that such a paint or coating should already be applied to the foil, which then goes through all further forming steps with the foil and is then finally cured, e.g. by UV exposure.

This results in a very special profile of properties for coated films that match this technology. In the prior art, the term "formable hardcoating" has become established for this product class, namely a film coating that is initially sufficiently block-resistant, but can then be thermally shaped three-dimensionally together with the substrate and finally acquires the properties of a protective layer through UV curing .

Such a combination of properties in terms of blocking resistance and thermoplastic behavior of the primary coating together with the large latent potential for UV crosslinking is difficult to achieve.

As a rule, good surface properties require a high crosslinking density of the coating. However, high crosslinking densities lead to duromer behavior with the maximum possible degree of stretching of only a few percent, so that the coating tends to crack during the forming process. This apparent conflict between the need for high crosslink density and the desired high degree of stretching can be resolved, for example, by carrying out the drying/curing of the coating in two steps, before and after deformation. A radiation-induced crosslinking reaction in the coating is particularly suitable for post-curing. In addition, if this process is to be used economically, it is necessary to wind up the coated, deformable film onto rolls in the meantime. The pressure loads occurring in the rollers place particular demands on the blocking resistance of the applied and dried but not yet fully cured coating.

Thermally deformable and then UV-curing coatings are described in the prior art, for example in Beck, Erich (BASF), Scratch resistant UV coatings for automotive applications, Pitture e Vemici, European Coatings (2006), 82(9), 10-19; Beck, Erich, Into the third dimension: three ways to apply UV coating technology to 3D automotive objects, European Coatings Journal (2006), (4), 32, 34, 36, 38-39; Petzoldt, Joachim; Coloma, Fermin (BMS), New three-dimensionally formable hardcoat films, JOT, Journal filer Oberflaechentechnik (2010), 50(9), 40-42 and Petzoldt et al., Development of new generation hard coated films for complex 3D-shaped FIM applications, RadTech Asia 2011, Conference Proceedings.

Most of these are based on so-called macromonomers, which are mainly produced by dual-cure processes. Thermoplastic macromonomers are formed by a first curing mechanism (e.g. PUR, polyaddition), the unaffected and UV-curing groups (e.g. acrylates), which are attached as end or side substituents, show up after deformation in the second curing step. The disadvantage here, however, is that such macromonomers themselves, or the components for them, have to be specially prepared synthetically, which gives rise to additional costs in production. Macromonomers obtainable by dual-cure processes are described, for example, in EP 2 113 527 A1.

WO 2005/080484 A1 describes a radiation-curable composite layered sheet or film composed of at least one substrate layer and a cover layer, which contains a radiation-curable composition with a glass transition temperature below 50° C. and a high double bond density.

WO 2005/118689 A1 discloses an analogous composite layered sheet or film in which the radiation-curable composition additionally contains acid groups. Both applications describe the top layer as non-adhesive, a higher blocking resistance, such as is required for rolling the film around a core, is not achieved. The possibility of winding up the composite films into rolls before radiation curing of the cover layer is therefore not mentioned either.

Consequently, there is still a need in the prior art for improved or at least alternative radiation-curing coatings. Such coatings would be desirable in which the coating, for example on films, after shaping and curing, exhibits high abrasion resistance, scratch resistance and solvent resistance combined with good adhesion to the film. In addition, improved or at least alternative coatings would be desirable in which the coating exhibits such high blocking resistance prior to forming that that the films coated with it can be rolled up without any problems, but that high degrees of stretching can still be achieved in the shaping process. Another important aspect relates to the economics of such coating systems. The macromonomers or their components for such coating systems are usually produced synthetically, which of course causes higher production costs. It would therefore also be desirable to design the coating system to be able to be produced in the simplest and most efficient manner possible. There is therefore a need in the prior art for coating agents which, on the one hand, are simple, efficient and therefore inexpensive to produce and, on the other hand, lead to coatings, in particular on films, which are block-resistant after application and drying and have high abrasion resistance after curing. Have scratch resistance and solvent resistance.

Since such coating agents can be used as a component of coated semi-finished products, in particular coated thermoplastic films, for the production of consumer goods using the so-called film insert molding process, it would be particularly desirable that the selected coating after shaping the film and curing and the final back injection molding Has flaking, delamination and/or in particular microcracks. Especially with production geometries that are manufactured with a high degree of stretching of the film during so-called thermoforming or high-pressure forming, or those in which the formed film reproduces narrow radii (typically up to the radius of twice or four times the film thickness), cracks often form in the hardened paint of the back-injected component observed. Developing a coating material with a sufficiently high elasticity for crack-free back-injection and at the same time high cohesion after curing, expressed by high abrasion resistance, scratch resistance and solvent resistance, is generally considered to be extremely demanding. In this respect, the provision of such coating materials and substrates coated therewith with the profile of properties described represents a particular challenge for the person skilled in the art.

The task is therefore to provide an economical coating system in which the coating has such a high blocking resistance before forming that the films coated with it can be rolled up without any problems, but high degrees of stretching can still be achieved in the forming process without flaking, delamination and/or especially microcracks occur. Furthermore, after curing, the coating should have high abrasion resistance, scratch resistance and solvent resistance.

A further object is the provision of a kit of parts for such a coating system. A further object is the provision of a method for producing such a coating system and a film insert molding method for producing a molded part comprising such a coating system.

In order to at least partially solve these problems, the present invention therefore provides the following:

Layered structure comprising at least the following directly consecutive, mutually adhesively bonded layers in the sequence A-B-C:

A: Top coat or top coat layer, obtainable or obtained by curing a composition (ZA), hereinafter also referred to as top coat, comprising:

Al) at least one thermoplastic polymer with an average molecular weight Mw (also called molecular weight Mw) of at least 100,000 g/mol, determined in accordance with DIN EN/ISO 16014-1, the chromatographic conditions being selected in accordance with DIN 55762-1 (2016) and in a content of at least 30% by weight of the solid fraction of the composition (ZA),

A2) at least one UV-curable monomer and/or at least one UV-curable oligomer in a content of at least 30% by weight of the solid fraction of the composition (ZA),

A3) at least one photoinitiator in a content of >0.1% by weight to <10% by weight of the solids content of the composition (ZA), and

A4) at least one organic solvent, where the proportion of ethylenically unsaturated groups is at least 3 mol per kg of the solids content of the composition (ZA) and component A2 has the arithmetic mean of at least 3 ethylenically unsaturated groups per molecule;

B: Adhesion promoter layer or basecoat layer obtainable or obtained by curing a composition (ZB), hereinafter also referred to as basecoat, comprising:

Bl) at least one aqueous hybrid dispersion comprising or consisting of at least one aliphatic polyurethane-polyurea, at least one further aliphatic polymer and at least one dispersant, wherein the at least one aliphatic polyurethane-polyurea is obtainable or was obtained from the reaction of a reaction mixture comprising: a) at least an acyclic aliphatic and/or a cycloaliphatic polyisocyanate, b) at least one polyol selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and copolymers thereof with aliphatic polyesters, polyesteramides, polyethers, polythioethers, polycarbonates, polyacetals, polyolefins or polysiloxanes and mixtures of at least two of these, c) at least one isocyanate-reactive compound which also contains dispersing groups or groups which can be converted into dispersing groups by salt formation, d) at least one chain extender, the at least one further aliphatic polymer being obtainable or obtained by the reaction of monomers selected from the group consisting of ethylenically unsaturated hydrocarbons, ethylenically unsaturated esters and ethylenically unsaturated ethers and mixtures of at least two of these, and

B2) at least one organic (co)solvent, and

C: thermoplastic polymer layer, also referred to below as film, plastic film, substrate or substrate layer, the polymer being selected from the group consisting of polyacrylate, poly(meth)acrylate, polysulfone, polyurethane, acrylonitrile-butadiene-styrene copolymer (ABS), Polyester, polyamide, polycarbonate and their copolymers, blends and coextrudates.

Another subject of the present invention relates to a kit of parts for producing the layer structure according to the invention, containing at least one uncured composition (ZA), at least one uncured composition (ZB) and a thermoplastic polymer layer (C), the composition (ZA):

Al) at least one thermoplastic polymer with an average molecular weight Mw of at least 100,000 g/mol, determined in accordance with DIN EN/ISO 16014-1, the chromatographic conditions being selected in accordance with DIN 55762-1 (2016) and in a content of at least 30 wt % of the solid part of the composition (ZA),

A2) at least one UV-curable monomer and/or at least one UV-curable oligomer in a content of at least 30% by weight of the solid fraction of the composition (ZA),

A3) at least one photoinitiator in a content of >0.1% by weight to <10% by weight of the solids content of the composition (ZA), and

A4) comprises at least one organic solvent and where the proportion of ethylenically unsaturated groups is at least 3 mol per kg of the solids content of the composition (ZA) and the arithmetic average of component A2 has at least 3 ethylenically unsaturated groups per molecule; where the composition (ZB):

Bl) at least one aqueous hybrid dispersion comprising or consisting of at least one aliphatic polyurethane-polyurea, at least one further aliphatic polymer and at least one dispersant, wherein the at least one aliphatic polyurethane-polyurea is obtainable or was obtained from the reaction of a reaction mixture comprising: a) at least an acyclic aliphatic and/or a cycloaliphatic polyisocyanate, b) at least one polyol selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and copolymers thereof with aliphatic polyesters, polyesteramides, polyethers, polythioethers, polycarbonates, Polyacetals, polyolefins or polysiloxanes and mixtures of at least two thereof, c) at least one isocyanate-reactive compound which also contains dispersing groups or contains groups which are formed by salt formation in dispersing groups can be converted, d) at least one chain extender, the at least one further aliphatic polymer being obtainable or obtained by reacting monomers selected from the group consisting of ethylenically unsaturated hydrocarbons, ethylenically unsaturated esters and ethylenically unsaturated ethers and mixtures at least two of these, and

B2) comprises at least one organic (co)solvent, and wherein the thermoplastic polymer layer C is selected from the group consisting of polyacrylate, poly(meth)acrylate, polysulfone, polyurethane, acrylonitrile-butadiene-styrene copolymer (ABS), Polyester, polyamide, polycarbonate and their copolymers, blends and coextmdaten.

Another object of the present invention is a method for producing the layer structure A-B-C according to the invention, comprising the steps:

(i) providing a thermoplastic polymer layer C, wherein the thermoplastic polymer layer C is selected from the group consisting of polyacrylate, poly(meth)acrylate, Polysulfone, polyurethane, acrylonitrile butadiene styrene copolymer (ABS), polyester, polyamide, polycarbonate and their copolymers, blends and coextmdaten;

(ii) coating the thermoplastic polymer layer C with a composition (ZB), wherein the composition (ZB):

Bl) at least wherein the one aqueous hybrid dispersion comprising or consisting of at least one aliphatic polyurethane-polyurea, at least one further aliphatic polymer and at least one dispersant, wherein the at least one aliphatic polyurethane-polyurea is obtainable or was obtained from the reaction of a reaction mixture comprising: a ) at least one acyclic aliphatic and/or a cycloaliphatic polyisocyanate, b) at least one polyol selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and copolymers thereof with aliphatic polyesters, polyester amides, polyethers, polythioethers, Polycarbonates, polyacetals, polyolefins or polysiloxanes and mixtures of at least two thereof, c) at least one isocyanate-reactive compound which also contains dispersing groups or contains groups which are formed by salt formation ng can be converted into dispersing groups, d) at least one chain extender, the at least one further aliphatic polymer being obtainable or obtained by reacting monomers selected from the group consisting of ethylenically unsaturated hydrocarbons, ethylenically unsaturated esters and ethylenically unsaturated ethers and mixtures of at least two of these, and

B2) comprises at least one organic (co)solvent, and

(iii) drying and optionally curing the composition (ZB) to obtain an adhesion promoter layer B;

(iv) coating the adhesion promoter layer B from step (iii) with a composition (ZA), wherein the composition (ZA):

Al) at least one thermoplastic polymer with an average molecular weight Mw of at least 100,000 g / mol, determined according to DIN EN / ISO 16014-1, the chromatographic Conditions were chosen according to DIN 55762-1 (2016) and in a content of at least 30% by weight of the solid fraction of the composition (ZA),

A2) at least one UV-curable monomer and/or at least one UV-curable oligomer in a content of at least 30% by weight of the solid fraction of the composition (ZA),

A3) at least one photoinitiator in a content of >0.1% by weight to <10% by weight of the solids content of the composition (ZA), and

A4) comprises at least one organic solvent, and wherein the proportion of ethylenically unsaturated groups is at least 3 mol per kg of the solids content of the composition (ZA) and component A2 has the arithmetic mean of at least 3 ethylenically unsaturated groups per molecule;

(v) drying the composition (ZA) to obtain an uncured top layer (A);

(vi) optionally cutting, delaminating, printing and/or thermally or mechanically deforming the layer structure from (v); and

(vii) subjecting the layer structure from (v) or (vi) to actinic radiation to cure the top layer A, with the layer structure A-B-C being obtained.

Surprisingly, it was found that the layer structure according to the invention has good solvent resistance, scratch resistance and abrasion resistance. Furthermore, the adhesion promoter layer B and the top layer A have good blocking resistance after they have been applied to the thermoplastic polymer layer C, such as a film, for example, and have dried. The formation of an interpenetration layer (IPL) at the interface between the basecoat layer and the substrate is conducive to the observed adhesion to the surfaces of various thermoplastic substrates, such as polycarbonate and polymethyl(meth)acrylate. It was also surprisingly found that components of the top layer penetrate the adhesion promoter layer and attach themselves to the corresponding boundary surface, as a result of which said adhesion of the top layer and adhesion promoter layer is significantly improved compared to known systems. Furthermore, with the layer structure according to the invention, high degrees of stretching can be achieved in deformation processes without chipping, delamination and/or, in particular, microcracks occurring.

In the context of the present invention, the word “a” in connection with countable variables is only to be understood as a numeral if this is expressly stated (e.g. by the expression “exactly a”). For example, when “a polyol” is mentioned below, the word is “a” is to be understood only as an indefinite article and not as a numeral, so it also includes an embodiment that contains a mixture of at least two polyols.

A hybrid dispersion B1) is understood as meaning a dispersion which, in addition to polyurethane(s), also contains at least one other polymeric component which is not polyurethane, such as a poly(meth)acrylate, and is dispersed in a liquid medium, frequently water. (see for example Ind. Eng. Chem. Res. 2019, 58, 46, 20902-20922)

According to the invention, the expressions “comprising” or “containing”, “consisting essentially of” and particularly preferably “consisting of” preferably mean.

The scratch resistance can be determined using the pencil hardness, which can be measured based on ASTM D 3363. The resistance to solvents can be evaluated based on EN ISO 2812-3:2007. It is noteworthy that the surface of the layer composite obtained by the inventive coating of the thermoplastic polymer layer with the inventive adhesion promoter layer and top layer and subsequent curing by UV radiation has good resistance even to the solvent acetone, which is otherwise very harmful to polycarbonate surfaces.

The proportion of ethylenically unsaturated groups in the top layer A is described using the so-called double bond density (DBD), which in turn relates to the functionality of a monomer or oligomer. Experts understand “functionality” to mean the nominal number of reactive groups, ie the number to be determined on the basis of the idealized molecular structure of a monomer or oligomer, e.g. B. ethylenically unsaturated double bonds, isocyanate or hydroxyl functions. The double bond density (DBD) of the reactive mono- or oligomer is calculated accordingly as follows: 1000 [g • kg ¹ ] • "functionality" [mol • mol ¹ ] / (molar mass of the monomer or oligomer [g • mol ¹ ]). The proportion of ethylenically unsaturated groups in the solid fraction of the composition (ZA) is calculated based on the double bond density of the reactive monomer(s) or oligomer/mers, taking into account the respective fractions in the solid fraction of the composition (ZA): solid fraction of monomer or oligomer 1 [%] • DBD; [mol- kg ¹ ] + solid fraction mono- or oligomer 2 [%] • DBD2 [mol- kg" ¹ ] + ... + solid fraction mono- or oligomer n [%] • DBDn [mol- kg-1] .

Unless stated otherwise, the molecular weight Mw (also called molecular weight Mw) was determined by gel permeation chromatography. In particular, the molecular weight Mw for at least one thermoplastic polymer A1) and for the at least one polyol (b) from which the at least one aliphatic polyurethane-polyurea of the composition (ZB) is built, determined according to DIN EN/ISO 16014-1, where the chromatographic conditions according to DIN 55762-1 (2016) were selected. The following devices and parameters were used for the measurement:

Chromatographic system:

Degassers: Agilent 1200 Series Degassers

Pump: Agilent 1100 Series IsoPump

Autosampler: Agilent 1260 Infinity ALS

Column oven: Agilent 1260 Infinity TCC

RI detector: Agilent 1260 Infinity RID

Software: PSS WinGPC UniChrom V 8.31, Build 8417

Chromatographic conditions:

DIN: DIN 55672-1

Column: 1. Agilent PLgel Mixed B, 7.5*300mm, 10pm

2. Agilent PLgel Mixed B, 7.5*300mm, 10pm

3. Agilent PLgel Mixed B, 7.5*300mm, 10pm

Number of floors: 31,428 1/m

Resolution factor: 4.134

Mobile phase: tetrahydrofuran +

Flow rate: 1mL/min

Temperature: 35°C

Cell temperature RI: 35°C

Injection volume: lOOpL

Sample concentration: Ig/L

Molecular weight standards: PSS Polymer-Standards-Service GmbH, Mainz; Germany CUR Part No/ Serial No. : CUR00007475

Mp [Da]: 7,520,000; 2,930,000; 1,210,000; 579,000; 277,000; 127,000;

67,000; 34,800; 17,800; 8,400; 3,420; 1,620

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the composition (ZA) consists of at least 80% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight % and more preferably at least 98% by weight of components A1), A2), A3) and A4) based on the total weight of the composition (ZA).

In a preferred embodiment of the layer structure according to the invention, the chain extender d) of Bl) of the composition (ZB) is a diamine. In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the at least one thermoplastic polymer A1) of the composition (ZA) has an average molecular weight Mw in the range from 100,000 g/mol to 500,000 g/mol , preferably in the range from 250,000 g/mol to 350,000 g/mol, determined in accordance with DIN EN/ISO 16014-1, the chromatographic conditions being selected in accordance with DIN 55762-1 (2016).

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the at least one thermoplastic polymer A1) of the composition (ZA) is selected from the group consisting of esters of acrylic acid and methacrylic acid, aromatic polyesters, cellulose esters , polyvinyl acetals, polystyrene and mixtures of at least two of these.

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the at least one thermoplastic polymer A1) of the composition (ZA) is a polymethyl methacrylate homopolymer or polymethyl methacrylate copolymer based on methyl methacrylate with a methyl methacrylate Proportion of more than 70% by weight, preferably at least one polymethyl methacrylate homopolymer or polymethyl methacrylate copolymer of in each case 70% by weight to 99.5% by weight methyl methacrylate and 0.5% by weight to 30% by weight Methyl acrylate, particularly preferably at least one polymethyl methacrylate homopolymer or polymethyl methacrylate copolymer of in each case 90% by weight to 99.5% by weight methyl methacrylate and 0.5% by weight to 10% by weight methyl acrylate. The percentages by weight relate in each case to the proportion of the total weight of the thermoplastic polymer A1).

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the at least one thermoplastic polymer has an average molecular weight Mw of at least 100,000 g/mol and preferably an average molecular weight Mw of at least 250,000 g/mol , determined according to DIN EN/ISO 16014-1, whereby the chromatographic conditions were selected according to DIN 55762-1 (2016).

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the at least one polyol b) from which the at least one aliphatic polyurethane-polyurea of the composition (ZB) is constructed is selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and mixtures of at least two thereof, preferably selected from the group consisting of aliphatic polyether polyols, aliphatic polyether-polyester polyols and mixtures of at least two thereof and more preferably an aliphatic polyether-polyester polyol.

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and / or the method according to the invention, the at least one polyol b) from which the at least one aliphatic polyurethane-polyurea of the composition (ZB) is made up has an average molecular weight im range from 500 g/mol to 6000 g/mol, preferably in the range from 700 g/mol to 3000 g/mol, determined according to DIN EN/ISO 16014-1, the chromatographic conditions according to DIN 55762-1 (2016) were chosen.

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the further aliphatic polymer of the composition (ZB) can be obtained or was obtained by reacting monomers selected from the group consisting of esters of acrylic acid and methacrylic acid, esters and ethers of vinyl alcohol and styrene and mixtures of at least two thereof, preferably selected from the group consisting of esters of acrylic acid and methacrylic acid and mixtures of at least two thereof.

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the thermoplastic polymer layer C is selected from the group consisting of polyacrylate, poly(meth)acrylate, polyurethane, acrylonitrile-butadiene-styrene copolymer (ABS), polyesters, polyamides, polycarbonate-polyester and polycarbonate (acrylonitrile butadiene styrene copolymer) blends and their poly(meth)acrylate coextrudates, polycarbonate and coextruded polycarbonate with a poly(meth)acrylate top layer , Preferably selected from the group consisting of polyacrylate, poly (meth) acrylate, polycarbonate-polyester and polycarbonate (acrylonitrile-butadiene-styrene copolymer) blends and their poly (meth) acrylate coextrudates, polycarbonate and coextruded polycarbonate with a Poly(meth)acrylate top layer, particularly preferably selected from the group consisting of polycarbonate-polyester and polycarbonate-(acrylonitrile-butadiene-styrene-C opolymer) blends and their poly(meth)acrylate coextrudates, polycarbonate and coextruded polycarbonate with a poly(meth)acrylate top layer.

In a preferred embodiment of the layer structure according to the invention and / or the method according to the invention, the dried and cured top layer A has a layer thickness in the range from 1 μm to 50 μm, preferably 5 μm to 25 μm, particularly preferably 8 μm to 15 μm, and the dried Adhesive layer B has a layer thickness in the range from 2 μm to 60 μm, preferably from 10 μm to 30 μm, particularly preferably from 18 μm to 25 μm. the Layer thickness was determined in each case by microtome sectioning of the layers and light microscopic evaluation of the microtome sections.

Top layer A

The top layer A can be obtained or is obtained by curing a composition (ZA). The composition (ZA) can be cured, for example, by actinic radiation. The composition (ZA) includes:

Al) at least one thermoplastic polymer with an average molecular weight Mw of at least 100,000 g/mol, determined in accordance with DIN EN/ISO 16014-1, the chromatographic conditions being selected in accordance with DIN 55762-1 (2016) and in a content of at least 30 wt % of the solid part of the composition (ZA),

A2) at least one UV-curable monomer and/or at least one UV-curable oligomer in a content of at least 30% by weight of the solid fraction of the composition (ZA),

A3) at least one photoinitiator in a content of >0.1% by weight to <10% by weight of the solids content of the composition (ZA), and

A4) at least one organic solvent, the proportion of ethylenically unsaturated groups being at least 3 mol per kg of the solids content of composition (ZA) and component A2 having the arithmetic mean of at least 3 ethylenically unsaturated groups per molecule.

In a preferred embodiment, the composition (ZA) consists of at least 80% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight and even more preferably at least 98% by weight of components A1 ), A2), A3) and A4) based on the total weight of the composition (ZA).

Examples of suitable thermoplastic polymers A1) are polymethyl methacrylate (PMMA), various types of polyester (e.g. PET, PEN, PBTP and UP), other plastics such as rigid PVC, cellulose esters (such as CA, CAB, CP), polystyrene (PS) and Copolymers (SAN, SB and MBS), polyacrylonitrile (PAN), AB S plastics, acrylonitrile methyl methacrylate (AMMA), acrylonitrile styrene acryl ester (ASA), polyurethane (PUR), polyethylene (PE, PE-HD, -LD, - LLD, -C), polypropylene (PP), polyamide (PA), polycarbonate (PC) or polyethersulfone (PES), and their physical mixtures. The abbreviations are defined in DIN EN/ISO 1043-1 (2016).

In a preferred embodiment of the invention, the at least one thermoplastic polymer A1) is a linear thermoplastic polymer In a further preferred embodiment of the present invention, the Vicat softening point VET (ISO 306-650) of the at least one thermoplastic polymer A1) is in the range of at least 90°C, preferably at least 95°C, particularly preferably at least 100°C.

In a preferred embodiment of the invention, the at least one thermoplastic polymer A1) has an average molecular weight Mw in the range from 100,000 g/mol to 500,000 g/mol, preferably in the range from 250,000 g/mol to 350,000 g/mol, determined according to DIN EN /ISO 16014-1, whereby the chromatographic conditions were selected according to DIN 55762-1 (2016).

In a preferred embodiment of the invention, the at least one thermoplastic polymer A1) is selected from the group consisting of esters of acrylic acid and methacrylic acid, aromatic polyesters, cellulose esters, polyvinyl acetals, polystyrene and mixtures of at least two of these.

In a preferred embodiment of the invention, the at least one thermoplastic polymer is polymethyl methacrylate.

Polymethyl methacrylate (PMMA) is understood to mean, in particular, polymethyl methacrylate homopolymer and copolymers based on methyl methacrylate with a methyl methacrylate proportion of more than 70% by weight. Such polymethyl methacrylates are available, for example, under the trade names Degalan®, Degacryl®, Plexyglas®, Acrylite® (Rohm), Altuglas, Oroglas (Arkema), Elvacite®, Colacryl®, Lucite® (Lucite) and others under names Acrylglas, Conacryl, Deglas, Diakon, Friacryl, Hesaglas, Limacryl, PerClax and Vitroflex available.

In a further advantageous embodiment, PMMA homopolymers and/or copolymers of 70% by weight to 99.5% by weight methyl methacrylate and 0.5% by weight to 30% by weight methyl acrylate are preferred. PMMA homopolymers and copolymers of 90% by weight to 99.5% by weight methyl methacrylate and 0.5% by weight to 10% by weight methyl acrylate are particularly preferred. The Vicat softening point VET (ISO 306) can be in the range of at least 90°C, preferably from >100°C to <115°C.

Particular preference is given to PMMA homopolymers and copolymers with an average molar weight Mw of at least 100,000 g/mol and very particularly preferably with an average molar weight Mw of at least 250,000 g/mol.

The molecular weight Mw is determined by gel permeation chromatography, as described above.

In a preferred embodiment of the invention, the at least one thermoplastic polymer A1) of the composition (ZA) is a polymethyl methacrylate homopolymer or Polymethyl methacrylate copolymer based on methyl methacrylate with a methyl methacrylate content of more than 70% by weight, preferably at least one polymethyl methacrylate homopolymer or polymethyl methacrylate copolymer of in each case 70% by weight to 99.5% by weight methyl methacrylate and 0, 5% by weight to 30% by weight of methyl acrylate, particularly preferably at least one polymethyl methacrylate homopolymer or polymethyl methacrylate copolymer of in each case 90% by weight to 99.5% by weight of methyl methacrylate and 0.5% by weight to 10 % by weight of methyl acrylate. The percentages by weight relate in each case to the proportion of the total weight of the thermoplastic polymer A1).

In a preferred embodiment of the invention, the at least one thermoplastic polymer has an average molecular weight Mw of at least 100,000 g/mol and preferably an average molecular weight Mw of at least 250,000 g/mol, determined according to DIN EN / ISO 16014-1 (chromatographic conditions according to DIN 55762-1 (2016)) or according to DIN EN/ISO 16014-5 (2019).

In a preferred embodiment of the invention, the at least one thermoplastic polymer is present in a content of at least 40% by weight, particularly preferably in a content of at least 45% by weight, of the solid fraction of the composition (ZA).

At least one UV-curable monomer and/or at least one UV-curable oligomer in a content of at least 30% by weight of the solids content of the composition (ZA) is used as component A2) in the composition (ZA).

Suitable as component A2) of the composition (ZA) are, for example, bifunctional, trifunctional, tetrafunctional, pentafunctional or hexafunctional acrylic and/or methacrylic monomers. They are preferably acrylic acid ester and/or methacrylic acid ester monomers, in particular acrylic acid ester functions. Suitable polyfunctional acrylic and/or methacrylic esters are derived from aliphatic polyhydroxy compounds having at least 2, preferably at least 3 and more preferably at least 4 hydroxy groups and preferably 2 to 12 carbon atoms.

Examples of such aliphatic polyhydroxy compounds are ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, tetramethylolethane and sorbitan. Examples of bi- to hexafunctional acrylic and/or methacrylic monomers, preferably suitable esters of the polyhydroxy compounds mentioned are glycol diacrylate and dimethacrylate, butanediol diacrylate or dimethacrylate, dimethylolpropane diacrylate or dimethacrylate, diethylene glycol diacrylate or dimethacrylate, divinylbenzene, trimethylolpropane triacrylate or trimethacrylate, glycerol triacrylate or trimethacrylate, pentaerythritol tetraacrylate or tetramethacrylate, Dipentaerythritol penta/hexaacrylate (DPHA), 1,2,3,4-butanetetraol tetraacrylate or tetramethacrylate, tetramethylolethane tetraacrylate or tetramethacrylate, 2,2-dihydroxypropanediol-1,3-tetraacrylate or tetramethacrylate, diurethane dimethacrylate (UDMA), sorbitan tetra -, -penta- or -hexa-acrylate or the corresponding methacrylates. Mixtures of crosslinking monomers having two to four or more ethylenically unsaturated, free-radically polymerizable groups can also be used.

Also suitable as component A2) of the composition (ZA) are alkoxylated di-, tri-, tetra-, penta- and hexa-acrylates or methacrylates. Examples of alkoxylated diacrylates or methacrylates are alkoxylated, preferably ethoxylated, methanediol diacrylate, methanediol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 2-butyl-2-ethyl-1,3- propanediol dimethacrylate, trimethylolpropane diacrylate or trimethylolpropane dimethacrylate.

Examples of alkoxylated triacrylates or methacrylates are alkoxylated, preferably ethoxylated, pentaerythritol triacrylate, pentaerythritol trimethacrylate, glycerol triacrylate, glycerol trimethacrylate, 1,2,4-butanetriol triacrylate, 1,2,4-butanetriol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecanedimethanol diacrylate,

tricyclodecanedimethanol dimethacrylate, ditrimethylolpropane tetraacrylate or

ditrimethylolpropane tetramethacrylate.

Examples of alkoxylated tetra-, penta- or hexaacrylates are alkoxylated, preferably ethoxylated, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate or dipentaerythritol hexamethacrylate.

In the alkoxylated diacrylates or methacrylates, triacrylates or methacrylates, tetraacrylates or methacrylates, pentaacrylates or methacrylates and/or alkoxylated hexaacrylates or methacrylates of component A2), all acrylate groups or methacrylate groups or only some of the acrylate groups or methacrylate groups in the respective monomer be bonded to the corresponding radical via alkylene oxide groups. Any mixtures of such fully or partially alkoxylated di-, tri-, tetra-, penta- or hexaacrylates or methacrylates can also be used. It is also possible for the acrylate or methacrylate group(s) to be bonded to the aliphatic, cycloaliphatic or aromatic radical of the monomer via a plurality of consecutive alkylene oxide groups, preferably ethylene oxide groups. The average number of alkylene oxide or ethylene oxide groups in the monomer is given by the degree of alkoxylation or degree of ethoxylation. The degree of alkoxylation or degree of ethoxylation can preferably be from 2 to 25, in particular degrees of alkoxylation or degrees of ethoxylation of from 2 to 15, very particularly preferably from 3 to 9, are preferred.

UV curable oligomers

Also according to the invention as component A2) of the composition (ZA) are UV-curable oligomers which belong to the class of aliphatic urethane acrylates or polyester acrylates or polyacrylic acrylates. Their use as paint binders is known and is described in Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Vol. 2, 1991, SITA Technology, London (PKT: Oldring (Ed.) on p.73-123 (Urethane Acrylates) or pages 123-135 (polyester acrylates) Commercially available and suitable in the sense of the invention are, for example, aliphatic urethane acrylates such as Ebecryl® 4858, Ebecryl® 284, Ebecryl® 265, Ebecryl® 264, Ebecryl® 8465, Ebecryl® 8402 (manufacturer Allnex SA), Craynor® 925 from Sartomer / Arkema SA, Viaktin® 6160 from Solvay, Desmolux VP LS 2265 from Allnex SA, Photomer 6891 from IGM Resins or aliphatic urethane acrylates such as Laromer® 8987 (70%) dissolved in reactive thinners in hexanediol diacrylate) from BASF SE, Desmolux U 680 H (80% in hexanediol diacrylate) Ebecryl® 294/25HD (75% in hexanediol diacrylate), Ebecryl® 8405 (80% in hexanediol diacrylate), Ebecryl® 4820 (65% in hexanediol diacrylate) (manufacturer Allnex SA respectively) and Craynor® 963B 80 (80% in hexanediol diacrylate) from Sartomer / Arkema SA, or also polyester acrylates such as Ebecryl® 810, 830 or polyacrylic acrylates such as Ebecryl®, 740, 745, 767 or 1200 from Allnex SA .. Reactive diluents are generally low-viscosity, UV-curable Called monomers, oligomers or mixtures thereof.

Component A2) or the reactive diluent preferably comprises alkoxylated diacrylates and/or dimethacrylates, alkoxylated triacrylates and/or trimethacrylates, alkoxylated tetraacrylates and/or tetramethacrylates, alkoxylated pentaacrylates and/or pentamethacrylates, alkoxylated hexaacrylates and/or hexamethacrylates, aliphatic urethane acrylates, polyester acrylates, polyacrylic acrylates and mixtures thereof.

Mixtures of such crosslinking multifunctional monomers and monofunctional monomers (such as methyl methacrylate) are also possible according to the invention. The proportion of the multifunctional monomers in such a mixture should not be less than 20% by weight.

The total proportion of component A2) in the solids content of the composition is at least 30% by weight. 40% by weight is particularly preferred, and 45% by weight is very particularly preferred.

The content of ethylenically unsaturated groups has a significant influence on the achievable durability properties of the radiation-cured coating. The composition (ZA) therefore contains a proportion of ethylenically unsaturated groups of at least 3.0 mol per kg of solid content of the composition (ZA), preferably at least 3.5 mol per kg, particularly preferably at least 4.0 mol per kg of solid content of the composition (ZA). The proportion of ethylenically unsaturated groups in the top layer A is described using the so-called double bond density (DBD), which in turn relates to the functionality of a monomer or oligomer. Experts understand “functionality” to mean the nominal number of reactive groups, ie the number to be determined on the basis of the idealized molecular structure of a monomer or oligomer, e.g. B. ethylenically unsaturated double bonds, isocyanate or hydroxyl functions. The double bond density (DBD) of the reactive mono- or oligomer is calculated accordingly as follows: 1000 [g • kg ¹ ] • "functionality" [mol • mol ¹ ] / (molar mass of the monomer or oligomer [g • mol ¹ ]). The proportion of ethylenically unsaturated groups in the solid fraction of the composition (ZA) is calculated based on the double bond density of the reactive monomer(s) or oligomer/mers, taking into account the respective fractions in the solid fraction of the composition (ZA): solid fraction of monomer or oligomer 1 [%] • DBD; [mol- kg ¹ ] + solid fraction of mono- or oligomer 2 [%] • DBD2 [mol- kg" ¹ ] + . . . + solid fraction of mono- or oligomer n [%] • DBD" [mol- kg" ¹ ].

At least one photoinitiator in a content of >0.1% by weight to <10% by weight of the solids fraction of the composition (ZA) is used as component A3) of the composition (ZA).

For example, the OMNIRAD (formerly IRGACURE®)® types from IGM Resins are used as photoinitiators, such as the types OMNIRAD® 184, OMNIRAD® 500, OMNIRAD® 1173, OMNIRAD®2959, OMNIRAD® 745, OMNIRAD® 651, OMNIRAD® 369 , OMNIRAD® 907, OMNIRAD® 1000, OMNIRAD® 1300, OMNIRAD® 819, OMNIRAD® 819DW, OMNIRAD® 2022, OMNIRAD® 2100, OMNIRAD® 784, OMNIRAD® 250, OMNIRAD® MBF, OMNIRAD® 1173, OMNIRAD® TPO ® 4265 is used. Among other things, the other UV photoinitiators are used, e.g. Esacure™ One (also IGM Resins).

The composition (ZA) also contains at least one organic solvent as component A4) in addition to the solids content of 100% by weight of components A1) to A3). Such organic solvents can be selected, for example, from the group containing aromatic solvents such as xylene or toluene, ketones such as acetone, 2-butanone, methyl isobutyl ketone, diacetone alcohol, alcohols such as methanol, ethanol, i-propanol, butanol, 1- Methoxy-2-propanol, ethers such as 1,4-dioxane, ethylene glycol n-propyl ether, or esters such as ethyl acetate, butyl acetate, 1-methoxy-2-propyl acetate or mixtures containing these solvents.

Ethanol, i-propanol, butanol, ethyl acetate, butyl acetate, 1-methoxy-2-propanol, diacetone alcohol, xylene or toluene and mixtures thereof are preferred. i-Propanol, butanol, ethyl acetate, butyl acetate, l-methoxy-2- propanol, diacetone alcohol and their mixtures. 1-Methoxy-2-propanol and diacetone alcohol, in particular 1-methoxy-2-propanol, are very particularly preferred.

Composition (ZA) preferably contains, in addition to the solid fraction with 100% by weight of components A1) to A3), 0 to 900% by weight, particularly preferably 0 to 850% by weight, very particularly preferably 200 to 800% by weight. -% of at least one organic solvent.

Adhesion layer B

The adhesion promoter layer B can be obtained or is obtained by curing a composition (ZB). The composition (ZB) can, for example, be cured physically, for example by drying by evaporation of the (co)solvent in which component B1) is dissolved or dispersed. The composition (ZB) includes:

Bl) at least one aqueous hybrid dispersion comprising or consisting of at least one aliphatic polyurethane-polyurea, at least one further aliphatic polymer and at least one dispersant, wherein the at least one aliphatic polyurethane-polyurea is obtainable or was obtained from the reaction of a reaction mixture comprising: a) at least an acyclic aliphatic and/or a cycloaliphatic polyisocyanate, b) at least one polyol selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and copolymers thereof with aliphatic polyesters, polyesteramides, polyethers, polythioethers, polycarbonates, Polyacetals, polyolefins or polysiloxanes and mixtures of at least two thereof, c) at least one isocyanate-reactive compound which also contains dispersing groups or contains groups which, by salt formation in dis penetrating groups can be converted, d) at least one chain extender, the at least one further aliphatic polymer being obtainable or obtained by reacting monomers selected from the group consisting of ethylenically unsaturated hydrocarbons, ethylenically unsaturated esters and ethylenically unsaturated ethers and mixtures at least two of these, and

B2) at least one organic (co)solvent. Suitable binder systems are, for example, in Kittel, Textbook of Paints and Coatings, Vol. 2 "Binders for solvent-based and solvent-free systems", Vol. 2 "Binders for water-dilutable systems", S. Hirzel Verlag, Stuttgart/Leipzig and in Ulrich Meier-Westhues, "Polyurethanes", Vincentz Network GmbH Verlag described.

Examples of suitable acyclic aliphatic and/or a cycloaliphatic polyisocyanate a) for producing the at least one aliphatic polyurethane-polyurea are ethylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. Mixtures of polyisocyanates can also be used. The same applies to polyisocyanates which have been modified by the introduction of urethane, allophanate, urea, biuret, carbodiimide, uretonimine or isocyanurate residues.

The polyol component b) is selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and copolymers thereof with aliphatic polyesters, polyesteramides, polyethers, polythioethers, polycarbonates, polyacetals, polyolefins or polysiloxanes and mixtures of at least two of these. Examples of suitable aliphatic polyether polyols are polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide and polytetrahydrofuran (pTHF 1000, pTHF 2000, BASF SE, Ludwigshafen, DE).

Examples of suitable aliphatic polyester polyols are polyethylene glycol butyrate, polyethylene glycol glutarate, polyethylene glycol adipate, polypropylene glycol butyrate, polypropylene glycol glutarate, polypropylene glycol adipate and polycaprolactonediol.

Examples of suitable aliphatic polyether-polyester polyols are polyester-polyether block copolymers as described in US Pat. No. 6,753,402 B1

In a preferred embodiment of the inventive layer structure, the inventive kit-of-part and/or the inventive method, the at least one polyol b) from which the at least one aliphatic polyurethane-polyurea of the composition (ZB) is constructed is selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and mixtures of at least two thereof, preferably selected from the group consisting of aliphatic polyether polyols, aliphatic polyether-polyester polyols and mixtures of at least two thereof and particularly preferably an aliphatic polyether polyester polyol.

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the at least one polyol b) from which the at least one aliphatic polyurethane-polyurea of the Composition (ZB) is built up, an average molecular weight in the range from 500 g/mol to 6000 g/mol, preferably in the range from 700 g/mol to 3000 g/mol, determined according to DIN EN/ISO 16014-1, where the chromatographic conditions were selected in accordance with DIN 55762-1 (2016).

Suitable isocyanate-reactive compounds c) which also contain dispersing groups or groups which can be converted into dispersing groups by salt formation are, for example, components containing sulphonate or carboxylate groups, such as diamino compounds or dihydroxy compounds which additionally carry sulphonate and/or carboxylate groups , Such as the sodium, lithium, potassium, tert-amine salts of N-(2-aminoethyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid, N-(3 -Aminoproyl) -3-aminopropanesulfonic acid, N-(2-aminoethyl)-3-aminopropanesulfonic acid, the analogous carboxylic acids, dimethylolpropionic acid, dimethylolbutyric acid, the reaction products in terms of a Michael addition of 1 mole of diamine such as 1,2-ethanediamine or isophoronediamine with 2 moles of acrylic acid or maleic acid, and mixtures of at least two of these.

The acids are often used directly in their salt form as sulphonate or carboxylate. However, it is also possible to add some or all of the neutralizing agents required for salt formation only during or after the preparation of the dispersion.

Tertiary amines which are particularly suitable and preferred for salt formation are, for example, triethylamine, dimethylcyclohexylamine and ethyldiisopropylamine. Other amines can also be used for salt formation, such as ammonia, diethanolamine, triethanolamine, dimethylethanolamine, methyldiethanolamine, aminomethylpropanol and also mixtures of the amines mentioned and other amines. It makes sense for these amines to be added only after the isocyanate groups have largely reacted.

It is also possible to use other neutralizing agents such as sodium, potassium, lithium, calcium hydroxide for neutralization purposes.

Further suitable components c) are mono- or difunctional polyethers which have a nonionic hydrophilic effect and are based on ethylene oxide polymers or ethylene oxide/propylene oxide copolymers started from alcohols or amines, such as polyether LB 25 (Covestro AG; Germany) or MPEG 750: methoxypolyethylene glycol, molecular weight 750 g/mol (e.g. Pluriol® 750, BASF SE, Ludwigshafen, Germany).

Preferred components c) are N-(2-aminoethyl)-2-aminoethanesulfonate and the salts of dimethylolpropionic acid and dimethylolbutyric acid. Examples of suitable ketene extenders d) are ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, butylenediamine, hexamethylenediamine, cyclohexylenediamine, piperazine, 2-methylpiperazine, methanediamine, isophoronediamine and adducts of diethylenetriamine with acrylate or hydrolyzed products thereof. This subheading also includes materials such as hydrazine, azines, eg acetonazine, substituted hydrazines, eg dimethylhydrazine, 1,6-hexamethylenebishydrazine, carbodihydrazine, hydrazides of dicarboxylic acids and sulfonic acids, eg adipic mono- or di-hydrazide, oxalic dihydrazide, isophthalic dihydrazide , tartaric dihydrazide, omega-aminocaproic dihydrazide, hydrazides obtained by reacting lactones with hydrazine such as gamma-hydroxybutyric hydrazide, bis-semi-carbazide, bis-hydrazide carbonic acid esters of glycols such as any of the glycols mentioned above. Also suitable are diols such as 1,4-butanediol or 1,6-hexanediol.

The at least one further aliphatic polymer is obtainable or was obtained by reacting monomers selected from the group consisting of ethylenically unsaturated hydrocarbons, ethylenically unsaturated esters and ethylenically unsaturated ethers and mixtures of at least two of these.

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the further aliphatic polymer of the composition (ZB) is obtainable or was obtained by reacting monomers selected from the group consisting of esters of acrylic acid and methacrylic acid, esters and ethers of vinyl alcohol and styrene and mixtures of at least two thereof, preferably selected from the group consisting of esters of acrylic acid and methacrylic acid and mixtures of at least two thereof.

The aliphatic polyurethane-polyurea is produced by reacting components a) to d), optionally in the presence of a catalyst and/or solvent. A prepolymer is preferably first formed from components a), b) and c) and is reacted in a further step with the chain extender d).

The dispersion of the at least one aliphatic polyurethane-polyurea and the at least one further aliphatic polymer in the aqueous system is achieved by either using external surfactants or by incorporating suitable ionic or non-ionic groups into the aliphatic polyurethane-polyurea in order to to make dispersible. Such ionic or nonionic groups are introduced, for example, by an isocyanate-reactive compound which also contains groups with a dispersing action or groups which can be converted into groups with a dispersing action by salt formation. For example, US Pat. No. 4,066,591 describes aqueous dispersions obtained by dispersing an isocyanate-terminated polyurethane prepolymer containing anionic groups in an aqueous medium and then reacting the dispersed prepolymer with suitable chain extenders to obtain polyurethane polyurea.

It is also known to modify the properties of polyurethane-polyurea dispersions by including other aliphatic polymers obtained by polymerization from vinylic monomers. Various patents such as US 3,705,164, 4,198,330 and 4,318,833 describe processes in which the aliphatic polymer is formed in situ by polymerizing one or more vinyl monomers in the presence of an aqueous dispersion of a polyurethane containing anionic salt groups will. In some cases, the polyurethane prepolymer is formed in the presence of, or subsequently diluted with, an organic solvent, which reduces the viscosity of the prepolymer and/or makes it easier to disperse in water. The solvent can then be removed from the dispersion by distillation or it can remain in the dispersion.

Typically, surfactant-free aqueous hybrid dispersions B1) obtainable in this way contain at least one anionic, water-dispersible, aliphatic polyurethane-polyurea and at least one further aliphatic polymer in a weight ratio of from 10:90 to 90:10.

Preferred surfactant-free aqueous hybrid dispersions B1) contain at least one anionic, water-dispersible, aliphatic polyurethane-polyurea and at least one other aliphatic polymer in a weight ratio of from 20:80 to 80:20.

The anionic, water-dispersible, isocyanate-terminated polyurethane prepolymer is a polyurethane prepolymer having acidic groups that impart water-dispersibility. Such prepolymers and methods of making them are well described in the technical literature.

Polyurethane prepolymers with acid centers are, for example, isocyanate-terminated reaction products from i) an organic polyisocyanate, ii) a polymeric polyol with an average molecular weight in the range from 500 g/mol to 6000 g/mol, iii) an isocyanate-reactive compound with at least one acid group and at least two groups which are more reactive towards isocyanates than the acid group, and optionally and iv) a low molecular weight polyol having a molecular weight below 500.

The anionic, water-dispersible, isocyanate-terminated polyurethane prepolymer can be prepared in a conventional manner by reacting a stoichiometric excess of the organic polyisocyanate a) with the polyol b), which has an average molecular weight in the range from 500 g/mol to 6000 g/mol, and the other required isocyanate reactive Compounds c) and d) under substantially anhydrous conditions at a temperature between about 30 and about 130°C until the reaction between the isocyanate groups and the hydroxyl groups is substantially complete. The polyisocyanate and active hydrogen-containing components are suitably reacted in such proportions that the ratio of the number of isocyanate groups to the number of hydroxyl groups is in the range of from about 1.1:1 to about 6:1, preferably in the range of 1.5 : 1 to 3: 1. Optionally, catalysts such as dibutyltin dilaurate and stannous octoate can be used to aid in prepolymer formation.

The solution of the water-dispersible polyurethane prepolymer in the vinyl monomer can be prepared by adding one or more other aliphatic polymerizates to the prepolymer or, which is preferred, by preparing the prepolymer in the presence of one or more vinyl monomers.

Suitable vinyl monomers in which the prepolymer can be dissolved contain one or more polymerizable ethylenically unsaturated groups and are selected from the group consisting of ethylenically unsaturated hydrocarbons, ethylenically unsaturated esters and ethylenically unsaturated ethers and from mixtures of at least two thereof. Preferred monomers are liquid under the temperature conditions of prepolymer formation, although the possibility of using solid monomers together with organic solvents is not excluded. It is also preferred to use monomers that do not contain isocyanate groups or isocyanate-reactive groups.

Thus, for example, suitable monomers are ethylenically unsaturated hydrocarbons, esters and ethers, especially esters of acrylic acid and methacrylic acid, esters and ethers of vinyl alcohol and styrene. Specific examples include butadiene, isoprene, styrene, substituted styrenes, the (Cl-6) lower alkyl esters of acrylic, methacrylic and maleic acid, vinyl acetate, butyrate, acrylate and methacrylate, acrylonitrile, allyl methacrylate, vinyl methyl, - propyl and butyl ether, divinyl ether, divinyl sulfide, vinyl chloride, vinylidene chloride, hexanediol diacrylate, trimethylolpropane triacrylate, and the like. Free acids should not be used as they can destabilize the dispersion.

The prepolymer/vinyl monomer solution can be dispersed in water using techniques known in the art. Preferably, the solution is added to the water with stirring. Alternatively, water can also be stirred into the solution.

The active hydrogen containing chain extender which is reacted with the prepolymer is suitably a polyol, an amino alcohol, ammonia, a primary or secondary aliphatic or alicyclic, aromatic, araliphatic or heterocyclic amine, especially a diamine, hydrazine or substituted hydrazine. Water soluble chain extenders are preferred. Water itself can also be useful. A diamine is particularly preferably used as chain extender.

When the chain extender is other than water, for example a diamine or hydrazine, it can be added to the aqueous dispersion of the prepolymer and vinyl monomer, or alternatively it can be present in the aqueous medium when the prepolymer and monomer are dispersed therein will.

The chain extension can be carried out at elevated, reduced or at room temperature. Suitable temperatures are, for example, from about 5 to 95°C or more, in particular from about 10 to about 45°C.

The amount of chain extender used should be approximately equivalent to the free NCO groups in prepolymer, with the ratio of active hydrogens in chain extender to NCO groups in prepolymer preferably being in the range of 0.7 to 2.00:1. Of course, if water is used as the chain extender then the ratios are not applicable since water acts both as a chain extender and as a dispersing medium and will be present in large excess relative to the free NCO groups.

Conversion of any acidic groups present in the prepolymer to anionic groups can be accomplished by neutralizing the acidic groups before, after, or simultaneously with formation of the aqueous dispersion. Suitable neutralizing agents are, for example, tertiary amines, e.g., triethylamine, 1-ethylmorpholine, 1-ethylpiperidine, dimethylpropan-2-olamine, methyldiethanolamine, or triethanolamine.

The polymerization of the vinyl monomer or monomers to form the at least one other aliphatic polymerizate can be carried out by either of two methods.

In the first method, further monomer (the same or a different vinyl monomer or mixture of vinyl monomers) is added, which can optionally swell the polyurethane. The monomer can then be polymerized using a conventional free radical initiator system. The proportion of the monomer used as a solvent for the prepolymer is usually between 1.5 and 95% by weight, preferably between 2.5 and 80% by weight and in particular between 7 and 50% by weight, based on the total monomers.

In the second method, the polymerization of the vinyl monomer diluent and the feed of the same or a different vinyl monomer or mixture of vinyl monomers are continued to completion. The proportion of monomer used as a solvent for the prepolymer can be as indicated in the first method. In both polymerization methods, those vinyl monomers which are added and polymerized can be used as mentioned above. Functional monomers such as hydroxyalkyl acrylates and methacrylates can also be incorporated at this point since the free isocyanate groups of the prepolymer have reacted with the chain extender.

Suitable free radical initiators are mixtures that partition between the aqueous and organic phases, such as a combination of t-butyl hydroperoxide, isoascorbic acid and Fe-EDTA.

The aqueous polymer dispersions produced by the process are stable for long periods despite the absence of emulsifiers. If appropriate, smaller amounts of solvent can be incorporated into the dispersions.

Surface-modified nanoparticles are optionally introduced during or after the production of the at least one aliphatic polyurethane-polyurea. This can be done by simply stirring in the particles. However, it is also conceivable to use increased dispersing energy, for example by means of ultrasound, jet dispersing or high-speed stirrers based on the rotor-stator principle. Simple mechanical stirring is preferred.

WO 2006/008120 A1 discloses an aqueous dispersion of nanoscale polymer particles made from organic binders, these nanoparticles being present as a highly disperse phase, water and/or an aqueous colloidal solution of a metal oxide as a continuous phase and optionally additives. Such aqueous compositions are used as paint compositions for coating purposes.

Inorganic oxides, mixed oxides, hydroxides, sulfates, carbonates, carbides, borides and nitrides of elements from main groups II to IV and/or elements from subgroups I to VIII of the periodic table, including the lanthanides, are suitable for the inorganic nanoparticles present in the coating. Preferred particles are those made of silicon oxide, aluminum oxide, cerium oxide, zirconium oxide, niobium oxide and titanium oxide, with silicon oxide nanoparticles being particularly preferred.

The particles used have average particle sizes from >1 nm to <200 nm, preferably from >3 nm to <50 nm, particularly preferably from >5 nm to <7 nm. The mean particle size can preferably be determined as a z-average value by means of dynamic light scattering in dispersion. Below 1 nm particle size, the nanoparticles reach the size of the polymer particles. Such small nanoparticles can then lead to an increase in the viscosity of the coating, which is disadvantageous. Above 200 nm particle size, some of the particles can be seen with the naked eye, which is undesirable. Preferably >75%, particularly preferably >90%, very particularly preferably >95% of all the particles used have the sizes defined above. The optical properties of the coating deteriorate with an increasing coarse fraction in the total particle population, and clouding can occur in particular.

The particles can be selected so that the index of refraction of their material matches the index of refraction of the cured radiation-curable coating. Then the coating has transparent optical properties. A refractive index in the range from >1.35 to <1.45 is advantageous, for example.

The non-volatile components of the physically drying layer can, for example, make up the following proportions. The nanoparticles can be present in amounts of >1% by weight to <60% by weight, preferably >5% by weight to <50% by weight and in particular from >10% by weight to <40% by weight. The polyurethane and polyacrylate components contained in the coating agent can then make up the difference to 100% by weight. In general, the specification applies that the sum of the individual parts by weight is < 100% by weight.

In principle, the particles can be used either in powder form or in the form of colloidal suspensions or dispersions in suitable solvents. The inorganic nanoparticles are preferably used in colloidally disperse form in organic solvents (organosols) or particularly preferably in water.

Solvents suitable for the organosols are methanol, ethanol, i-propanol, acetone, 2-butanone, methyl isobutyl ketone, butyl acetate, ethyl acetate, 1-methoxy-2-propyl acetate, toluene, xylene, 1,4-dioxane, diacetone alcohol, ethylene glycol n-propyl ether or any mixture of such solvents. Suitable organosols have a solids content of >10% by weight to <60% by weight, preferably >15% by weight to <50% by weight. Suitable organosols are, for example, silicon dioxide organosols, as are available, for example, under the trade names Organosilicasol® and Suncolloid® (Nissan Chem. Am. Corp.) or under the name Highlink® NanO G (Clariant GmbH).

If the nanoparticles are used in organic solvents (organosols), they are mixed with the polyurethanes during their production before they are dispersed with water. The resulting mixtures are then dispersed by adding water or by transferring them to water. The organic solvent of the organosol can, if required, be removed by distillation with water before or after the dispersing with water, preferably after the dispersing.

For the purposes of the present invention, preference is also given to using inorganic particles in the form of their aqueous preparations. The use of inorganic is particularly preferred Particles in the form of aqueous preparations of surface-modified, inorganic nanoparticles. These can be modified by silanization, for example, before or at the same time as they are incorporated into the silane-modified, polymeric organic binder or an aqueous dispersion of the silane-modified, polymeric organic binder.

Preferred aqueous, commercial nanoparticle dispersions are available under the name Levasil® (Nouryon/Carlyle Group).

If the nanoparticles are used in aqueous form, they are added to the aqueous dispersions of the polyurethanes. In a further embodiment, the aqueous nanoparticle dispersion, which is preferably further diluted with water, is used in the preparation of the polyurethane dispersions instead of water.

Examples of suitable organic (co)solvents B2) are butyl glycol, propylene glycol, propylene glycol mono-n-butyl ether, or diethylene glycol monoethyl ether.

Additives and production of the composition (ZA) and the composition (ZB)

Both the composition (ZA) of the topcoat and the composition (ZB) of the adhesion promoter layer can optionally contain one or more further paint additives. Such paint additives can be selected, for example, from the group containing stabilizers, leveling agents, thickeners, surface additives, pigments, dyes, inorganic nanoparticles, adhesion promoters, UV absorbers, IR absorbers, matting agents, refractive index modifiers, preferably from the group containing stabilizers, leveling agents, Surface additives and inorganic nanoparticles. In preferred embodiments, the composition (ZA) and the composition (ZB) according to the present invention can contain, in addition to the 100% by weight of the non-solvent fractions, 0 to 35% by weight, particularly preferably 0 to 30% by weight particularly preferably 0.1 to 20% by weight of at least one further paint additive. The total proportion of all paint additives present in the paint composition is preferably from 0 to 20% by weight, particularly preferably from 0 to 10% by weight, very particularly preferably from 0.1 to 10% by weight.

As already explained above for the composition (ZB), the paints can also contain inorganic nanoparticles to increase the mechanical resistance, such as scratch resistance and/or pencil hardness.

Inorganic oxides, mixed oxides, hydroxides, sulfates, carbonates, carbides, borides and nitrides of elements from main groups II to IV and/or elements from subgroups I to VIII of the periodic table, including the lanthanides, are suitable as nanoparticles. Preferred nanoparticles are silicon oxide, aluminum oxide, cerium oxide, zirconium oxide, niobium oxide, zinc oxide or titanium oxide nanoparticles, with silicon oxide nanoparticles being particularly preferred. The particles used preferably have average particle sizes (measured by dynamic light scattering in dispersion, determined as the z-average value) of less than 200 nm, preferably from 5 to 100 nm, particularly preferably from 5 to 50 nm. Preferably at least 75%, particularly preferably at least 90%, very particularly preferably at least 95% of all nanoparticles used have the sizes defined above.

Both the composition (ZA) and the composition (ZB) can be produced in a simple manner. In the case of the composition (ZB), the components are mixed with one another at room temperature in compliance with the usual working instructions and are thereby homogenized. In the preparation of the composition (ZA), the thermoplastic polymer is first completely dissolved in the solvent at room temperature or at elevated temperatures. The other obligatory and optionally the optional components are then added to the solution, which has been cooled to room temperature, either in the absence of solvent(s) and mixed together by stirring, or in the presence of solvent(s), for example in the solvent(s) and also through Stir mixed together. The photoinitiator is preferably first dissolved in the solvent or solvents and then the other components are added. Optionally, a further purification by means of filtration, preferably by means of fine filtration, then takes place.

Thermoplastic polymer layer C

Polymers selected from the group consisting of polyacrylate, poly(meth)acrylate, polysulfone, polyurethane, acrylonitrile-butadiene-styrene copolymer (ABS), polyester, polyamide, polycarbonate and their copolymers, blends and coextrudates are used as thermoplastic polymer layer C.

In a preferred embodiment of the layer structure according to the invention, the kit-of-part according to the invention and/or the method according to the invention, the thermoplastic polymer layer C is selected from the group consisting of polyacrylate, poly(meth)acrylate, polyurethane, acrylonitrile-butadiene-styrene copolymer (ABS), polyester, polyamides, polycarbonate-polyester and polycarbonate (acrylonitrile butadiene styrene copolymer) blends and their poly(meth)acrylate coextrudates, polycarbonate and coextruded polycarbonate with a poly(meth)acrylate top layer , Preferably selected from the group consisting of polyacrylate, poly (meth) acrylate, polycarbonate-polyester and polycarbonate (acrylonitrile-butadiene-styrene copolymer) blends and their poly (meth) acrylate coextrudates, polycarbonate and coextruded polycarbonate with a Poly(meth)acrylate top layer, particularly preferably selected from the group consisting of polycarbonate-polyester and polycarbonate-(acrylonitrile-butadiene-styrene) Copolymer) blends and their poly(meth)acrylate coextrudates, polycarbonate and coextruded polycarbonate with a poly(meth)acrylate top layer. Examples of suitable thermoplastics are polyacrylates, poly(meth)acrylates (e.g. PMMA; e.g. Plexiglas® from Röhm), cycloolefin copolymers (COC; e.g. Topas® from Topas Advanced Polymers or Apel® from Mitsui Chemicals, Inc.), polysulfones (Ultrason® from BASF SE or Udel® from Solvay), polyesters such as PET or PEN, acrylonitrile-butadiene-styrene copolymer (ABS, Terlux® from Ineos Styrolution), polycarbonate (PC), polycarbonate/polyester blends, for example PC/PET, polycarbonate/polycyclohexyl methanolcyclohexanedicarboxylate (PCCD), polycarbonate/PBT and mixtures thereof.

Polycarbonates or copolycarbonates and their blends are preferably used, and in particular they are preferably used in the form of a film.

Particular preference is given to using polycarbonate, copolycarbonate or polycarbonate blend or copolycarbonate blend films with a coextruded layer of poly(meth)acrylate.

Suitable polycarbonates for the production of the plastic composition to be used according to the invention as the thermoplastic polymer layer C are all known polycarbonates. These are homopolycarbonates, copolycarbonates and thermoplastic polyester carbonates. The suitable polycarbonates preferably have average molecular weights from 18,000 to 40,000, preferably from 26,000 to 36,000 and in particular from 28,000 to 35,000, determined by measuring the relative solution viscosity in dichloromethane or in mixtures of equal weight amounts of phenol/o-dichlorobenzene, calibrated by light scattering.

The polycarbonates are preferably produced by the phase interface process or the melt transesterification process, which are widely described in the literature. For example on the phase interface method, see H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 p. 33 ff, Polymer Reviews, Vol. 10, “Condensation Polymers by Interfacial and Solution Methods” , Paul W. Morgan, Interscience Publishers, New York 1965, chap. VIII, p. 325, on Drs. U. Grigo, K. Kircher and P. R- Müller "Polycarbonate" in Becker/Braun, Kunststoff-Handbuch, volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna 1992, pp. 118-145 and to EP-A 0 517 044. The melt transesterification process is described, for example, in Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and in Patent specifications DE-B 10 31 512 and US-B 6 228 973 are described.

The polycarbonates are obtained from reactions of bisphenol compounds with carbonic acid compounds, in particular phosgene or, in the melt transesterification process, diphenyl carbonate or dimethyl carbonate. Here homopolycarbonates based on bisphenol-A and copolycarbonates based on the monomers bisphenol-A and l,l-bis-(4- hydroxyphenyl)-3,3,5-trimethylcyclohexane is particularly preferred. Other bisphenol compounds that can be used for polycarbonate synthesis are disclosed, inter alia, in WO-A 2008037364, EP-A 1 582 549, WO-A 2002026862, WO-A 2005113639.

The polycarbonates can be linear or branched. Mixtures of branched and unbranched polycarbonates can also be used.

Suitable branching agents for polycarbonates are known from the literature and are described, for example, in US Pat in literature cited herein. In addition, the polycarbonates used can also be intrinsically branched, in which case no branching agent is added during the production of the polycarbonate. An example of intrinsic branches are so-called Fries structures, as disclosed for melt polycarbonates in EP-A 1 506 249.

In addition, chain breakers can be used in polycarbonate production. Preferred chain terminators are phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof.

The plastic composition(s) of the thermoplastic polymer layer C or the thermoplastic polymer layers C can also contain additives, such as UV absorbers, IR absorbers and other customary processing aids, in particular mold release agents and flow aids, and the customary stabilizers, in particular thermal stabilizers and antistatic agents, pigments, Colorants and optical brighteners included. Different additives or concentrations of additives can be present in each thermoplastic polymer layer C.

The thermoplastic polymer layer C is preferably used in a thickness of >10 μm to <1500 μm, more preferably from >50 μm to <1000 μm and particularly preferably from >200 μm to <500 μm. In addition, the material of the film can contain additives and/or processing aids for film production, such as stabilizers, light stabilizers, plasticizers, fillers such as fibers and dyes. The side of the film intended for coating and the other side of the film can be smooth or have a surface structure, with a smooth surface of the side to be coated being preferred.

In one embodiment, the thermoplastic polymer layer C has a thickness of >10 μm to <1500 μm. This also includes a polycarbonate film with the aforementioned additives and/or processing aids. The thickness of the foil can also be >50 μm to <1000 μm or >200 μm to <500 μm. In a further preferred embodiment, the thermoplastic polymer layer C is a polycarbonate film with a PMMA layer coextruded on at least one side, the thickness of which is in the range of >10 μm and <100 μm, preferably in the range of >15 μm and <60 μm.

Another subject of the present invention is a film insert molding method for producing a molded part, comprising the steps:

(i) providing a layer structure according to the invention, and

(ii) back layers of the layer structure on the uncoated outside of the thermoplastic polymer layer C with a thermoplastic polymer.

Film insert molding in the context of the present invention is a process in which the layer structure according to the invention is three-dimensionally deformed, for example thermally, and then the layer structure is back-coated or back-injected with the thermoplastic polymer on the side facing away from the film. The coating can already include a drying process. Before the backcoating operation, the coating on the surface of the layer structure is preferably cured by means of actinic radiation, preferably UV radiation.

In a preferred embodiment of the method according to the invention, the rear layering in step (ii) takes place by means of extrusion or injection molding, preferably with a polycarbonate melt.

The layer structure according to the invention was preferably produced before being provided in step (i) by a multi-stage process comprising the following steps:

(a) providing a thermoplastic polymer layer C;

(b) coating the thermoplastic polymer layer C with the composition (ZB) to form an adhesion promoter layer B;

(c) drying of the adhesion promoter layer B of the layer structure B-C;

(d) coating the layer structure B-C on the side of the adhesion promoter layer with the composition (ZA) to form a top layer A;

(e) drying the top layer A of the layer construction A-B-C;

(f) optionally cutting, delaminating, printing and/or thermally or mechanically deforming the layered structure ABC; and (g) subjecting the layer structure to actinic radiation to cure top layer A.

Coating with the compositions (ZA) and (ZB) as coating materials can be carried out by the usual processes for coating substrates, in particular films, with liquid coating materials, such as knife coating, spraying, pouring, flooding, dipping, spraying, rolling or spin coating. The flow coating process can be carried out manually with a hose or a suitable coating head or automatically in a continuous flow using flow coating robots and, if necessary, slot nozzles. Preference is given to applying the coating agent by means of a roll-to-roll transfer. The surface of the substrate to be coated (thermoplastic polymer layer C) can be pretreated by cleaning or activation.

Drying follows the application of the coating agent. For this purpose, work is carried out in particular with elevated temperatures in ovens and with moving and optionally also dehumidified air such as, for example, in convection ovens or by means of jet dryers and thermal radiation such as IR and/or NIR. Furthermore, microwaves can be used. It is possible and advantageous to combine several of these drying processes. The drying of the coating in steps (c and e) preferably comprises flashing off at room temperature and/or elevated temperature, such as preferably at 20-200° C., particularly preferably at 40-120° C. After the coating has dried, it is block-resistant, so that the coated thermoplastic polymer layer C, in particular the coated film, can be laminated, printed and/or thermally deformed. In particular, shaping is preferred, since the shape for a three-dimensional plastic part produced using the film insert molding process can be predetermined simply by shaping a coated film.

Advantageously, the conditions for the drying are chosen such that the elevated temperature and/or the thermal radiation does not trigger any polymerization (crosslinking) of the at least one UV-curable monomer and/or at least one UV-curable oligomer of the topcoat layer A, since this is the deformability of the coated film would be disadvantageous. On the other hand, no UV-curable monomers and/or UV-curable oligomers should be removed together with the solvent during drying, since this can impair the desired UV curing. Furthermore, the maximum temperature reached should be selected so low that the film does not deform in an uncontrolled manner.

After the drying/curing step, the coated thermoplastic polymer layer C, in particular the coated film, can be rolled up, optionally after lamination with a protective film on the coating. The rolling up can take place without the coating sticking to the back of the layer structure or the laminating film. It is also possible to cut the layer structure to size and feed the cuts individually or as a stack for further processing.

Curing with actinic radiation is understood as meaning the radical polymerization of ethylenically unsaturated carbon-carbon double bonds by means of initiator radicals which are liberated, for example from the photoinitiators described above, by exposure to actinic radiation. The at least one UV-curable monomer and/or the at least one UV-curable oligomer A2) of the composition (ZA) contain ethylenically unsaturated carbon-carbon double bonds.

Radiation curing is preferably carried out by exposure to high-energy radiation, i.e. UV radiation or daylight, for example with a wavelength of >200 nm to <750 nm, or by irradiation with high-energy electrons (electron radiation, for example from >90 keV to <300 keV) . Medium or high-pressure mercury vapor lamps, for example, serve as radiation sources for light or UV light, it being possible for the mercury vapor to be modified by doping with other elements such as gallium or iron. Lasers, pulsed lamps (known as UV flashlight lamps), halogen lamps or excimer lamps can also be used. The emitters can be installed immovably, so that the item to be irradiated is moved past the radiation source by means of a mechanical device, or the emitters can be movable, and the item to be irradiated does not change its location during curing. The radiation dose usually sufficient for crosslinking in UV curing is in the range from >80 mJ/cm ² to <5000 mJ/cm ² .

In a preferred embodiment, the actinic radiation is therefore light in the UV range.

If appropriate, the irradiation can also be carried out in the absence of oxygen, for example under an inert gas atmosphere or an oxygen-reduced atmosphere. Nitrogen, carbon dioxide, noble gases or combustion gases are preferably suitable as inert gases. Furthermore, the irradiation can take place by covering the coating with media that are transparent to the radiation. Examples of this are plastic foils, glass or liquids such as water.

Depending on the radiation dose and the curing conditions, the type and concentration of any initiator used can be varied or optimized in a manner known to those skilled in the art or by means of preliminary preliminary tests. To harden the deformed foils, it is particularly advantageous to carry out the hardening with a plurality of emitters, the arrangement of which should be selected in such a way that every point of the coating receives the optimal dose and intensity of radiation for hardening. In particular, non-irradiated areas (shadow zones) should be avoided. Furthermore, depending on the thermoplastic polymer layer C used, it can be advantageous to select the irradiation conditions in such a way that the thermal stress on layer C does not become too great. In particular, thin foils and foils made of materials with a low glass transition temperature can tend to uncontrolled deformation if a certain temperature is exceeded as a result of the irradiation. In these cases, it is advantageous to allow as little infrared radiation as possible to act on the substrate using suitable filters or the design of the emitters. Furthermore, the uncontrolled deformation can be counteracted by reducing the corresponding radiation dose. However, it should be noted that a certain dose and intensity of the radiation are necessary for as complete a polymerization as possible. In these cases it is particularly advantageous to cure under inert or reduced-oxygen conditions, since reducing the proportion of oxygen in the atmosphere above the coating reduces the dose required for curing.

Particular preference is given to using mercury lamps or UV LEDs for curing, the latter optionally in combination with IR heat sources, in stationary systems. Photoinitiators are then used in concentrations of >0.1% by weight to <10% by weight, particularly preferably from >0.2% by weight to <3.0% by weight, based on the solids content of the coating. A dose of >80 mJ/cm ² to <5000 mJ/cm ² is preferably used to cure these coatings.

The coated surface of the resulting hardened, coated and optionally shaped layer C, i.e. the layer structure according to the invention, shows very good resistance to solvents, coloring liquids, such as those found in households, and high hardness, good scratch and abrasion resistance with high optical transparency.

The layered structure according to the invention can be used, for example, to produce molded bodies which have structural elements with very small radii of curvature. After curing, the top layer A and the adhesion promoter layer B have good abrasion resistance and chemical resistance.

The layer structure according to the invention is a valuable material for the production of everyday objects. The layer structure according to the invention can be used in the production of vehicle add-on parts, plastic parts such as covers for vehicle (interior) construction and/or aircraft (interior) construction, furniture construction, electronic devices, communication devices, housings and decorative objects. The present invention therefore also relates to the use of the inventive layer structure in the production of vehicle add-on parts, plastic parts such as covers for vehicle (interior) construction and/or aircraft (interior) construction, furniture construction, electronic devices, communication devices, housings and decorative objects. In particular, the layer structure according to the invention is suitable for Manufacture of covers, in particular display and console covers, decorative and light strips, housing parts and components for human-machine interaction components, used both by end users and industrially, in the areas of telecommunications and mobile communications, household appliances, electrical and Electronic devices (incl. gaming, personal care, home care, gardening, toys, leisure, hobbies, sports, gambling, eroticism, etc.), transportation incl. automobiles, motorcycles, agricultural and construction vehicles, non-classic means of transport (segways, scooters, etc.) and aviation including drones, medical technology, packaging and automation / robotics.

A further object of the present invention is a molding obtainable or obtained by the process according to the invention.

Another object of the present invention is a product comprising at least one layer structure according to the invention or at least one molded part according to the invention, the product being selected from the group consisting of covers, decorative and light strips and components for human-machine interaction components, preferably selected from the group consist of display and console covers, decorative and light strips, housing parts, components for human-machine interaction components from the areas of telecommunications, mobile communications, household appliances, electrical and electronic devices for the areas of gaming, personal care, home Care, gardening, toys, leisure, hobbies, sports, gambling and eroticism, transportation from the automotive, motorcycle, agricultural vehicle, construction vehicle, non-classical means of transport, aviation and drones, medical technology, packaging and automation / robotics sectors.

Another object of the present invention is the use of a layer structure according to the invention or a molded part according to the invention for the production of products selected from the group consisting of covers, decorative and light strips and components for human-machine interaction components, preferably selected from the group consisting of Display and console covers, decorative and light strips, housing parts, components for human-machine interaction components in the areas of telecommunications, mobile communications, household appliances, electrical and electronic devices for the areas of gaming, personal care, home care, gardening, toys , leisure, hobbies, sports, gambling and eroticism, transportation from the areas of automobiles, motorcycles, agricultural vehicles, construction vehicles, non-classic means of transport, aviation and drones, medical technology, packaging and automation / robotics.

A further object of the present invention is the use of the kit-of-parts according to the invention in the method according to the invention for producing the layer structure ABC according to the invention. A further object of the present invention is the use of the layer structure ABC according to the invention in the film insert molding process according to the invention for producing a molded part.

The present invention is explained in more detail below with reference to the following figures:

Fig. 1 - Analysis of a layer structure A-B-C according to the invention by means of chemical imaging for

Evidence of an interpenetration layer (IPL) at the B-C interface

Fig. 2 - Comparison of the IR spectra of the individual layers of the layer structure A-B-C according to the invention. Spectrum 1 - IR spectrum substrate layer (PMMA), Spectrum 2 - IR spectrum of the penetration layer (IPL) between substrate and base coat, Spectrum 3 - IR spectrum base coat (PUR-PAC based), Spectrum 4 - IR spectrum top coat (acrylate based).

Fig. 3 - Comparison of the test results of the surface adhesion of paints on thermoplastic films a) OK after cross-cut (GT 0) and b) Not OK after cross-cut (GT 5)

Fig. 4 - Comparison of the test results of the formation of microcracks in paints on thermoplastic films using light microscopy: a) OK after back-injection (no micro-cracks) and b) not OK after back-injection (micro-cracks on edge/corner).

FIG. 1 shows 2 images, an upper image and a lower image, with the upper image forming an enlarged section of the lower image. In Figure 1, the upper figure shows BC part of a layer structure ABC according to the invention shown underneath (lower figure), which comprises a top coat A according to Example A from Table 3, a base coat B according to Examples 11-11 from Table 2 and a polymer layer C made of PMMA. As can be seen in the enlarged upper image, an IPL layer has formed between the base coat layer B and the polymer layer C. The images were created using so-called "chemical imaging", which was carried out with the aid of IR measurements using a Perkin-Elmer IR microscope (Spotlight 400 model). With the combination of ATR technology and array detector (16) a spatial resolution of approx. 2 pm was achieved. In chemical imaging, data from the generated IR spectra are used.

FIG. 2 shows the comparison of the IR spectra of the layers of the layer structure ABC according to the invention. The following individual spectra are shown here: Spectrum 1—IR spectrum of substrate layer (PMMA); Spectrum 2- IR spectrum of the penetration layer (IPL) between substrate and basecoat layer; Spectrum 3 - IR spectrum base coat layer (PUR-PAC based); Spectrum 4 - IR Spectrum Top coat layer (acrylate based). In the so-called fingerprint range (below 1500 cm ¹ ), the following can be clearly seen from the band structure: While the spectra 1 and 4 are very similar due to their chemically comparable structure, this differs Spectrum 3 of the PUR-PAC-based base coat differs greatly from spectrum 1 and 4. Spectrum 2 of the IPL layer contains bands from both spectrum 1 and spectrum 3, which indicates chemical "penetration" of the two layers.

Figure 3 shows the comparison of the test results of the surface adhesion of paints on thermoplastic films according to the cross-cut test according to DIN EN ISO 2409 described in the test methods section: a) after cross-cut with a result that is OK (GT 0) and b) after cross-cut with a result that is not in order and therefore not acceptable (GT 5), since paint detachment from the surface (in the edge area of the incisions) can be clearly seen. The cross-cut test is a generally accepted test of the adhesion of paints up to a thickness of approx. 250 micrometers. In the example shown, a layer structure according to the invention (ABC), Fig. 3 a) compared to the existing prior art (non-inventive, single-layer PUD-based paint), Fig. 3 b) after hydrolysis test (90 ° C, 96% relative humidity , 72 h test duration in the climatic chamber). The advantages of the layer structure according to the invention are clear, as mentioned above.

Figure 4 shows the comparison of the test results of the formation of microcracks in paints on thermoplastic films using light microscopy (table microscope, 10x magnification): a) component after back-injection, which is OK (because there are no micro-cracks) and b) component after back-injection, which is not in order is (since micro cracks on edge / corner). In the example shown, a layer structure according to the invention (ABC), Fig. 4a), compared to the existing prior art (not according to the invention, single-layer acrylate-based paint according to Table 3, Example A), Fig. 4b) after deformation, UV - Hardening and back-molding with polycarbonate (Makrolon®) evaluated as indicated in the example section. The advantages of the layer structure according to the invention also emerge clearly here.

In the combination of Figure 3 and Figure 4, it becomes clear that the layer structure according to the invention unexpectedly combines the application advantages of the two paint systems forming the previous state of the art (hydrolytic stability / paint adhesion and very good processability in injection molding after shaping / curing) and thus progress in terms of of the application properties of paint systems with high chemical resistance. examples

The present invention is further illustrated by the following examples, without however being restricted thereto. Unless otherwise noted, percentages in the examples are % by weight.

In the examples, the compounds listed under their trade names mean:

Bayhydrol® UH XP2648: aliphatic, polyether-polycarbonatediol containing anionic

Polyurethane polyacrylate dispersion, solvent-free (Covestro Deutschland AG, Leverkusen, DE)

Neopac™ E123: aliphatic, polyether-polyesterdiol-containing anionic polyurethane

Polyacrylate dispersion, solvent-free (DSM Coating Resins BV, Waalwijk, NL)

JonCryl® HYB6336: aliphatic, polyether-polyesterdiol-containing, anionic polyurethane-polyacrylate dispersion, solvent-free (BASF SE, Ludwigshafen a. Rh., DE)

JonCryl® HYB6340: araliphatic, polyether-polyesterdiol-containing anionic polyurethane-polyacrylate dispersion, solvent-free (BASF SE, Ludwigshafen a. Rh., DE)

Degalan® M920: Polymethyl methacrylate (gritty, average molar mass approx. 300,000 g/mol)

(Rohm GmbH, Darmstadt, DE)

Bindzil® CC401 : amorphous silica, aqueous colloidal solution

(Levasil® CC401) (Nouryon, Amsterdam, NL)

Esacure™ One: functional 1-hydroxyalkyl aryl ketone photoinitiator

(IGM, Geranzano, IT)

Omnirad® 819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

Edaplan® LA451 Solution of an anionic polyester-polyether additive in water / ethanol

(Muenzing Chemie GmbH, Abstatt, DE)

Tego® Wet KL245 : Polyether siloxane copolymer

(Evonik Resource Efficiency GmbH, Essen, DE) Tego® Glide 450: organomodified polysiloxane

(Evonik Resource Efficiency GmbH, Essen, DE)

BYK 306/346: Solution of a polyether-modified siloxane

(Byk Chemie GmbH, Wesel, DE)

BYK 3560/3565/3566: Polyether macromer modified acrylates

(Byk Chemie GmbH, Wesel, DE)

Borchi®Gel 0625 : non-ionic, polyurethane-based thickener for aqueous media

(Borchers, Westlake OH, USA)

Miramer® M600: Dipentaerythritol penta/hexa-acrylate

(DPHA, Lff. 100%, CAS 60506-81-2, Miwon, Gwanggyo, SK)

DMEA: N,N-dimethylethylamine

(CAS 598-56-1, Merck KGaA, Darmstadt, DE)

Makrofol® DE 1-1: Polycarbonate film (Covestro Deutschland AG, Leverkusen, DE)

Makrofol® SR906: Polycarbonate-polymethacrylate film, coextruded

(Covestro Deutschland AG, Leverkusen, Germany)

Makrofol® HF312: coated polycarbonate film, coating based on an anionic, aliphatic polyurethane dispersion, physically drying and radiation-curing (not according to the invention)

Makrofol® HF338: coated polycarbonate film, coating based on a solvent-based formulation (polymeric, thermoplastic binder and radiation-curing reactive diluent, not according to the invention)

test methods

Assessment of blocking resistance

Classic test methods such as those described in DIN 53150 are not sufficient to simulate the blocking resistance of rolled up, pre-dried coated films, which is why the following test was used: The coating materials were applied to Makrofol® DE 1-1 (375 μm ) applied. After a flash-off phase of 10 minutes at 20° C. to 25° C., the coated films were dried in a forced-air oven at 110° C. for 10 minutes. After a cooling phase of 1 min, a commercially available adhesive laminating film GH-X173 nature (Bischof u. Klein, Lengerich, Germany) with a Plastic roller applied wrinkle-free to an area of 100 mm x 100 mm on the dried coated film. The laminated piece of film was then loaded over its entire area with a weight of 10 kg for 1 hour. The laminating film was then removed and the coated surface assessed visually.

Steel wool scratch rating

The steel wool scratch is determined by using a steel wool no. 00 (Oskar Weil GmbH Rakso, Lahr, Germany) is glued onto the flat end of a 500 g locksmith's hammer, the area of the hammer being 2.5 cm×2.5 cm, ie approx. 6.25 cm ² . The hammer is placed on the surface to be tested without additional pressure, so that a defined load of approx. 560 g is reached. The hammer is then moved back and forth 10 times in double strokes. The exposed surface is then cleaned of fabric residue and paint particles with a soft cloth. The scratching is characterized by haze and gloss values, measured transversely to the direction of scratching using the Micro HAZE plus (20° gloss and haze; Byk-Gardner GmbH, Geretsried, Germany). The measurement is made before and after scratching. The difference values for gloss and haze before and after exposure are given as A gloss and A haze.

Scratch resistance using pencil hardness tester according to ISO 15184/ASTM D3363:

A flat test specimen was prepared from the coated film previously cured by actinic radiation and fixed on a glass plate. The pencil hardness was determined using the Wolf-Wilbum pencil hardness tester from BYK-Gardner and pencils from Cretacolor. Here, based on ISO 15184, the designation of the pencil was specified which, in the test arrangement, caused no surface damage at a pressure of 500 g at an angle of 45°.

Adhesion by cross-cut test according to EN ISO 2409/ASTM D3359:

The adhesive strength of the only predried paint layer of the coated paint film and the adhesive strength of the coating cured by actinic radiation on the paint film were determined. A.) the crosscut with and without adhesive tape tear (adhesive tape used: Scotch™ 610-1 PK from 3M), and b.) the crosscut after storage in hot water at 98 °C after adhesive tape tear (used

adhesive tape see above) for a total of 4 hours, with the assessment being made after each hour. chemical resistance

The shaped component (heating ventilation cover of an automobile) that is cured by actinic radiation and back-injected with thermoplastic material (e.g. Makrolon® 3108) has critical deformation radii of up to r = 0.8 mm. Chemical resistance at these highly deformed and stressed areas of thin paint thickness was evaluated as follows. Aggressive lotions and creams known to those skilled in the art (for example Atrix hand cream, Daimler Chrysler AG - sun oil test mixture DBL7384, Gamier- Ambre Solaire Children SF30 and Nivea Sun - caring sun milk children SF30) were applied to the described areas and then for 24 hours at 80 ° C stored in a heating cabinet. After the load had been applied, residues were carefully removed with water and the samples dried. A visual assessment of the surface in the impact zone was carried out.

Layer thickness of the paint layer

The layer thickness of the lacquer layers cured by actinic radiation was determined a) using an ETA-SST white-light interferometer from ETA-Optik GmbH or b) by means of a light-microscopic thickness measurement after a microtome section.

Rating of solvent resistance

The solvent resistance of the coatings was usually tested with technical grade isopropanol, xylene, 1-methoxy-2-propyl acetate, ethyl acetate, acetone. The solvents were applied to the coating with a soaked cotton swab and covered to prevent evaporation. Unless otherwise stated, an exposure time of 60 minutes at approx. 23 °C was observed. After the end of the exposure time, the cotton swab is removed and the test area wiped clean with a soft cloth. The matching takes place immediately visually and after light scratching with the fingernail.

The following stages are distinguished:

• 0 = unchanged; no visible change; not injured by scratching.

• 1 = slight swelling visible, but not vulnerable to scratching.

• 2 = change clearly visible, hardly injured by scratching.

3 = noticeably altered after firm fingernail pressure destroyed on the surface.

4 = greatly altered after firm fingernail pressure scratched through to the substrate. 5 = destroyed; just wiping off the chemical will destroy the paintwork; the test substance cannot be removed (eaten in).

Within this assessment, the test is usually passed with the characteristic values 0 and 1. Characteristic values > 1 stand for "failed".

Formulation examples

The following steps 1 and 2 as well as Tables 1 to 3 show the production of the paints, which were then subjected to the performance test in the form of the layer structure A-B-C. Table 1 shows the development of the basecoats according to the invention. Table 2 serves to show the optimization of the basecoat formulation according to the invention from Example 11 in Table 1. It is intended to show here that, in principle, various additives can be used in basecoats of this type. Table 3 shows the different top coat formulations tested.

Step 1: Formulation of an aqueous, physically drying base coat ^ composition (ZB) for the production of adhesion promoter layer B according to example 11 from table 1)

A. Preparation of the solvent mixture. Butyl glycol and water were mixed together with stirring (500 rpm).

B. The PUR/PAC hybrid dispersion B1) (eg NeoPac™ E-123) was initially taken and the solvent mixture was added with stirring (1000 rpm) within 5 min. Thereafter, the respective additives, as indicated in Table 1 for formulation examples 1 to 13 (in the case of example 11: BYK 346 etc.), were added stepwise with stirring (500 rpm) with a subsequent stirring time of 5 minutes. The pH was determined and adjusted to a pH of 7.9-8.2 with stirring (500 rpm) by adding N,N-dimethylethylamine in portions. With further stirring (500 rpm), the Levasil® CC 401 was added within 10 minutes and stirred for a further 20 minutes. The thickener Borchi®Gel 0625 was dispersed with the dissolver while stirring vigorously (1000 rpm) and left to remain dispersed for 30 minutes. The pH was determined again; if this was found to be <7.9, it was adjusted again to a value of 7.9-8.2 with N,N-dimethylethylamine. Finally, the lacquer was filtered through a 10 μm bag filter. Table 1: Examples of basecoat formulations I (Nos. 1, 2, 11 according to the invention, gray background = not according to the invention) (in each case in parts by weight):

Table 2: Examples of basecoat formulations II (in each case in parts by weight):

Step 2: Formulation of a solvent-based, physically drying and UV-curing top coat (composition (ZA) for the production of top coat A) (Example A from Table 3)

A. Production of the semi-finished product. 1-Methoxy-2-propanol (MPA) was submitted. BYK 306, Esacure™ One, Omnirad® 819 Tinuvin® 400 and Tinuvin® 123 were added with stirring (500 rpm). It was stirred at room temperature until Esacure™ One was completely dissolved. The solution was filtered through a 5 µm bag filter. When storing the solution, care had to be taken to exclude light. (photoinitiator)

B. 1-Methoxy-2-propanol (MPA) was placed in an inerted stirred reactor. Grit-like Degalan® M 920 was added to the MPA with constant stirring (500 rpm) so that a suspension formed and the granules did not settle. The mixture was slowly heated to 100° C. (boiling point MPA: 119-122° C.) with constant stirring and with the reflux condenser fitted. The wall temperature should not exceed 120 °C. The mixture was stirred at 100° C. for about 4 hours. During this time, a clear solution of the polymer was formed (control: glass drain; no gel particles should be discernible). The viscosity increased. The solution was then cooled to 30.degree. With stirring (100 rpm) the Ha/6/a6nto was added. Stirring was continued at 30° C. for a further 30 minutes in order to produce a homogeneous mixture. More 1-methoxy-2-propanol could either be initially introduced at the beginning or used accordingly for rinsing the receiver. The mixture was then stirred for 2 hours in order to produce a homogeneous mixture (visual inspection: no streaks should be visible). Finally, the product was bottled and filtered through a 100 μm filter.

Table 3: Examples of top coat formulations (based on WO2014198749A1):

Step 3: Production of multi-layer coated plastic films C (coating/drying/laminating - example) The coating of the plastic films C with the aforementioned coating agents took place consecutively on the test coating system using a magnetic doctor blade system over a total width of 300 mm. In a first step, the base paint was coated with a wet film thickness of approx. 65 μm at a feed rate of 1 m/min. The drying section contained 7 zones, each 1 m long. Temperature zone 1: 23 °C, temperature zones 2-6: 110 °C. In a first step, the top coat was coated with a wet layer thickness of approx. 35 μm at a feed rate of 1 m/min. The drying section contained 7 zones, each 1 m long. Temperature zone 1: 23 °C, temperature zones 2-6: 110 °C. After each coating, the dry and non-blocking but still soft paint layer was laminated with a PE/PP protective film to minimize scratches and dust on the surface of the semi-finished product. The substrates used and the semi-finished products obtained are characterized as follows: Table 4: Substrate and semi-finished product characterization

Steps 4 to 7 represent the processing that has been carried out of the layer systems according to the invention and relevant comparative samples, which are required for a final evaluation of the features in terms of application technology (step 8). The expert processing of the layer systems in the so-called film insert molding process (FIM) is a prerequisite for the comparative evaluation of the different layer systems.

Step 4: Screen printing of plastic foils coated on one side (generic example)

PC and (Makrofol® DE 1-1), PC/PMMA (Makrofol® SR906) were partially screen printed and dried as sheets according to the manufacturer's instructions. Noriphan® HTR was specially developed for back-injection molding of films and has been in use since 1997. On the one hand, back-printing can be used to create a decoration on the foil, on the other hand, the color also serves as an adhesion promoter for back-injection molding with PC/ABS materials.

Semi-automatic screen printing machine: ESC (Europa Siebdruck Centrum)

Screen fabric: 80 THT polyester

Squeegee: RKS squeegee

Dry film layer thickness: 10-12 pm

The printed sheets were predried using a continuous tunnel oven (hot air/IR flat channel, manufacturer SPS, Wuppertal) at a speed of 3 m/min (film temperature 85° C.). All film goods were then dry to the touch and block-resistant. Screen printing ink: Noriphan® HTR 952

Number of print layers: 2x

Post-drying: 3 hours at 80°C

The manufacturer recommends post-drying for back-injection of the foils or colors in order to reduce the residual solvent content.

Step 5: Thermoforming / High Pressure Forming of Back Printed and Front Paint Coated Plastic Sheets (Generic Example)

The HPF deformation tests were carried out on a SAMK 360 system (manufacturer HDVF Kunststoffmaschinen GmbH). The tool was electrically heated to 100 °C. The foil was heated by means of an IR radiator at 240-260-280 °C. The heating time was 16 seconds (sec). A foil temperature of approx. 170 °C was reached. The deformation took place at a deformation pressure of 100 bar. The deformation tool was an HL bezel.

The film sheet was fixed in the exact position on a pallet. The pallet drove through the forming station into the heating zone and stayed there for the set time (16 s). The film was heated in such a way that the film briefly experienced a temperature above the softening point, the core of the film was approx. 10-20° C. colder. As a result, the film was relatively stable as it entered the forming station.

In the shaping station, the film was fixed over the actual tool by closing the tool; at the same time, the film was formed over the tool using gas pressure. The pressure holding time ensured that the film molded the tool precisely. After the holding time, the gas pressure was released again. The tool opened and the formed film was moved out of the forming station.

The film was then removed from the pallet and could now be cured with UV light.

With the tool used, radii were mapped down to 1 mm.

Mold Tool : HVAC Panel TCF= Internal Test Tool;

Heating ventilation screen for the production of foils for the

car interior design

Machine: HD VF Penzberg, plastics machines (Type: SAMK 360)

Temp. Radiant heater: Upper heater: 280 °C - 260 °C - 240 °C

Bottom heater: 280℃ - 260℃ - 240℃

Deformation pressure : 100 bar

Pressure holding time: 10 seconds (sec) Air heating: 300°C

Closing speed: 75%

Opening speed: 40%

Heating times: 16 seconds for Makrofol® DE1-1, approx. 180°C surface temperature

16 seconds for Makrofol® SR906, approx. 180°C surface temperature

Step 6: UV curing of formed, printed and coated plastic films

(generic example)

The UV curing of the coating according to the invention was carried out using an evo 7 dr high-pressure mercury vapor lamp (ssr engineering GmbH, Lippstadt, Germany). The system was equipped with dichroic reflectors and quartz discs and had a specific power of 160 W/cm. The surface temperature during UV curing should reach > 60 °C.

The information on the UV dose was determined using a Lightbug ILT 490 (International Light Technologies Inc., Peabody MA, USA). The data on the surface temperature were determined using temperature test strips from the RS brand (order number 285-936; RS Components GmbH, Bad Hersfeld, Germany).

UV system: SSR

Lamp type: Mercury CM emitter 80W/cm

Lamp spacing: 50mm

UV intensity: 1200mW/ ^cm2

UV dose: 2 passes each 1300mJ/cm ²

Tape feed: 4 m/min

Step 7: Making Injection Molding (FIM) Mold Parts

The tests were carried out on an Arburg Allrounder 560 C 2000-675/350 injection molding machine. The machine has a screw diameter of 45 mm and either the Covestro fan heater screen or a special test geometry for testing microcracks was used as the tool.

The three-dimensional (3D) shaped, transparent films were back-injected with Makrolon® 2447 (polycarbonate, Bayer) with a melt temperature of 280 °C. The filling time for filling the mold was 2 seconds. The mold temperature was varied. Good results were achieved with a mold temperature in the range of > 60 °C and < 80 °C. There was no visual negative effect in this regard. The holding pressure time was 12 seconds and the cooling time was 20 seconds. Plant type: ARBURG 570C, Arburg (Type: Allrounder 2000-675)

Injection temperature: 280°C mass

Mold temperature: sprue side = foil side 60°C; Closing side= 80°C

Injection pressure: 890 bar

Back injection material: Makrolon® 2447 (polycarbonate, Covestro AG, Leverkusen, DE)

Filling time: 2 sec

Step 8: Checking the surfaces of the formed foils and molded parts

Step 8 serves to document which performance test results were obtained with different layer systems according to the invention or corresponding to the prior art. It was thus possible to show that each paint layer of the layer structure according to the invention, taken on its own, provides unsatisfactory or worse application-related results than the overall layer system ABC: the adhesion promoter layer alone does not pass all the tests (in particular: solvent resistance is poor) like the top layer (in particular: adhesion only on PMMA surfaces, not on PC). Only a combination of adhesion promoter layer and top layer provides a combination of properties that is advantageous in comparison to commercial systems and superior to the prior art (cf. Tables 5 and 6 vs. Tables 7 and 8).

Moldings that were produced with commercially available comparison products were used as reference materials. The following surfaces were evaluated as examples:

Makrofol® HF312, Covestro AG, Leverkusen, DE (PUD-based paint on polycarbonate film)

Makrofol® HF338, Covestro AG, Leverkusen, DE (acrylic paint based on PC/PMMA film)

1 h Regeneration bei 23 °C) GT 0 (PMMA) GT 0 (PMMA) Table 5: Experimental results - adhesion promoter layers according to the invention (adhesion to polycarbonate and poly(meth)acrylate surfaces):

1 h regeneration at 23 °C) GT 0 (PMMA) GT 0 (PMMA)

Table 6: Experimental results - topcoats according to the invention (adhesion only to poly(meth)acrylate surfaces):

Table 7: Experimental results - coating systems according to the invention (adhesion to polycarbonate and poly(meth)acrylate surfaces):

Table 8: Experimental results—not according to the invention, commercially available coating systems (adhesion either (exclusively) to polycarbonate or poly(meth)acrylate surfaces):

Claims

- 56 - patent claims 1. Layer structure comprising at least the following directly consecutive, mutually adhesively bonded layers in the sequence A-B-C: A: Top layer obtainable or obtained by curing a composition (ZA) comprising: Al) at least one thermoplastic polymer with an average molecular weight Mw of at least 100,000 g/mol, determined in accordance with DIN EN/ISO 16014-1, the chromatographic conditions being selected in accordance with DIN 55762-1 (2016) and in a content of at least 30 wt % of the solid part of the composition (ZA), A2) at least one UV-curable monomer and/or at least one UV-curable oligomer in a content of at least 30% by weight of the solid fraction of the composition (ZA), A3) at least one photoinitiator in a content of >0.1% by weight to <10% by weight of the solids content of the composition (ZA), and A4) at least one organic solvent, where the proportion of ethylenically unsaturated groups is at least 3 mol per kg of the solids content of the composition (ZA) and component A2) has an arithmetic average of at least 3 ethylenically unsaturated groups per molecule; B: Adhesion promoter layer obtainable or obtained by curing a composition (ZB) comprising: Bl) at least one aqueous hybrid dispersion comprising or consisting of at least one aliphatic polyurethane-polyurea, at least one further aliphatic polymer and at least one dispersant, wherein the at least one aliphatic polyurethane-polyurea is obtainable or was obtained from the reaction of a reaction mixture comprising: a) at least an acyclic aliphatic and/or a cycloaliphatic polyisocyanate, b) at least one polyol selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and copolymers thereof with aliphatic polyesters, polyesteramides, polyethers, polythioethers, polycarbonates, Polyacetals, polyolefins or polysiloxanes and mixtures of at least two of these, - 57 - c) at least one isocyanate-reactive compound which also contains dispersing groups or groups which can be converted into dispersing groups by salt formation, d) at least one chain extender, where the at least one further aliphatic polymer is obtainable or was obtained by the reaction of monomers selected from the group consisting of ethylenically unsaturated hydrocarbons, ethylenically unsaturated esters and ethylenically unsaturated ethers and mixtures of at least two of these, and B2) at least one organic (co)solvent, and C: thermoplastic polymer layer, where the polymer is selected from the group consisting of polyacrylate, poly(meth)acrylate, polysulfone, polyurethane, acrylonitrile butadiene styrene copolymer (ABS), polyester, polyamide, polycarbonate and their copolymers, blends and coextrudates . Kit of parts for producing a layer structure according to Claim 1, containing at least one uncured composition (ZA), at least one uncured composition (ZB) and a thermoplastic polymer layer C, the composition (ZA): Al) at least one thermoplastic polymer with an average molecular weight Mw of at least 100,000 g/mol, determined in accordance with DIN EN/ISO 16014-1, the chromatographic conditions being selected in accordance with DIN 55762-1 (2016) and in a content of at least 30 wt % of the solid part of the composition (ZA), A2) at least one UV-curable monomer and/or at least one UV-curable oligomer in a content of at least 30% by weight of the solid fraction of the composition (ZA), A3) at least one photoinitiator in a content of >0.1% by weight to <10% by weight of the solids content of the composition (ZA), and A4) comprises at least one organic solvent, and wherein the proportion of ethylenically unsaturated groups is at least 3 mol per kg of the solids content of the composition (ZA) and component A2) has an arithmetic mean of at least 3 ethylenically unsaturated groups per molecule; where the composition (ZB): - 58 - Bl) at least one aqueous hybrid dispersion comprising or consisting of at least one aliphatic polyurethane-polyurea, at least one further aliphatic polymer and at least one dispersant, wherein the at least one aliphatic polyurethane-polyurea is obtainable or was obtained from the reaction of a reaction mixture comprising: a) at least one acyclic aliphatic and/or a cycloaliphatic polyisocyanate, b) at least one polyol selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and copolymers thereof with aliphatic polyesters, polyesteramides, polyethers, polythioethers, polycarbonates, polyacetals , Polyolefmen or polysiloxanes and mixtures of at least two thereof, c) at least one isocyanate-reactive compound which also contains dispersing groups or contains groups which are formed by salt formation in di dispersing groups can be converted, d) at least one chain extender, the at least one further aliphatic polymer being obtainable or obtained by reacting monomers selected from the group consisting of ethylenically unsaturated hydrocarbons, ethylenically unsaturated esters and ethylenically unsaturated ethers and from mixtures at least two of these, and B2) comprises at least one organic (co)solvent, and wherein the thermoplastic polymer layer C is selected from the group consisting of polyacrylate, poly(meth)acrylate, polysulfone, polyurethane, acrylonitrile-butadiene-styrene copolymer (ABS), Polyester, polyamide, polycarbonate and their copolymers, blends and coextmdaten. Method for producing a layer structure A-B-C according to Anspmch 1, comprising the steps: (i) Providing a thermoplastic polymer layer C, wherein the thermoplastic polymer layer C is selected from the group consisting of polyacrylate, poly(meth)acrylate, polysulfone, polyurethane, acrylonitrile-butadiene-styrene copolymer (ABS), polyester, polyamide, polycarbonate and their copolymers, blends and coextmdaten; - 59 - (ii) coating the thermoplastic polymer layer C with a composition (ZB), wherein the composition (ZB): Bl) at least wherein the one aqueous hybrid dispersion comprising or consisting of at least one aliphatic polyurethane-polyurea, at least one further aliphatic polymer and at least one dispersant, wherein the at least one aliphatic polyurethane-polyurea is obtainable or was obtained from the reaction of a reaction mixture comprising: a ) at least one acyclic aliphatic and/or a cycloaliphatic polyisocyanate, b) at least one polyol selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and copolymers thereof with aliphatic polyesters, polyester amides, polyethers, polythioethers, Polycarbonates, polyacetals, polyolefins or polysiloxanes and mixtures of at least two of these, c) at least one isocyanate-reactive compound which also contains groups having a dispersing action or groups which are formed by salt formation ung can be converted into dispersing groups, d) at least one chain extender at least one further aliphatic polymer is obtainable or was obtained by reacting monomers selected from the group consisting of ethylenically unsaturated hydrocarbons, ethylenically unsaturated esters and ethylenically unsaturated ethers and mixtures of at least two of these, and B2) comprises at least one organic (co)solvent, and (iii) drying and optionally curing the composition (ZB) to obtain an adhesion promoter layer B; (iv) coating the adhesion promoter layer B from step (iii) with a composition (ZA), wherein the composition (ZA): Al) at least one thermoplastic polymer with an average molecular weight Mw of at least 100,000 g/mol, determined in accordance with DIN EN/ISO 16014-1, the chromatographic conditions being selected in accordance with DIN 55762-1 (2016) and in a content of at least 30 wt % of the solid part of the composition (ZA), - 60 - A2) at least one UV-curable monomer and/or at least one UV-curable oligomer in a content of at least 30% by weight of the solid fraction of the composition (ZA), A3) at least one photoinitiator in a content of >0.1% by weight to <10% by weight of the solids content of the composition (ZA), and A4) comprises at least one organic solvent, and wherein the proportion of ethylenically unsaturated groups is at least 3 mol per kg of the solids content of the composition (ZA) and component A2) has an arithmetic mean of at least 3 ethylenically unsaturated groups per molecule; (v) drying the composition (ZA) to obtain an uncured top layer A; (vi) optionally cutting, delaminating, printing and/or thermally or mechanically deforming the layer structure from (v); and (vii) subjecting the layer structure from (v) or (vi) to actinic radiation to cure the top layer A, with the layer structure ABC being obtained. Layer structure according to claim 1, kit-of-part according to claim 2, or method according to claim 3, wherein the at least one thermoplastic polymer Al) of the composition (ZA) has an average molecular weight Mw in the range from 100,000 g/mol to 500,000 g/mol, preferably in the range from 250,000 g/mol to 350,000 g/mol, determined in accordance with DIN EN/ISO 16014-1, the chromatographic conditions being selected in accordance with DIN 55762-1 (2016). Layer structure according to claim 1 or 4, kit-of-part according to claim 2 or 4, or method according to claim 3 or 4, wherein the at least one thermoplastic polymer Al) of the composition (ZA) is selected from the group consisting of esters of acrylic acid and Methacrylic acid, aromatic polyesters, cellulose esters, polyvinyl acetals, polystyrene and mixtures of at least two of these. Layer structure according to claim 1 or 4, kit-of-part according to claim 2 or 4, or method according to claim 3 or 4, wherein the at least one thermoplastic polymer Al) of the composition (ZA) is a polymethyl methacrylate homopolymer or polymethyl methacrylate copolymer on methyl methacrylate base with a methyl methacrylate content of more than 70% by weight, preferably at least one polymethyl methacrylate homopolymer or polymethyl methacrylate copolymer of in each case 70% by weight to 99.5% by weight methyl methacrylate and 0.5% by weight up to 30% by weight of methyl acrylate, particularly preferably at least one polymethyl methacrylate homopolymer or Polymethyl methacrylate copolymer of in each case 90% by weight to 99.5% by weight methyl methacrylate and 0.5% by weight to 10% by weight methyl acrylate, in particular where the at least one thermoplastic polymer has an average molecular weight Mw of at least 100,000 g/mol and preferably has an average molecular weight Mw of at least 250,000 g/mol, determined according to DIN EN/ISO 16014-1, the chromatographic conditions being selected according to DIN 55762-1 (2016). Layer structure according to claim 1 or 4 to 6, kit-of-part according to claim 2 or 4 to 6, or method according to claim 3 to 6, wherein the at least one polyol b) from which the at least one aliphatic polyurethane-polyurea of the composition ( ZB) is constructed, is selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aliphatic polyether-polyester polyols and mixtures of at least two thereof, preferably selected from the group consisting of aliphatic polyether polyols, aliphatic polyether-polyester polyols and mixtures at least two of these, and most preferably an aliphatic polyether-polyester polyol. Layer structure according to claim 1 or 4 to 7, kit-of-part according to claim 2 or 4 to 7, or method according to claim 3 to 7, wherein the at least one polyol b) from which the at least one aliphatic polyurethane-polyurea of the composition ( ZB) is constructed, has an average molecular weight in the range from 500 g / mol to 6000 g / mol, preferably in the range from 700 g / mol to 3000 g / mol, determined according to DIN EN / ISO 16014-1, the chromatographic Conditions according to DIN 55762-1 (2016) were selected. Layer structure according to claim 1 or 4 to 8, kit-of-part according to claim 2 or 4 to 8, or The method according to claim 3 to 8, wherein the further aliphatic polymer of Composition (ZB) is obtainable or was obtained by the reaction of monomers selected from the group consisting of esters of acrylic acid and methacrylic acid, esters and ethers of vinyl alcohol and styrene and mixtures of at least two thereof, preferably selected from the group consisting of esters of acrylic acid and methacrylic acid and mixtures of at least two thereof. Layer structure according to claim 1 or 4 to 9, kit-of-part according to claim 2 or 4 to 9, or method according to claim 3 to 9, wherein the thermoplastic polymer layer C is selected from the group consisting of polyacrylate, poly(meth)acrylate, Polyurethane, acrylonitrile-butadiene-styrene copolymer (ABS), polyester, polyamides, polycarbonate-polyester and polycarbonate (acrylonitrile-butadiene-styrene-copolymer) blends and their poly(meth)acrylate coextrudates, polycarbonate and coextruded polycarbonate a poly(meth)acrylate top layer, preferably selected from the group consisting of polyacrylate, poly (Meth)acrylate, polycarbonate-polyester and polycarbonate (acrylonitrile-butadiene-styrene copolymer) blends and their poly(meth)acrylate coextrudates, polycarbonate and coextruded polycarbonate with a poly(meth)acrylate top layer, particularly preferably selected is from the group consisting of polycarbonate-polyester and polycarbonate-(acrylonitrile-butadiene-styrene-copolymer) blends and their poly(meth)acrylate coextrudates, polycarbonate and coextruded polycarbonate with a poly(meth)acrylate top layer. 11. Layer structure according to claim 1 or 4 to 10 or method according to claim 3 to 10, wherein the dried and cured top layer A has a layer thickness in the range from 1 μm to 50 μm, preferably 5 μm to 25 μm, particularly preferably 8 μm to 15 μm and wherein the dried adhesion promoter layer B has a layer thickness in the range from 2 μm to 60 μm, preferably from 10 μm to 30 μm, particularly preferably from 18 μm to 25 μm. 12. Film insert molding process for producing a molded part, comprising the steps: (i) providing a layer structure according to any one of claims 1 or 4 to 11, and (ii) back layers of the layer structure on the uncoated outside of the thermoplastic polymer layer C with a thermoplastic polymer. 13. The method according to claim 12, wherein the rear layering in step (ii) takes place by means of extrusion or injection molding, preferably with a polycarbonate melt. 14. molding obtainable or obtained by the method according to any one of claims 12 and 13. 15. Product comprising at least one layer structure according to one of claims 1 or 4 to 11 or at least one molded part according to claim 14, wherein the product is selected from the group consisting of covers, decorative and light strips and components for human-machine interaction Components, preferably selected from the group consisting of display and console covers, decorative and light strips, housing parts, components for human-machine interaction components from the fields of telecommunications, mobile communications, household appliances, electrical and electronic devices for gaming, Personal care, home care, gardening, toys, leisure, hobbies, sports, gambling and eroticism, transportation from the automotive, motorcycle, agricultural vehicle, construction vehicle, non-classical means of transport, aviation and drones, medical technology, packaging and automation / robotics sectors. 16. Use of a layer structure according to one of claims 1 or 4 to 11 or a molded part according to claim 14 for the production of products is selected from the group consisting of covers, decorative and light strips and components for human-machine interaction components, preferably selected from the group consist of display and - 63 - Console covers, decorative and light strips, housing parts, components for human-machine interaction components in the areas of telecommunications, mobile communications, household appliances, electrical and electronic devices for the areas of gaming, personal care, home care, gardening, toys, leisure, Hobbies, sports, gambling and eroticism, transportation from the areas of automobiles, motorcycles, agricultural vehicles, construction vehicles, non-classic means of transport, Aviation and drones, medical technology, packaging and automation / robotics.