Acrylic film with improved uv protection properties

Abstract

The present invention relates to a transparent weatherable film for protecting various substrates against solar radiation. In one embodiment of the invention, the film comprises at least two layers A and B, wherein the layer A has a spectral transmittance of no more than 10% at any wavelength λ A ; wherein 270 nm ≤ λ A ≤ 360 nm; and the layer B has a spectral transmittance of no more than 10% at any wavelength λ B ; wherein 270 nm ≤ λ B ≤ 370 nm. In another embodiment of the invention, the film comprises at least two layers A and B, wherein the layer A has a spectral transmittance of no more than 20% at any wavelength λ A ; wherein 270 nm ≤ λ A ≤ 310 nm; and the layer B has a spectral transmittance of no more than 10% at any wavelength λ B ; wherein 270 nm ≤ λ B ≤ 370 nm.

Description

Technical Field

[0001] This invention relates to a multilayer PMMA-based film comprising at least two distinct layers, each containing at least one UV absorber. Typically, the film of this invention is a co-extruded film. The film exhibits exceptionally high UV resistance, high weather resistance, and excellent mechanical properties. Therefore, the film of this invention is highly suitable for outdoor applications, such as surface protection of materials (e.g., polyvinyl chloride (PVC)), and is suitable for use in high-pressure laminates (HPLs).

[0002] HPL is typically prepared by laminating melamine and phenolic resin-impregnated paper onto each other under high pressure (at least 3 MPa, spec.) and at temperatures above 120°C for a cycle time typically between 30 and 100 minutes. The resulting composite material is fitted with a decorative outer layer to achieve visual effects such as wood-like finishes or monochromatic decorative effects. These decorative HPLs are used in a variety of applications, including but not limited to tabletops, doors, furniture, kitchen countertops, and sheets for cladding walls, balconies, or facades. Indoor applications generally do not require special protection against UV radiation, but the melamine resin surface must be fitted with an additional protective layer for outdoor use, where unprotected melamine resin surfaces can exhibit significant degradation even after a relatively short period. Background Technology

[0003] Polymethyl methacrylate (PMMA) exhibits excellent weather resistance and is therefore particularly suitable for any application in outdoor areas subject to climate aging. For this reason, PMMA-based films are already well-established in the market as surface protective films for colored polyvinyl chloride (PVC) window profiles. The demand for surface protective films that significantly exceed existing requirements for weather resistance is growing. Commercially available films typically use benzotriazole-type UV absorbers for stabilization against UV radiation (wavelengths 300 to 400 nm). These UV absorbers are known to significantly lose their activity over approximately 15 years. Climate-resistant protective films modified with them first become dull, then develop microcracks, and subsequently crack. However, these UV absorbers also have advantageous properties: they are color-neutral (no yellowing index), non-volatile (important for film extrusion), and inexpensive.

[0004] WO 2007 / 0074138 A1 describes a PMMA-based membrane that outperforms commercially available membranes to date in terms of weather resistance and provides improved climate aging stability for more than 10 years. The membrane typically uses a combination of benzotriazole-type UV absorbers, triazine-type UV absorbers, and hindered amines (HALS, hindered amine light stabilizers). These components are used as a mixture during the manufacturing process of the membrane.

[0005] US2008 / 0311406 A1 teaches a three-layer membrane consisting of the following layers: an outer PVDF layer, an intermediate layer composed of a PVDF-PMMA blend, and a layer containing, for example, a PVDF-PMMA blend. The film contains a UV absorber (234) and an adhesion promoter layer, which in particular comprises an anhydride of methacrylic acid. A particular advantage of the film is that it does not exhibit white discoloration when tested in water at 100°C for 2 hours, and it also shows good adhesion to melamine-impregnated paper. However, the film only has moderate long-term weather resistance.

[0006] WO 2015 / 180995 A1 discloses a UV protective film suitable for lamination onto a high-pressure laminate (HPL). The film has the following layers bonded to each other from the outside to the inside: a layer A comprising a fluoropolymer, a PMMA layer B comprising at least one UV stabilizer and / or UV absorber, and a layer C comprising at least one adhesion promoter and at least one poly(meth)acrylate, wherein layer C can be laminated with resin-impregnated paper to obtain the HPL, and layers B and / or C comprising at least one impact modifier. This film exhibits excellent long-term weather resistance, does not show delamination, has no bluish sheen, and possesses favorable optical properties, particularly a low haze value.

[0007] In recent years, HPL has been increasingly used in building applications in countries with relatively warm and humid climates and longer average sunshine durations. Furthermore, due to ongoing global warming and ozone layer depletion, HPL used in such applications is exposed to higher temperatures and increasingly intense solar UV radiation. This places even more stringent requirements on PMMA-based membranes used in these countries.

[0008] For example, unplasticized polyvinyl chloride (PVC-U) window profiles and doors with laminated decorative films need to meet standard RAL-GZ 716 (Climate M, 30 GJ / m²). 2(Total irradiation exposure). Manufacturers of PVC window profiles and doors with laminated decorative films are constantly developing products with increasingly higher long-term weather resistance. Therefore, decorative PVC films with protective acrylic films used in these applications are expected to withstand climate aging in Central Europe for approximately 30 years. Summary of the Invention

[0009] Purpose of the invention

[0010] There remains a persistent demand for PMMA-based films that offer superior weather resistance compared to those currently available on the market, and particularly provide improved outdoor stability over a longer period (up to 15 years), even in regions with warm and humid climates and long average daylight hours. Such films should provide inherently improved stability against UV exposure and weathering, as well as improved stability in their UV protection (identifiable by the stability of the color gamut of the colored layer covering the protective film). Furthermore, it is desirable that the films be substantially color-neutral, possess good mechanical properties, and exhibit virtually no stress whitening.

[0011] As used herein, the term "stability" refers not only to the inherent stability of the membrane relative to the effects of climate aging and mechanical damage, but also to the sustainability of its protective function. Invention Overview

[0013] This invention is based on the surprising discovery that the long-term climate stability of the membrane described in WO 2007 / 0074138 A1 can be further improved by placing the UV absorber used in WO 2007 / 0074138 A1 in at least two separate layers. In particular, it has been shown to be advantageous for the layer exposed to outdoor solar radiation to contain at least one triazine-type UV absorber, while the underlying layer contains at least one benzotriazole-type UV absorber. Although the UV absorbers of WO2007 / 0074138 A1 are located in separate layers in the membrane of this invention, the synergistic effect resulting from their presence is even enhanced. Furthermore, the inventors of this invention have found that the triazine-type UV absorber can be replaced by inorganic UV absorbers of glass, such as titanium dioxide, tin dioxide, or glass beads or glass powder, without affecting the long-term stability of the resulting membrane.

[0014] Therefore, the diaphragm of the present invention successfully solves the technical problems described above.

[0015] In addition, the diaphragm of the present invention provides the following advantages:

[0016] It can be used to laminate various substrates at varying temperatures and when using different laminating equipment. The resulting laminated products have a highly uniform appearance and are largely unaffected by processing conditions such as lamination temperature or lamination roller material.

[0017] It has excellent weather resistance and, for example, very good chemical resistance with respect to commercially available cleaning compositions.

[0018] It maintains an attractive, uniform appearance over a longer period of time.

[0019] It can be manufactured in an extrusion machine in a cost-effective manner.

[0020] As will be readily understood by those skilled in the art, the term "film" as used herein refers to a sheet with a thickness of less than 5 mm, more preferably less than 1 mm. Although the films of the present invention can be advantageously used as protective coatings, the term "film" as used herein should generally be distinguished from the term "coating." A coating is typically the top layer of a multilayer substrate and cannot be processed separately from said substrate. In contrast to a coating, the film of the present invention is not necessarily a layer of a multilayer article, i.e., it is not necessarily attached to any substrate, and therefore can be processed separately and used for a variety of different purposes.

[0021] In a first aspect, the present invention relates to a multilayer film comprising at least layer A and layer B, wherein...

[0022] Layer A includes a total weight meter based on layer A:

[0023] 0.0 to 99.9% by weight of poly(meth)acrylate;

[0024] 0.0 to 95.0% by weight of one or more impact modifiers;

[0025] 0.0 to 30.0% by weight of fluoropolymers;

[0026] 0.1 to 5.0% by weight of the first UV absorber;

[0027] 0.0 to 5.0% by weight of one or more UV stabilizers;

[0028] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer A is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 99.9% by weight, based on the weight of layer A; and the cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer A is at any wavelength λ A The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ A ≤360nm; and

[0029] Layer B includes a total weight meter based on layer B:

[0030] 0.0 to 99.9% by weight of poly(meth)acrylate;

[0031] 0.0 to 85.0% by weight of one or more impact modifiers;

[0032] 0.1 to 5.0% by weight of a second UV absorber that is different from the first UV absorber;

[0033] 0.0 to 5.0% by weight of one or more UV stabilizers; and

[0034] 0.0 to 20.0% by weight of an adhesion-promoting copolymer, the adhesion-promoting copolymer comprising

[0035] Contains: based on the weight of the adhesion-promoting copolymer:

[0036] (i) 70.0 to 95.0% by weight of methyl methacrylate;

[0037] (ii) 0.5 to 15.0% by weight of maleic anhydride; and

[0038] (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers, which have no functional groups other than vinyl functional groups; and

[0039] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer B is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 99.9% by weight, based on the weight of layer B; and the cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer B is at any wavelength λ B The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ B ≤370nm.

[0040] Additionally, layer A contains no more than 0.1% by weight, preferably no more than 0.05% by weight, of the second UV absorber, and layer B contains no more than 0.1% by weight, preferably no more than 0.05% by weight, of the first UV absorber.

[0041] According to the present invention, the first UV absorber is different from the second UV absorber.

[0042] According to the present invention, the film is applied to a substrate such that layer A faces the environment and layer B faces the surface of the substrate.

[0043] In this embodiment, the first UV absorber is typically an organic UV absorber, such as a triazine-type UV absorber. In a particularly preferred embodiment, layer A comprises a triazine-type compound as the first UV absorber, and layer B comprises a benzotriazole-type compound as the second UV absorber.

[0044] The spectral transmittance of layers A and B can be measured using a suitable instrument (e.g., a Cary 5000 spectrophotometer available from the former Varian Inc. (Palo Alto, California, USA)) with an extruded monolayer film of a given thickness. For this purpose, the thickness of the monolayer film used for the measurement corresponds to the thickness of the corresponding layer of the multilayer film of the present invention. Optionally, particularly if the thickness of the layer is less than 10 μm, the spectral transmittance of the layer can be determined by applying a monolayer coating to a quartz glass (fused silica) plate and measuring the spectral transmittance of the coating. There are no particular limitations on the manner of applying the coating, and it includes, for example, extruding onto the quartz glass plate, laminating, applying a solution of the layer material, and then evaporating the solvent. For example, the monolayer can be advantageously applied by spin-coating a solution / dispersion of the layer material in acetone.

[0045] Alternatively, to determine the spectral transmittance, the layer in question can be co-extruded with a polymeric thermoplastic material that has particularly low spectral transmittance at the wavelength of interest. For example, the layer in question can be co-extruded with a polymeric thermoplastic material available from... (Darmstadt, Germany) Co-extrusion of a 40μm thick layer with 7H.

[0046] The spectral transmittance of layers A and B was measured as a function of wavelength according to ISO 13468-2:1999. Furthermore, the instrument must have an extended wavelength range to enable measurements in the UV spectral region. The measurements were performed at a temperature of 23 ± 2 °C and a relative humidity of 50 ± 5%.

[0047] In yet another aspect, the present invention relates to a multilayer film comprising at least layer A and layer B, wherein

[0048] Layer A includes a total weight meter based on layer A:

[0049] 0.0 to 99.0% by weight of poly(meth)acrylate;

[0050] 0.0 to 95.0% by weight of one or more impact modifiers;

[0051] 0.0 to 30.0% by weight of fluoropolymers;

[0052] 1.0 to 30.0% by weight of a first UV absorber, wherein the first UV absorber is an inorganic particulate material, preferably selected from zinc oxide, titanium dioxide, cerium dioxide, tin dioxide, silicon dioxide and glass;

[0053] 0.0 to 5.0% by weight of one or more UV stabilizers;

[0054] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer A is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 97.0% by weight; and the cumulative content of layer A in any wavelength λ A The spectral transmittance at a certain point is no greater than 20%; where 270 nm ≤ λ A ≤310nm; and

[0055] Layer B includes a total weight meter based on layer B:

[0056] 0.0 to 99.9% by weight of poly(meth)acrylate;

[0057] 0.0 to 85.0% by weight of one or more impact modifiers;

[0058] 0.1 to 5.0% by weight of a second UV absorber that is different from the first UV absorber;

[0059] 0.0 to 5.0% by weight of one or more UV stabilizers; and

[0060] 0.0 to 20.0% by weight of an adhesion-promoting copolymer, the adhesion-promoting copolymer comprising

[0061] Contains: based on the weight of the adhesion-promoting copolymer:

[0062] (i) 70.0 to 95.0% by weight of methyl methacrylate;

[0063] (ii) 0.5 to 15.0% by weight of maleic anhydride; and

[0064] (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers, which have no functional groups other than vinyl functional groups; and

[0065] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer B is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 99.9% by weight, based on the weight of layer B; and the cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer B is at any wavelength λ B The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ B ≤370nm.

[0066] In another aspect of the invention, the multilayer film comprises at least layer A and layer B, wherein

[0067] Layer A includes a total weight meter based on layer A:

[0068] 0.0 to 97.0% by weight of poly(meth)acrylate;

[0069] 0.0 to 95.0% by weight of one or more impact modifiers;

[0070] 0.0 to 30.0% by weight of fluoropolymers;

[0071] 3.0 to 30.0% by weight of a first UV absorber, wherein the first UV absorber is an inorganic particulate material, preferably selected from zinc oxide, titanium dioxide, cerium dioxide, tin dioxide, silicon dioxide, and glass; and

[0072] 0.0 to 5.0% by weight of one or more UV stabilizers;

[0073] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer A is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 97.0% by weight, based on the weight of layer A; and wherein

[0074] Layer A at any wavelength λ A The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ A ≤310nm; and

[0075] Layer B includes a total weight meter based on layer B:

[0076] 0.0 to 99.9% by weight of poly(meth)acrylate;

[0077] 0.0 to 85.0% by weight of one or more impact modifiers;

[0078] 0.1 to 5.0% by weight of a second UV absorber that is different from the first UV absorber;

[0079] 0.0 to 5.0% by weight of one or more UV stabilizers; and

[0080] 0.0 to 20.0% by weight of an adhesion-promoting copolymer, the adhesion-promoting copolymer comprising

[0081] Contains: based on the weight of the adhesion-promoting copolymer:

[0082] (i) 70.0 to 95.0% by weight of methyl methacrylate;

[0083] (ii) 0.5 to 15.0% by weight of maleic anhydride; and

[0084] (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers, which have no functional groups other than vinyl functional groups; and

[0085] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer B is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 99.9% by weight, based on the weight of layer B; and wherein

[0086] Layer B at any wavelength λ B The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ B ≤370nm; and

[0087] Layer A contains no more than 0.1% by weight, preferably no more than 0.05% by weight, of the second UV absorber, and

[0088] The layer B contains no more than 0.1% by weight, preferably no more than 0.05% by weight, of the first UV absorber.

[0089] Similarly, layer A contains no more than 0.1% by weight, preferably no more than 0.05% by weight, of the second UV absorber, and layer B contains no more than 0.1% by weight, preferably no more than 0.05% by weight, of the first UV absorber.

[0090] In this embodiment, preferably, the inorganic particulate material acting as the first UV absorber is substantially uniformly dispersed in the material of layer A. As used herein, the term "uniform" means that the concentration of the particulate material within the membrane is substantially constant.

[0091] Another aspect of the invention relates to a coated article having a film of the invention on its surface. The coated article comprises a substrate at least partially covered by the film, such that the layers of the film are arranged in the following order:

[0092] Layer D, if present, forms the outer surface of the coated article;

[0093] Layer A is located between layer D and the substrate;

[0094] Layer E, if it exists, is located between layer A and layer B;

[0095] Layer B is located between layer A and the substrate; and

[0096] Layer C, if present, is located between layer B and the substrate.

[0097] Finally, another aspect of the invention relates to the use of films as defined above for coating substrates, preferably by a method selected from co-extrusion, lamination or extrusion lamination. Attached Figure Description

[0098] Figure 1 The lamination method in preparation examples 7-16 is illustrated schematically.

[0099] 1. Steel plate

[0100] 2. Rubber sheet

[0101] 3. Separator paper

[0102] 4. Single-layer membrane 1

[0103] 5. Single-layer membrane 2

[0104] Detailed description of the preferred implementation scheme

[0105] The multilayer film of the present invention comprises at least layers A and B. Preferably, the film of the present invention is a co-extruded film.

[0106] According to the present invention, layer B has the following composition:

[0107] 0.0 to 99.9% by weight of poly(meth)acrylate;

[0108] 0.0 to 85.0% by weight of one or more impact modifiers;

[0109] 0.1 to 5.0% by weight of a second UV absorber that is different from the first UV absorber of layer A;

[0110] 0.0 to 5.0% by weight of one or more UV stabilizers; and

[0111] 0.0 to 20.0% by weight of adhesion-promoting copolymers;

[0112] The layer B contains no more than 0.1% by weight, preferably no more than 0.05% by weight, of the first UV absorber.

[0113] Adhesion-promoting copolymers are known in the art and are commonly used in acrylic films to improve their adhesion to substrates. If present, the adhesion-promoting copolymer in layer B comprises: based on the weight of the adhesion-promoting copolymer...

[0114] (i) 70.0 to 95.0% by weight of methyl methacrylate;

[0115] (ii) 0.5 to 15.0% by weight of maleic anhydride; and

[0116] (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers, which have no other functional groups besides the vinyl functional group.

[0117] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer B is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 99.9% by weight, based on the weight of layer B. Those skilled in the art can readily adjust the content of the one or more impact modifiers in layer B depending on the intended application. For example, in applications requiring highly flexible soft films, a relatively high content of impact modifier, up to 85% by weight, can be used. On the other hand, for applications requiring relatively brittle hard films, layer B may have a lower content of impact modifier, or even be substantially free of impact modifier.

[0118] To ensure adequate protection of the substrate material beneath the multilayer film, layer B is used at any wavelength λ. B The spectral transmittance at all locations is no greater than 10%; where 270nm ≤ λ B ≤370nm. Furthermore, the optical transmittance of layer B at a wavelength of 370nm is preferably selected to be no greater than 10%.

[0119] The exact composition of layer A depends on the properties of the first UV absorber used therein.

[0120] In one aspect of the invention, layer A comprises:

[0121] 0.0 to 99.9% by weight of poly(meth)acrylate;

[0122] 0.0 to 95.0% by weight of one or more impact modifiers;

[0123] 0.0 to 30.0% by weight of fluoropolymers;

[0124] 0.1 to 5.0% by weight of the first UV absorber;

[0125] 0.0 to 5.0% by weight of one or more UV stabilizers;

[0126] The layer A contains no more than 0.1% by weight, preferably no more than 0.05% by weight, of the second UV absorber.

[0127] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer A is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 99.9% by weight, based on the weight of layer A. Similarly, as described above, those skilled in the art can readily adjust the content of the one or more impact modifiers in layer A depending on the intended application.

[0128] Not wanting to be bound by theory, the inventors of this invention surprisingly discovered that, in order to achieve excellent long-term climate aging stability in this embodiment, it is important that layer A, at any wavelength λ... A The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ A ≤360nm.

[0129] In yet another embodiment of the invention, layer A has the following composition:

[0130] 0.0 to 99.0% by weight of poly(meth)acrylate;

[0131] 0.0 to 95.0% by weight of one or more impact modifiers;

[0132] 0.0 to 30.0% by weight of fluoropolymers;

[0133] 1.0 to 30.0% by weight of a first UV absorber, wherein the first UV absorber is an inorganic particulate material, preferably selected from zinc oxide, titanium dioxide, cerium dioxide, tin dioxide, silicon dioxide and glass;

[0134] 0.0 to 5.0% by weight of one or more UV stabilizers;

[0135] The layer A contains no more than 0.1% by weight, preferably no more than 0.05% by weight, of the second UV absorber.

[0136] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer A is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 97.0% by weight.

[0137] In this particular implementation, layer A at any wavelength λ A The spectral transmittance at a certain point is no greater than 20%; where 270 nm ≤ λ A ≤310nm.

[0138] In addition to layers A and B described above, the multilayer film of the present invention may further include an adhesion-promoting layer C. This layer C further improves the adhesion of the film of the present invention to the substrate and is particularly advantageous for the manufacture of HPL. Typically, layer C comprises, based on the total weight of layer C:

[0139] 0.0 to 95.0% by weight of poly(meth)acrylate;

[0140] 0.0 to 75.0% by weight of one or more impact modifiers;

[0141] 0.0 to 5.0% by weight of a UV absorber, preferably the second UV absorber;

[0142] 0.0 to 5.0% by weight of one or more UV stabilizers; and

[0143] 5.0 to 80.0% by weight of the adhesion-promoting copolymer as clearly stated above.

[0144] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer C is at least 20.0% by weight, preferably at least 30.0% by weight, more preferably at least 40.0% by weight, and not more than 95.0% by weight, based on the weight of layer C. Additionally, to ensure good adhesion between the film of the present invention and the substrate, the adhesion-promoting layer C contains at least 5% by weight, preferably at least 10% by weight, of one or more impact modifiers.

[0145] Further evidence demonstrates that, advantageous in terms of the mechanical properties of the diaphragm, the total content of one or more impact modifiers in the adhesion promoting layer C is lower than the total content in the layer B, and the total content of one or more impact modifiers in the layer B is lower than the total content in the layer A.

[0146] If the adhesion-promoting layer C is present, then layer B contains less than 3.0% by weight, preferably less than 1.0% by weight, of the adhesion-promoting copolymer based on the weight of layer B.

[0147] If desired, the multilayer membrane of the present invention may optionally be made particularly weather-resistant by providing a fluoropolymer-based layer D on top of and adjacent to layer A. The layer D may comprise a total weight based on the following:

[0148] At least one fluoropolymer, comprising 40.0 to 100.0% by weight;

[0149] 0.0 to 60.0% by weight of poly(meth)acrylate; and

[0150] 0.0 to 30.0% by weight of substantially spherical glass beads.

[0151] The structure and composition of layer D are described in detail in patent application WO 2018 / 104293 A1, the entire disclosure of which is incorporated herein by reference.

[0152] The fluoropolymer in layer D may be selected from polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polyethylene-tetrafluoroethylene (ETFE), fluorinated ethylene-propylene (FEP), or mixtures or copolymers thereof.

[0153] Additionally, in some embodiments, the film may further comprise a layer E located between layer A and layer B and comprising a combination of a first UV absorber and a second UV absorber as described above. Typically, layer E has the following composition:

[0154] 0.0 to 99.9% by weight of poly(meth)acrylate;

[0155] 0.0 to 95.0% by weight of one or more impact modifiers;

[0156] 0.0 to 30.0% by weight of fluoropolymers;

[0157] 0.0 to 20.0% by weight of an adhesion-promoting copolymer, wherein the adhesion-promoting copolymer comprises: based on the weight of the adhesion-promoting copolymer:

[0158] (i) 70.0 to 95.0% by weight of methyl methacrylate;

[0159] (ii) 0.5 to 15.0% by weight of maleic anhydride; and

[0160] (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers, which have no functional groups other than vinyl functional groups; and

[0161] A combination of the first UV absorber and the second UV absorber, in amounts ranging from 0.1 to 5.0% by weight;

[0162] 0.0 to 5.0% by weight of one or more UV stabilizers;

[0163] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer E is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 99.9% by weight.

[0164] Advantageously, layer E includes a total weight meter based on layer E:

[0165] 0.0 to 99.9% by weight of polymethyl methacrylate;

[0166] 0.0 to 95.0% by weight of one or more impact modifiers;

[0167] A combination of the first UV absorber and the second UV absorber, in amounts ranging from 0.1 to 5.0% by weight;

[0168] 0.0 to 5.0% by weight of one or more UV stabilizers.

[0169] The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer E is at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, particularly preferably at least 95% by weight and not more than 99.9% by weight.

[0170] Depending on the intended purpose, the membrane of the present invention may have a total thickness between 1.0 μm and 300.0 μm, more preferably between 1.0 μm and 200.0 μm, and even more preferably between 30.0 μm and 150.0 μm.

[0171] The PMMA-based layer A typically has a thickness of 10.0 μm to 100.0 μm, preferably 15.0 μm to 50.0 μm, and more preferably 20.0 μm to 40.0 μm.

[0172] The PMMA-based layer B typically has a thickness of 10.0 μm to 80.0 μm, preferably 15.0 μm to 50.0 μm, and more preferably 20.0 μm to 40.0 μm.

[0173] The adhesion promoting layer C, if present, has a thickness of 1.0 μm to 20.0 μm, preferably 2.0 μm to 15.0 μm, and more preferably 3.0 μm to 10.0 μm.

[0174] The fluoropolymer-based layer D, if present, has a thickness of 1.0 μm to 40.0 μm, preferably 2.0 μm to 30.0 μm, and more preferably 3.0 μm to 20.0 μm.

[0175] The PMMA-based layer E, if present, has a thickness of 10.0 μm to 80.0 μm, preferably 15.0 μm to 50.0 μm, and more preferably 20.0 μm to 40.0 μm.

[0176] The thickness of the membrane and its layers of the present invention can be determined by mechanical scanning according to standard ISO 4593-1993. However, preferably, the thickness of the membrane and its individual layers of the present invention is determined using photomicrography, which is obtained using a scanning electron microscope such as the JEOL JSM-IT300 (commercially available from JEOL GmbH, Freising, Germany). For this purpose, the membrane sample can be frozen in liquid nitrogen, mechanically broken up, and the newly obtained surface analyzed. For example, the measurement can be performed using the following parameters:

[0177] Current source: Variable electron flow from a tungsten filament (cathode)

[0178] Vacuum system: rotary pump / oil diffusion pump

[0179] XYZ-Rotation-Tilt: Fully Mechanized

[0180] Working distance (WD): 5 to 70 mm (typically: 10 mm)

[0181] Sample rotation: 360°

[0182] Sample tilt: -5° to a maximum of 90° (depending on WD)

[0183] Magnification: 10x to 300,000x

[0184] Maximum resolution: approximately 3nm

[0185] Detector: Secondary electron (SE)

[0186] Backscattered electrons (BSE, 5-segment)

[0187] Energy-dispersive X-ray analysis (EDS)

[0188] In summary, the multilayer film of the present invention has layers in the following order:

[0189] The fluoropolymer-based layer D, if present, is directly exposed to the environment;

[0190] The PMMA-based layer A is located below the layer D;

[0191] If the PMMA-based layer E exists, it is located between layer A and layer B;

[0192] The PMMA-based layer B is located below layer A, or, if layer E exists, below layer E; and

[0193] The adhesion-promoting layer C, if present, is located below the layer B.

[0194] The following embodiments of the multilayer film of the present invention exhibit particularly advantageous properties:

[0195] (1) Layer A, which contains glass beads as a first UV absorber; and

[0196] Layer B contains a benzotriazole-type UV absorber, preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or mixtures thereof.

[0197] (2) Layer A, which comprises an inorganic particulate material as a first UV absorber, said inorganic particulate material being selected from cerium oxide, titanium dioxide, or zinc oxide; and

[0198] Layer B contains a benzotriazole-type UV absorber, preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or mixtures thereof.

[0199] (3) Layer A, which contains a triazine-type UV absorber as the first UV absorber, wherein the triazine-type UV absorber is preferably selected from 6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-imide]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-diene.

[0200] -1-one, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)benzene

[0201] Phenols or combinations of at least two of them; and

[0202] Layer B contains a benzotriazole-type UV absorber, preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or mixtures thereof.

[0203] (4) Layer D, which contains glass beads dispersed in a fluoropolymer matrix;

[0204] Layer A, which contains a triazine-type UV absorber as the first UV absorber, preferably selected from 6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-pyridyl]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-diene.

[0205] -1-one, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)benzene

[0206] Phenols or combinations of at least two of them; and

[0207] Layer B contains a benzotriazole-type UV absorber, preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or mixtures thereof.

[0208] (5) A fluoropolymer-based layer D, which preferably contains at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, and even more preferably at least 99% by weight of PVDF based on the weight of said layer D;

[0209] Layer A, which contains a triazine-type UV absorber as the first UV absorber, preferably selected from 6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-pyridyl]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-diene.

[0210] -1-one, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)benzene

[0211] Phenols or combinations of at least two of them; and

[0212] Layer B contains a benzotriazole-type UV absorber, preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or mixtures thereof.

[0213] (6) Layer A, which contains inorganic particulate material as a first UV absorber, wherein the inorganic particulate material is selected from cerium oxide, titanium dioxide or zinc oxide;

[0214] Layer E, which contains a triazine-type UV absorber as the first UV absorber, preferably selected from 6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-pyridyl]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-diene.

[0215] -1-one, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)benzene

[0216] Phenols or combinations of at least two of them; and

[0217] Layer B contains a benzotriazole-type UV absorber, preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or mixtures thereof.

[0218] (7) Layer A, which contains a triazine-type UV absorber as the first UV absorber, wherein the triazine-type UV absorber is preferably selected from 6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-imide]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-diene.

[0219] -1-one, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)benzene

[0220] Phenols or combinations of at least two of them;

[0221] Layer E, which contains a triazine-type UV absorber as the first UV absorber, preferably selected from 6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-pyridyl]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-diene.

[0222] -1-one, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol or combinations thereof, and benzotriazole-type UV absorbers, said benzotriazole-type UV absorbers preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazin-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazin-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol or mixtures of at least two thereof; and

[0223] Layer B contains a benzotriazole-type UV absorber, preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or mixtures thereof.

[0224] (8) Layer D, which contains glass beads dispersed in a fluoropolymer matrix;

[0225] Layer A, which contains a triazine-type UV absorber as the first UV absorber, preferably selected from 6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-pyridyl]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-diene.

[0226] -1-one, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)benzene

[0227] Phenols or combinations of at least two of them;

[0228] Layer B, comprising a benzotriazole-type UV absorber, preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or mixtures thereof; and

[0229] Layer C.

[0230] (9) Layer A, which contains glass beads as a first UV absorber;

[0231] Layer E, which contains a triazine-type UV absorber as the first UV absorber, preferably selected from 6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-pyridyl]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-diene.

[0232] -1-one, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)phenol,

[0233] 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol or a combination of at least two of them, and a benzotriazole-type UV absorber, said benzotriazole-type UV absorber preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol or a mixture thereof; and

[0234] Layer B contains a benzotriazole-type UV absorber, preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or mixtures thereof.

[0235] (10) Layer A, which contains glass beads as a first UV absorber;

[0236] Layer E, which contains a triazine-type UV absorber as the first UV absorber, preferably selected from 6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-pyridyl]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-diene.

[0237] -1-one, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy)phenol,

[0238] 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol or a combination of at least two of them; and

[0239] Layer B contains a benzotriazole-type UV absorber, preferably selected from 2,2'-methylene-bis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or mixtures thereof.

[0240] The components of layers A, B, C, D, and E will be described in more detail below.

[0241] Poly(methyl methacrylate)

[0242] As mentioned above, the PMMA-based layers A and B may contain up to 99.9% by weight of poly(methyl methacrylate) (PMMA). PMMA is typically obtained by free radical polymerization of mixtures containing methyl methacrylate. These mixtures typically contain at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight, and even more preferably at least 90% by weight of methyl methacrylate (MMA) based on the monomers.

[0243] The mixtures used to prepare PMMA may also contain other (meth)acrylates capable of copolymerizing with methyl methacrylate. As used herein, the term "(meth)acrylate" means to encompass methacrylates, acrylics, and mixtures thereof. (Meth)acrylates can be derived from saturated alcohols, such as methyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, and 2-ethylhexyl methacrylate; or from unsaturated alcohols, such as oleyl methacrylate, 2-propynyl methacrylate, allyl methacrylate, and vinyl methacrylate; and aryl methacrylates, such as benzyl methacrylate or phenyl methacrylate; cycloalkyl methacrylates, such as 3-vinylcyclohexyl methacrylate and borneol methacrylate; hydroxyalkyl methacrylates, such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, and so on. 2-Hydroxypropyl acrylate; diol di(meth)acrylate, such as 1,4-butanediol (meth)acrylate; ether alcohol (meth)acrylate, such as tetrahydrofurfuryl methacrylate, ethyleneoxyethoxyethyl methacrylate; amides and nitriles of (meth)acrylate, such as N-(3-dimethylaminopropyl)(meth)acrylamide, N-(diethylphosphono)-(meth)acrylamide, 1-methacryloylamino-2-methyl-2-propanol; sulfur-containing methacrylates, such as ethyl sulfinyl methacrylate, 4-thiocyanate butyl methacrylate, ethyl sulfonyl methacrylate, methyl thiocyanate methyl methacrylate, methyl sulfinyl methacrylate, bis((meth)acryloyloxyethyl) sulfide; polyfunctional (meth)acrylates, such as trimethylolpropane tri(meth)acrylate.

[0244] Polymerization reactions are typically initiated by known free radical initiators. Preferred initiators are, in particular, azo initiators well known to those skilled in the art, such as AIBN and 1,1-azobiscyclohexanenitrile, and peroxides, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauroyl peroxide, tert-butyl 2-ethylperhexanoate, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, and 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane. 2-Ethylperoxyhexanoate tert-butyl ester, 3,5,5-trimethylperoxyhexanoate tert-butyl ester, dicumyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl hydroperoxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, mixtures of two or more of the compounds mentioned above, and mixtures of the compounds mentioned above with compounds not mentioned but also capable of forming free radicals.

[0245] The polymerizable composition may contain not only the (meth)acrylic acid compounds described above, but also other unsaturated monomers capable of copolymerizing with methyl methacrylate and with the (meth)acrylic acid compounds mentioned above. These monomers are particularly 1-enes, such as 1-hexene and 1-heptene; branched alkenes, such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, and 4-methyl-1-pentene; acrylonitrile; vinyl esters, such as vinyl acetate; styrene, substituted styrene having alkyl substituents in the side chain, such as α-methylstyrene and α-ethylstyrene, substituted styrene having alkyl substituents on the ring, such as vinyltoluene and p-methylstyrene, halostyrene, such as monochlorostyrene, dichlorostyrene, tribromostyrene, and tetrabromostyrene; heterocyclic vinyl compounds, such as 2-vinylpyridine, 3-Vinylpyridine, 2-Methyl-5-vinylpyridine, 3-Ethyl-4-vinylpyridine, 2,3-Dimethyl-5-vinylpyridine, Vinylpyrimidine, Vinylpiperidine, 9-Vinylcarbazole, 3-Vinylcarbazole, 4-Vinylcarbazole, 1-Vinylimidazolium, 2-Methyl-1-Vinylimidazolium, N-Vinylpyrrolidone, 2-Vinylpyrrolidone, N-Vinylpyrrolidine, 3-Vinylpyrrolidine, N-Vinylcaprolactam, N-Vinylbutyrolactam, Vinyloxacyclopentane, Vinylfuran, Vinylthiophene, Vinylthiocyclopentane, Vinylthiazole and Hydrogenated Vinylthiazole, Vinyl azole and hydrogenated vinyl Azoles; vinyl ethers and isoprene ethers; maleic acid derivatives, such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide; and dienes, such as divinylbenzene.

[0246] The typical amount of these comonomers is from 0.0% to 60.0% by weight, preferably from 0.0% to 40.0% by weight, and particularly preferably from 0.0% to 20.0% by weight, based on the weight of the monomers, and the compounds described herein may be used alone or in the form of mixtures.

[0247] Further preferred PMMA can be obtained by polymerizing the following composition, wherein the composition has the following as a polymerizable component:

[0248] (a) 50.0 to 99.9% by weight, preferably 80.0 to 99.9% by weight, more preferably 91.0 to 99.9% by weight of methyl methacrylate.

[0249] (b) 0.1 to 50.0% by weight, preferably 0.1 to 20.0% by weight, more preferably 0.1 to 9.0% by weight of acrylates of C1-C4 alcohols,

[0250] (c) 0.0 to 10.0% by weight of at least one other monomer capable of copolymerizing with said monomers (a) and (b).

[0251] Using component (c) (preferably n-butyl acrylate) in the range of 8.0 to 10.0% by weight improves the inherent stability of the membrane. The stability of the membrane increases with increasing proportion of component (c). However, increases exceeding certain limits are detrimental.

[0252] In yet another embodiment, a preferred PMMA is composed of 80.0 to 99.9 wt% methyl methacrylate and 0.1 to 20.0 wt% methyl acrylate, the amounts described herein being based on 100 wt% of the polymerizable component. Particularly advantageous copolymers are those obtained by copolymerizing 95.0 to 99.9 wt% methyl methacrylate and 0.1 to 5.0 wt% methyl acrylate, the amounts being based on 100 wt% of the polymerizable component. For example, the PMMA may contain 96.0 wt% methyl methacrylate and 4.0 wt% methyl acrylate, 98.0 wt% methyl methacrylate and 2.0 wt% methyl acrylate, or 99.0 wt% methyl methacrylate and 1.0 wt% methyl acrylate. The Vicat softening point VSP (ISO 306-B50) of the PMMA is typically at least 90°C, preferably 95°C to 112°C.

[0253] The chain length and molecular weight of the PMMA polymer can be adjusted by polymerizing the monomer mixture in the presence of a molecular weight regulator, specific examples of which are thiols known for this purpose, such as n-butylthiol, n-dodecylthiol, 2-mercaptoethanol, or 2-ethylhexyl thioglycolate, or pentaerythritol tetrathioglycolate; the molecular weight regulator is typically used in an amount of 0.05 to 5.0% by weight based on the weight of the monomer mixture, preferably in an amount of 0.1 to 2.0% by weight based on the weight of the monomer mixture, and particularly preferably in an amount of 0.2 to 1.0% by weight (see H. Rauch-Puntigam, Th.). "Acryl-und Methacrylverbindungen" (Acrylic and Methacrylic Compounds), Springer, Heidelberg, 1967; Houben-Weyl, Method of Organic Chemistry, Vol. XIV / 1, p. 66, Georg Thieme, Heidelberg, 1961; or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, p. 296 and subsequent pages, J. Wiley, New York, 1978).

[0254] The weight-average molar mass (Mw) of the PMMA used is typically higher than 80,000 g / mol, determined by gel permeation chromatography (GPC, with PMMA as a calibration standard, for all Mw determinations against the PMMA matrix), more preferably ≥120,000 g / mol. For the purposes of this invention, if the weight-average molar mass (Mw) of the PMMA is higher than 140,000 g / mol, membranes with even greater weather resistance can be obtained. The weight-average molar mass (Mw) of the PMMA is typically in the range of 80,000 g / mol to 220,000 g / mol. Films made of PMMA with an average molar mass Mw in the range of 80,000 g / mol to 180,000 g / mol, preferably in the range of 100,000 g / mol to 180,000 g / mol, more preferably in the range of 120,000 g / mol to 180,000 g / mol, were obtained with particular good weather resistance, in each case determined by GPC relative to a PMMA calibration standard.

[0255] The particularly favorable weathering stability and processability of the membrane are observed when the poly(meth)acrylate is PMMA having an average molecular weight Mw of 80,000 g / mol to 220,000 g / mol and can be obtained by polymerizing a composition whose polymerizable component comprises, based on the weight of the polymerizable composition:

[0256] (a) 50.0 to 99.9% by weight, preferably 80.0 to 99.9% by weight, more preferably 91.0 to 99.9% by weight of methyl methacrylate.

[0257] (b) 0.1 to 50.0% by weight, preferably 0.1 to 20.0% by weight, more preferably 0.1 to 9.0% by weight of acrylates of C1-C4 alcohols,

[0258] (c) 0.0 to 10.0% by weight of at least one other monomer capable of copolymerizing with said monomers (a) and (b).

[0259] Typically, the PMMA is not crosslinked, and therefore it is suitable for thermoplastic processing. However, in an alternative embodiment, crosslinked PMMA may be used in one or more layers, for example as an electron beam, UV, or thermally crosslinkable PMMA coating.

[0260] Impact modifier

[0261] The impact modifiers used in this invention are known in themselves and can have different chemical compositions and different polymer architectures. The impact modifiers can be crosslinked or thermoplastic. Furthermore, the impact modifiers can be in particulate form, as core-shell or core-shell-shell particles. Typically, particulate impact modifiers have an average particle diameter between 20 and 400 nm, preferably between 50 and 300 nm, more preferably between 100 and 285 nm, and most preferably between 150 and 270 nm. In this context, "particulate" means a crosslinked impact modifier that typically has a core-shell or core-shell-shell structure.

[0262] In its simplest form, the particulate impact modifier is a cross-linked particle obtained by emulsion polymerization, with an average particle size in the range of 10 to 150 nm, preferably 20 to 100 nm, particularly 30 to 90 nm. These typically consist of: at least 40.0% by weight, preferably 50.0 to 70.0% by weight, 20.0 to 40.0% by weight, preferably 25.0 to 35.0% by weight, 0.1 to 2.0% by weight, preferably 0.5 to 1.0% by weight, a cross-linking monomer, such as a polyfunctional (meth)acrylate, such as allyl methacrylate, and, if appropriate, other monomers, such as 0.0 to 10.0% by weight, preferably 0.5 to 5.0% by weight, of C1-C4 alkyl methacrylates, such as ethyl acrylate or butyl methacrylate, preferably methyl acrylate, or other vinyl polymerizable monomers, such as styrene.

[0263] Preferred impact modifiers are polymer particles that may have a two- or three-layered core-shell structure and are obtained through emulsion polymerization (see, for example, EP-A 0 113 924, EP-A 0 522351, EP-A 0 465 049, and EP-A 0 683028). Typically, the present invention requires suitable particle sizes of these emulsion polymers in the range of 10 to 150 nm, preferably 20 to 120 nm, and particularly preferably 50 to 100 nm.

[0264] A three-layered or three-phase structure with a core and two shells can be prepared as follows. The innermost (hard) shell can, for example, consist essentially of methyl methacrylate, a small proportion of comonomers (e.g., ethyl acrylate), and a certain proportion of crosslinking agents (e.g., allyl methacrylate). The middle (soft) shell can, for example, consist of butyl acrylate and, if suitable, styrene, while the outermost (hard) shell is essentially the same as the matrix polymer, thus providing compatibility and good bonding with the matrix. The proportion of polybutyl acrylate in the impact modifier is decisive for the impact modification effect and is preferably in the range of 20.0 to 40.0% by weight, particularly preferably in the range of 25.0 to 35.0% by weight.

[0265] Further preferred is the use of a system known in principle from EP 0 528 196 A1, which is a two-phase impact-modified polymer composed of the following substances:

[0266] a1) 10.0 to 95.0% by weight of a cohesive hard phase with a glass transition temperature (Tg) above 70°C, composed of the following substances:

[0267] (a11) 80.0 to 100% by weight (based on a1) methyl methacrylate, and

[0268] a12) 0.0 wt% to 20.0 wt% of one or more other olefinic unsaturated monomers capable of free radical polymerization, and

[0269] a2) 90.0 to 5.0 wt% of a toughening phase having a glass transition temperature (Tg) below -10 °C, distributed in the hard phase, and composed of the following substances:

[0270] a21) 50.0 to 99.5% by weight acrylic acid C1-C 10 -Alkyl esters (based on a2)

[0271] a22) 0.5 to 5.0 wt% of a crosslinked monomer capable of free radical polymerization having two or more olefinic unsaturated groups, and

[0272] a23) If appropriate, other olefinic unsaturated monomers capable of free radical polymerization.

[0273] At least 15.0% by weight of the hard phase a1) has covalent bonds connecting it to the tough phase a2).

[0274] The two-phase impact modifier can be prepared by a two-stage emulsion polymerization reaction in water, as described, for example, in DE-A38 42 796. In the first stage, the toughening phase a2) is prepared, which consists of at least 50.0% by weight, preferably more than 80.0% by weight, of a lower alkyl acrylate, thus for which a glass transition temperature Tg is obtained below -10°C. The crosslinking monomer a22) used comprises a diol (meth)acrylate, such as ethylene glycol dimethacrylate or 1,4-butanediol dimethacrylate, an aromatic compound having two vinyl or allyl groups, such as divinylbenzene, or other crosslinking agents capable of free radical polymerization having two olefinically unsaturated groups, such as allyl methacrylate, as a grafting agent. Crosslinking agents that can be mentioned by example and have three or more unsaturated groups (e.g., allyl groups or (meth)acrylate groups) capable of free radical polymerization are triallyl cyanurate, trimethylolpropane triacrylate and trimethylolpropane tri(meth)acrylate, as well as pentaerythritol tetraacrylate and pentaerythritol tetra(meth)acrylate. Further examples of them are given in US 4,513,118.

[0275] The olefinic unsaturated monomers capable of free radical polymerization mentioned under a23) can be, for example, acrylic acid or methacrylic acid or their alkyl esters having 1 to 20 carbon atoms, but not mentioned above, and the alkyl groups mentioned herein can be linear, branched, or cyclic. Additionally, a23) may include further aliphatic comonomers capable of free radical polymerization and copolymerizing with the alkyl acrylates a21). However, significant proportions of aromatic comonomers, such as styrene, α-methylstyrene, or vinyltoluene, are excluded because they can lead to undesirable properties of the resulting products, particularly in terms of weather aging.

[0276] When preparing the toughening phase in the first stage, special attention must be paid to setting the particle size and its polydispersity. Here, the particle size of the toughening phase depends substantially on the concentration of the emulsifier. The particle size can advantageously be controlled by using seed latex. The average (weight-average) particle size is below 130 nm, preferably below 70 nm, and the particle size polydispersity P... 80 Below 0.5 (P) 80 It is determined by a cumulative evaluation of particle size distribution measured by ultracentrifugation; the relationship is: P 80 =[(r 90 -r 10 ] / r 50 ]-1, where r 10 ,r 50 ,r 90 =The average cumulative particle radius (a value greater than 10%, 50%, and 90% of the particle radius and less than 90%, 50%, and 10% of the particle radius), preferably less than 0.2, is achieved using an emulsifier concentration of 0.15 to 1.0 wt% based on the aqueous phase. This is particularly suitable for anionic emulsifiers, examples of which are particularly preferred alkoxylated and sulfated paraffins. Examples of polymerization initiators used are based on 0.01 to 0.5 wt% of alkali metal persulfate or ammonium persulfate based on the aqueous phase, and the polymerization reaction is initiated at a temperature of 20 to 100°C. A redox system is preferred, an example of which is a combination of 0.01 to 0.05 wt% organic hydrogen peroxide and 0.05 to 0.15 wt% sodium hydroxymethyl sulfinate at a temperature of 20 to 80°C.

[0277] The hard phase a1 (which has at least 15% by weight of covalent bonds to the tough phase a2) has a glass transition temperature of at least 70°C, and this phase may consist solely of methyl methacrylate. Up to 20% by weight of one or more other olefinically unsaturated monomers capable of free radical polymerization may be present in the hard phase as comonomer a12, and the amount of alkyl (meth)acrylate (preferably alkyl acrylate having 1 to 4 carbon atoms) used herein ensures that the glass transition temperature is not lower than the glass transition temperature mentioned above.

[0278] The polymerization of the hard phase a1) is also carried out in the second stage in the emulsion using conventional auxiliaries, such as those also used to polymerize the tough phase a2).

[0279] The mechanism of action of thermoplastic impact modifiers differs from that of particulate impact modifiers. They are typically mixed with the matrix material. In the case of microdomain formation, such as when block copolymers are used, the preferred size of these microdomains (whose size can be determined, for example, by electron microscopy) corresponds to the preferred size of the core-shell particles.

[0280] There are various categories of thermoplastic impact modifiers. One example is aliphatic TPU (thermoplastic polyurethane), such as those commercially available from Covestro AG. Products. For example, TPU. WDP 85784A, WDP 85092A, WDP 89085A and WDP 89051D (all of which have refractive indices between 1.490 and 1.500) are particularly suitable as impact modifiers.

[0281] Another type of thermoplastic polymer used as an impact modifier in the film according to the invention is a methacrylate-acrylate block copolymer, especially an acrylic TPE, which comprises a PMMA-n-butyl polyacrylate-PMMA triblock copolymer, and which can... The product name is purchased from Kuraray. The polybutyl acrylate block forms nanoregions with a size between 10 and 20 nm in the polymer matrix.

[0282] UV absorber

[0283] This invention is based on the surprising discovery that the climate aging stability of the resulting multilayer film can be significantly improved by placing different UV absorbers in separate PMMA-based layers. Therefore, the selection of the first and second UV absorbers is particularly important.

[0284] In one embodiment, the first UV absorber in layer A is an organic UV absorber. The first UV absorber and its amount in layer A are selected such that layer A is suitable for any wavelength λ. A The spectral transmittance is no greater than 10%; where 270nm ≤ λ A ≤360nm.

[0285] Preferably, the first UV absorber is a triazine-type UV absorber, particularly preferably 2-(2-hydroxyphenyl)-1,3,5-triazine. Preferred 2-(2-hydroxyphenyl)-1,3,5-triazines include, in particular, 2,4,6-tris-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine. 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tetrazyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4 6-Bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy / tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl 1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine. Triazine-type UV absorbers, such as 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, can also be used. These compounds can be trademarked, for example. 1600 1577 or Purchased from BASF SE (Ludwigshafen, Germany) in 1545.

[0286] The amount of the triazine-type UV absorber in layer A is 0.1 to 5.0% by weight, preferably 0.2 to 3.0% by weight, and very particularly preferably 0.5 to 2.0% by weight, based on the weight of layer A. A mixture of different triazine-type UV absorbers may also be used.

[0287] In a further preferred embodiment, the first UV absorber in layer A is an inorganic particulate material. This material can advantageously be selected from zinc oxide, titanium dioxide, cerium dioxide, tin dioxide, iron oxides, silicon dioxide, or glass in the form of glass beads or glass powder. The first UV absorber and its amount in layer A are selected such that layer A is suitable for any wavelength λ. A The spectral transmittance is no greater than 10%, where 270nm ≤ λ. A ≤310nm. Suitable examples of inorganic particulate materials are, for example, Solasorb. TM UV100 (titanium dioxide dispersion containing 45% by weight of inorganic and organic coated titanium dioxide, average particle size 40 nm), Solasorb TM UV200 (zinc oxide dispersion containing 60% by weight of zinc oxide, average particle size 60 nm) is available from Croda International Plc (Snays, UK).

[0288] In embodiments where glass is used as the primary UV absorber, the use of glass powder or glass beads with a particle size of less than 10 μm is particularly advantageous for effective UV absorption and high visible light transmittance. While there are no particular limitations on the choice of glass for this purpose, glass types such as GG395, GG400, GG420, GG435, GG475, OG515, and OG 530, available from Schott AG (Mainz, Germany), have proven particularly useful. The glass beads used in layer A will be described in more detail below in the "Glass Beads" section.

[0289] According to the present invention, the second UV absorber in layer B is different from the first UV absorber in layer A. The second UV absorber and its amount in layer B are selected such that layer B is suitable for any wavelength λ. B The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ B ≤370nm. Preferably, the optical transmittance of layer B at a wavelength of 370nm is not greater than 10%.

[0290] Preferably, the second UV absorber is an organic compound, which may advantageously be selected from substituted benzophenones, salicylates, cinnamic acid esters, oxaloyl aniline, benzo[a]benzene, etc. Phosphine ketones, hydroxyphenylbenzotriazoles, or benzylidene malonate. However, it has been shown that using benzotriazole-type UV absorbers as the second UV absorber is particularly advantageous.

[0291] In particular, the combination of a triazine-type compound in layer A as a first UV absorber and a benzotriazole-type compound in layer B as a second UV absorber surprisingly results in exceptionally high weathering stability of the multilayer film of the present invention. For example, layer A may contain 0.5 to 3.0 wt% of a triazine-type compound as a first UV absorber based on the weight of layer A; and layer B may contain 0.5 to 4.0 wt% of a benzotriazole-type compound as a second UV absorber based on the weight of layer B.

[0292] Benzotriazole-type UV absorbers are known in the art, and typically 2-(2'-hydroxyphenyl)benzotriazole. Relevant compounds include, in particular, 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-methyl ... '-Octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-pentyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2-metH-oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl-ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy-phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxy-carbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole- [2-ylphenol]; transesterification product formed by 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole and polyethylene glycol 300; [R-CH2CH2-COO-CH2CH2-, where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazole-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-phenyl]-benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]benzotriazole.Other examples of usable benzotriazole-type UV absorbers are 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-butyl-5-methylphenyl)-5-chlorobenzotriazole, and 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole. 1-Chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)benzotriazole and 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, phenol, 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)]. These compounds can be used, for example, as... 360 and Purchased from BASF SE (Ludwigshafen, Germany) by 234.

[0293] Benztriazole-type UV absorbers can also be used in combination with other UV absorbers, such as dimalonate-type UV absorbers. An example of such a combination is commercially available from Eutec Chemical Co., Ltd. BLA 4200M (included) 329 and B-CAP's commercial products).

[0294] The amount of the benzotriazole-type UV absorber in layer B is 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, and very particularly preferably 0.5 to 3.0% by weight, based on the weight of the PMMA-based layer B. A mixture of different benzotriazole-type UV absorbers may also be used.

[0295] Suitable 2-hydroxybenzophenones may include, in particular, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0296] Suitable substituted and unsubstituted esters of benzoic acid are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoic acid, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoic acid, and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid.

[0297] Other additives

[0298] If desired, the layers of the film of the present invention may further contain one or more UV stabilizers that typically function as antioxidants, free radical scavengers, etc. Particularly preferred UV stabilizers are sterically hindered phenols and HALS-type additives.

[0299] Staggered amines, or HALS (hindered amine light stabilizers), are known UV stabilizers. They can be used to suppress aging in paints and plastics, especially in polyolefin plastics (Kunststoffe, 74(1984)10, pp. 620-623; Farbe+Lack, Vol. 96, 9 / 1990, pp. 689-693). The tetramethylpiperidine group present in the HALS compounds is responsible for the stabilizing effect. These compounds may be unsubstituted on the piperidine nitrogen or have substitution on the piperidine nitrogen via alkyl or acyl groups. The sterically hindered amines do not absorb in the UV region. They scavenge already formed free radicals, which UV absorbers cannot do. Examples of HALS compounds that have stabilizing properties and can also be used in mixture form are: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)-decane-2,5-dione, bis(2,2,6,6-tetramethyl-4-piperidinyl) succinate, poly(N-β-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidinyl succinate) or bis(N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0300] The amount of the HALS compound used in the layer is typically 0.0 to 5.0% by weight, preferably 0.1 to 3.0% by weight, and very particularly preferably 0.2 to 2.0% by weight, based on the weight of the layer. Mixtures of different HALS compounds may also be used.

[0301] Other co-stabilizers that can be used are the HALS compounds described above, metabisulfites, such as sodium metabisulfite, and sterically hindered phenols and phosphites or esters. Such co-stabilizers can be present at a concentration of 0.1 to 5.0% by weight per layer.

[0302] Stericly hindered phenols are also suitable for use in the membranes of the present invention. Preferred sterically hindered phenols particularly include 6-tert-butyl-3-methylphenyl derivatives, 2,6-di-tert-butyl-p-cresol, 2,6-tert-butyl-4-ethylphenol, 2,2'-methylenebis-(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-m-cresol), 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-dihydroxydiphenylcyclohexane, alkylated bisphenols, styreneated phenols, 2,6-di-tert-butyl-4-methylphenol, and octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. 2,2'-Methylenebis(4-methyl-6-tert-butylphenol), 4,4'-Thiobis(3-methyl-6-tert-butylphenyl), 4,4'-Butylidenebis(3-methyl-6-tert-butylphenol), β-(3,5-di-4-butyl-4-hydroxyphenyl)propionate stearyl ester, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane. Commercially available space-hindered phenols include Sumilizer. TM BHT BP-76, WXR, GA-80 and BP-101 (Sumitomo Chemical, Osaka, Japan) 1076, 565, 1035, 1425WL, 3114, 1330 and 1010 (BASF SE, Ludwigshafen, Germany), MARK AO -50, -80, -30, -20, -330 and -60 (ADEKA Polymer Addtives, Mulhouse, France) and SS, TT (Mitsubishi Chemical Corporation, Yoshitomi, Japan).

[0303] Adhesion-promoting copolymers

[0304] The adhesion-promoting copolymer in layer B and / or layer C (if layer C is present) comprises: based on the weight of the adhesion-promoting copolymer.

[0305] (i) 70.0 to 95.0% by weight of methyl methacrylate;

[0306] (ii) 0.5 to 15.0% by weight of maleic anhydride; and

[0307] (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers, which have no other functional groups besides the vinyl functional group.

[0308] The monomer (i) is selected from alkyl methacrylates having 1 to 6 carbon atoms in the ester group, such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2,2-dimethylbutyl methacrylate, cyclopentyl methacrylate and cyclohexyl methacrylate, and particularly preferred methyl methacrylate.

[0309] The monomer (iii) may be selected from vinyl aromatic substances, such as α-halostyrene, p-methylstyrene, p-tert-butylstyrene, vinylnaphthalene, and preferably, α-methylstyrene and styrene, wherein styrene is particularly preferred.

[0310] The adhesion-promoting monomers (ii) are those monomers capable of free radical polymerization, possessing functional groups that can interact with the material to be coated. This interaction is at least induced via chemical (covalent) bonds. Furthermore, it can be promoted, for example, through hydrogen bonding, complexation, dipole forces, or thermodynamic compatibility (entanglement of polymer chains). These interactions typically involve heteroatoms, such as nitrogen or oxygen. Functional groups that may be mentioned include amino groups, particularly dialkylamino groups, (cyclic)amide groups, imide groups, hydroxyl groups, (epoxy)oxy groups, carboxyl groups, (iso)cyano groups, carboxylic acid groups, anhydride groups, or imino groups. These monomers are known in themselves (see H. Rauch Puntigam, Th.). Acrylund Methacrylverbindungen (Acrylic and Methacrylic Acid Compounds), Springer-Verlag 1967; Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Volume 1, pp. 394-400, J. Wiley 1978; DE-A 25 56 080; DE-A 26 34 003).

[0311] Therefore, the bonding-improving monomers preferably belong to the following monomer categories: preferably nitrogen-containing vinyl heterocycles having 5-membered and 6-membered rings, and / or copolymerizable vinyl carboxylic acids, and / or esters, anhydrides, or amides formed from fumaric acid, maleic acid, itaconic acid, acrylic acid, or methacrylic acid substituted with hydroxyalkyl-, alkoxyalkyl-, epoxy-, or aminoalkyl-substituted monomers. Nitrogen heterocyclic monomers that may be specifically mentioned are those selected from the categories of vinylimidazole, vinyllactam, vinylcarbazole, and vinylpyridine. Examples of these monomeric imidazole compounds are not intended to represent any form of limitation; they are N-vinylimidazole (also known as vinyl-1-imidazole), N-vinylmethyl-2-imidazole, N-vinylethyl-2-imidazole, N-vinylphenyl-2-imidazole, N-vinyldimethyl-2,4-imidazole, N-vinylbenzimidazole, N-vinylimidazoline (also known as vinyl-1-imidazole), N-vinylmethyl-2-imidazole, N-vinylphenyl-2-imidazole, and vinyl-2-imidazole.

[0312] Specific examples of monomers derived from lactams include compounds such as: N-vinylpyrrolidone, N-vinylmethyl-5-pyrrolidone, N-vinylmethyl-3-pyrrolidone, N-vinylethyl-5-pyrrolidone, N-vinyldimethyl-5,5-pyrrolidone, N-vinylphenyl-5-pyrrolidone, N-allylpyrrolidone, N-vinylthiopyrrolidone, N-vinylpiperidone, N-vinyldiethyl-6,6-piperidone, N-vinylcaprolactam, N-vinylmethyl-7-caprolactam, N-vinylethyl-7-caprolactam, N-vinyldimethyl-7,7-caprolactam, N-allylcaprolactam, and N-vinyloctylcaprolactam.

[0313] Among the monomers derived from carbazole, the following are particularly noteworthy: N-vinylcarbazole, N-allylcarbazole, N-butenylcarbazole, N-hexenylcarbazole, and N-(methyl-1-ethylene)carbazole. Among the copolyvinylcarboxylic acids, the following are particularly noteworthy: maleic acid, fumaric acid, itaconic acid, and their suitable salts, esters, or amides. Also mentioned are the following epoxy-, oxy-, or alkoxy-substituted alkyl esters of (meth)acrylic acid: glycidyl methacrylate, 2-hydroxyethyl (meth)acrylic acid, hydroxypropyl (meth)acrylic acid, 2-methoxyethyl (meth)acrylic acid, 2-ethoxyethyl (meth)acrylic acid, 2-butoxyethyl (meth)acrylic acid, 2-(2-butoxyethoxy)ethyl (meth)acrylic acid, 2-(ethoxyethyloxy)ethyl (meth)acrylic acid, 4-hydroxybutyl (meth)acrylic acid, 2-[2-(2-ethoxyethoxy)ethoxy]ethyl (meth)acrylic acid, 3-methoxy1-butyl (meth)acrylic acid, 2-alkoxymethylethyl (meth)acrylic acid, and 2-hexyloxyethyl (meth)acrylic acid.

[0314] Also mentioned are the following amine-substituted alkyl esters of (meth)acrylic acid: 2-dimethylaminoethyl (meth)acrylic acid, 2-diethylaminoethyl (meth)acrylic acid, 3-dimethylamino-2,2-dimethyl-1-propyl (meth)acrylic acid, 3-dimethylamino-2,2-dimethyl-1-propyl (meth)acrylic acid, 2-morpholinoethyl (meth)acrylic acid, 2-tert-butylaminoethyl (meth)acrylic acid, 3-(dimethylamino)propyl (meth)acrylic acid, and 2-(dimethylaminoethoxyethyl) (meth)acrylic acid.

[0315] The following monomers may be mentioned as representative of the (meth)acrylamide, for example: N-methyl (meth)acrylamide, N-dimethylaminoethyl (meth)acrylamide, N-dimethylaminopropyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-isobutyl (meth)acrylamide, N-decyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-[3-(dimethylamino)-2,2-dimethylpropyl]methylacrylamide, and N-[2-hydroxyethyl](meth)acrylamide.

[0316] Particularly advantageous is the use of "adhesion-promoting monomers" selected from the following: GMA (glycidyl methacrylate), maleic acid derivatives such as maleic acid, maleic anhydride (MA), methylmaleic anhydride, maleimide, methylmaleimide, maleamide (MA), phenylmaleimide and cyclohexylmaleimide, fumaric acid derivatives, methacrylic anhydride, acrylic anhydride.

[0317] Preferably, the adhesion-promoting monomer (ii) is maleic anhydride.

[0318] Optionally, the alkyl acrylate (iv) may be introduced in an amount up to 5.0% by weight to improve the rheological properties of the adhesive-promoting copolymer. The alkyl acrylate having 1 to 6 carbon atoms in the ester group may be, for example, ethyl acrylate, isopropyl acrylate, propyl acrylate, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, and preferably, butyl acrylate and particularly preferred, methyl acrylate.

[0319] In a preferred embodiment, the adhesion-promoting copolymer comprises:

[0320] Based on the weight of the copolymer

[0321] (i) 50.0 to 95.0% by weight, preferably 60.0 to 90.0% by weight, more preferably 70.0 to 85.0% by weight, and even more preferably 70 to 80% by weight of methyl methacrylate;

[0322] (ii) 0.2 to 25.0% by weight, preferably 0.5 to 20.0% by weight, more preferably 1.0 to 15.0% by weight, and even more preferably 5.0 to 12.0% by weight of maleic anhydride; and

[0323] (iii) 0.0 to 25.0% by weight, preferably 2.0 to 15.0% by weight, of other vinyl copolymerizable monomers, which have no functional groups other than vinyl functional groups.

[0324] In a particularly preferred embodiment, the adhesion-promoting copolymer is a copolymer formed from MMA, styrene, and maleic anhydride.

[0325] The adhesion-promoting copolymer can be obtained via free radical polymerization in a manner known per se. For example, EP 264590A1 describes a method for preparing a copolymer from a monomer mixture (comprising methyl methacrylate, a vinyl aromatic compound, and maleic anhydride) and, if appropriate, from a lower alkyl acrylate, by the following process: polymerization to 50% conversion in the presence or absence of an organic solvent that cannot polymerize, and, in the presence of an organic solvent, continuing the polymerization at a temperature range of 75 to 150°C to exceed at least 50% conversion, reaching at least 80% conversion, and then evaporating the low molecular weight volatile components.

[0326] JP-A 60-147 417 describes a method for preparing a suitable adhesion-promoting copolymer by feeding a monomer mixture consisting of methyl methacrylate, maleic anhydride, and at least one vinyl aromatic compound into a polymerization reactor suitable for solution polymerization or bulk polymerization at a temperature of 100 to 180°C, and polymerizing the material. DE-A44 40 219 describes an alternative preparation method.

[0327] Advantageously, the adhesion-promoting copolymers described in EP 264 590A1 and JP-A 60-147417 can be used in the films of the present invention.

[0328] Fluoropolymers

[0329] Depending on the intended use of the membrane of the present invention, the fluoropolymer may be selected from polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polyethylene-tetrafluoroethylene (ETFE), fluorinated ethylene-propylene (FEP), or mixtures or copolymers thereof. To further improve the weathering stability of the membrane of the present invention, the fluoropolymer may further comprise a copolymerized UV absorber.

[0330] The PVDF polymer used in the membrane is typically a transparent, semi-crystalline thermoplastic fluoroplastic. Advantageously, the PVDF has a high fusing point. The membrane exhibits particularly high heat resistance when the fusing point of the PVDF is at least 150°C, and more preferably at least 160°C. The upper limit of the fusing point is preferably about 175°C, which is equal to the fusing point of the PVDF. Further preferably, the weight-average molecular weight (Mw) of the PVDF is in the range of 50,000 to 300,000 g / mol, more preferably 80,000 to 250,000 g / mol, and even more preferably 150,000 to 250,000 g / mol, as determined by GPC.

[0331] The basic unit of PVDF is vinylidene fluoride, which is polymerized in high-purity water under controlled pressure and temperature conditions using a specific catalyst. Vinylidene fluoride can be obtained, for example, using dichlorofluoroethane as a precursor from hydrogen fluoride and methyl chloroform as starting materials. In principle, any commercially available PVDF, such as that produced by Arkema, can be produced... Grade, manufactured by Dyneon Grade, or produced by Solvay All grades are suitable for use in this invention. For example, the following commercial products can be used: 720 (vinylidene fluoride content: 100% by weight, melting point: 169℃) and 710 (vinylidene fluoride content: 100 wt%, crystallization melting point: 169°C), manufactured by ARKEMA; T850 (vinylidene fluoride content: 100 wt%, crystallization melting point: 173°C), manufactured by KUREHA Corporation. 1006 (vinylidene fluoride content: 100% by weight, melting point: 174℃) and 1008 (trade name) (ethylene vinylidene fluoride content: 100% by weight, crystallization melting point: 174°C), manufactured by Solvay Solexis.

[0332] PVDF has three bonding methods as monomer bonding methods: head-to-head bonding; tail-to-tail bonding; and head-to-tail bonding, wherein the head-to-head bonding and the tail-to-tail bonding are referred to as "irregular bonding". When the "irregular bonding ratio" in the PVDF is not greater than 10 mol%, the chemical resistance of layer A is particularly high. From the viewpoint of reducing the ratio of irregular bonding, the PVDF is preferably a resin prepared by suspension polymerization.

[0333] The ratio of heterogeneous connections can be determined by the PVDF. 19Peak determination of F-NMR spectra, as clearly described in EP 2 756 950A1.

[0334] Typically, the fluoropolymer is not crosslinked, and therefore it is suitable for thermoplastic processing.

[0335] The PVDF can maintain the transparency of layer A to a certain extent by using a flatting agent. Organic and inorganic flatting agents can be used as flatting agents.

[0336] In one embodiment, the fluoropolymer is primarily amorphous or microcrystalline PVDF with a haze value of less than 5. For this purpose, the haze value is measured at 23°C for a 30 μm thick pure fluoropolymer (PVDF) film according to ASTM D1003. An example of a PVDF type with particularly good suitability and a suitably low haze value is derived from Solvay. 6008, obtained from Kureha's T850 and from Arkema 9000HD.

[0337] glass beads

[0338] The fluoropolymer-based layer D, if present, may optionally contain glass beads. In this embodiment, the content of glass beads dispersed in the polymer matrix of layer D is typically 3.0 to 30.0% by weight, more preferably 5.0 to 20.0% by weight, and particularly preferably 7.0 to 15.0% by weight, based on the total weight of layer D.

[0339] In addition, glass beads can be used as a first UV absorber in layer A.

[0340] The glass beads may have an aspect ratio of at least about 4:1, more preferably at least about 2:1. Ideally, the glass beads are substantially spherical, i.e., having an aspect ratio of about 1:1.

[0341] The glass beads advantageously have a narrow size distribution. This size distribution can be measured using conventional equipment, such as a Malvern particle size analyzer, for example, by a Mastersizer 2000. Typically, the glass beads are solid (i.e., non-hollow) glass beads, not limited to any chemical composition, and may have a smooth or etched surface. The surface etching can be conveniently performed by contacting the glass beads with nitric acid for a sufficient time to produce the desired degree of surface etching. To achieve optimal adhesion between the glass beads and the fluoropolymer-based matrix, the glass beads may also have a siloxane layer.

[0342] Depending on the desired optical properties and surface roughness of the diaphragm, the size (average diameter, weight average) of the glass beads is typically selected from 2.0 μm to 30.0 μm, preferably from 3.0 μm to 20.0 μm, and even more preferably from 5.0 μm to 15.0 μm. Typically, if glass beads with an average diameter below 2.0 μm are used, the surface of the resulting diaphragm no longer exhibits a matte finish. On the other hand, using glass beads with an average diameter above 30.0 μm results in a relatively high surface roughness, which is undesirable for many applications.

[0343] The size of the glass bead is indicated by what is called d. 50 The value (i.e., 50% by volume of the particles having a particle size lower than the specified average particle size) can be measured according to the standard specification ISO 13320 (2009) for laser diffraction measurements. Typically, in each case (where the refractive index of the dispersion of the particles in butyl acetate is 1.462), the size of the glass beads is determined by laser scattering (at room temperature 23°C) using a Malvern Mastersizer 2000 (with microdispersion MS1) from Malvern Instruments at 2000 rpm, and evaluated by Fraunhofer. Another equally suitable instrument for this purpose is the Beckman Coulter LS13 320 laser diffraction particle size analyzer.

[0344] To achieve good mechanical properties of the diaphragm, the glass beads are preferably non-hollow, i.e., solid.

[0345] The refractive index of the glass beads (which is measured at 20°C for the Na-D line (589 nm)) is selected such that it differs from the refractive index of the polymer material matrix in the fluoropolymer-based layer A by 0.01 to 0.2 units.

[0346] There are no particular limitations on the chemical composition of the glass beads, and virtually any commercially available type of glass can be used. These specifically include fused silica glass, soda-lime silica glass, sodium borosilicate glass, lead oxide glass, aluminosilicate glass, and oxide glass, with soda-lime silica glass being particularly preferred.

[0347] The refractive index of soda-lime silica glass is typically between 1.51 and 1.52. In a particularly preferred embodiment, the glass beads have the following composition:

[0348] 70.0 to 75.0% by weight of SiO2

[0349] 12.0 to 15.0% by weight of Na₂O

[0350] 0.0 to 1.5% by weight of K2O

[0351] 7.0 to 12.0% by weight of CaO

[0352] 0.0 to 5.0% by weight of MgO

[0353] 0.1 to 2.5 wt% Al2O3

[0354] 0.0 to 0.5% by weight of Fe2O3

[0355] Suitable examples of glass beads are available from Potters Industries LLC. Products, such as 7025 and 5000, or may be obtained from Sovitec MondialS.A. glass beads NP3 and NP5. Furthermore, the use of colored glass beads with a particle size of less than 10 μm is particularly advantageous in terms of effective UV absorption and high transmittance of visible light. While there are no particular limitations on the choice of glass for this purpose, glass varieties such as GG395, GG400, GG420, GG435, GG475, OG515, and OG 530, available from Schott AG (Mainz, Germany), are particularly useful.

[0356] Diaphragm performance

[0357] Typically, the diaphragm of the present invention has an average transmittance of no more than 40%, preferably no more than 30%, and more preferably no more than 10% in the wavelength interval of 350 nm to 390 nm.

[0358] As noted above, the diaphragm of the present invention exhibits excellent weathering stability and mechanical properties. In particular, after 6,000 hours of accelerated weathering testing according to standard ISO 4892-2, Method A, Cycle 1 (2013), the elongation at break of the diaphragm (which is measured by a common method (e.g., one described in standard ISO 527-3 (2003)) is at least 60%, preferably at least 70%, and even more preferably at least 90% of the initial elongation at break of the diaphragm.

[0359] Furthermore, even when relatively small amounts of the first and second UV absorbers are used in the multilayer film, accelerated aging tests are conducted for 15,000 hours (30 GJ / m²) according to standard ISO 4892-2 (2013) Method A, Cycle 1. 2After radiation exposure, the optical transmittance of the diaphragm at any wavelength λ is generally no greater than 10%, preferably no greater than 5%, more preferably no greater than 2%, and even more preferably no greater than 1%; wherein 270nm≤λ≤370nm.

[0360] According to DIN EN ISO 4892-2 (2013), Method A, using Cycle 1, the climate aging test was conducted under the following conditions:

[0361]

[0362] Typically, for each wavelength from 400 nm to 800 nm, the diaphragm of the present invention has a light transmittance (D) greater than 60%, preferably greater than 70%, more preferably greater than 80%, as measured according to standard DIN EN ISO 13468-2 (2006) prior to climate aging testing. 65 ).

[0363] Methods for manufacturing membranes

[0364] Depending on the intended application, the membranes of the present invention can be prepared at virtually any desired thickness. A surprising factor here is the ability to achieve excellent weather resistance and mechanical stability, as well as to provide very high levels of weathering and mechanical protection to the substrate. However, for the purposes of the invention, relatively thin membranes are preferred, characterized by a thickness in the range of 10.0 to 200.0 μm, preferably in the range of 40.0 to 120.0 μm, and particularly preferably in the range of 50.0 to 90.0 μm.

[0365] The mixture of components of the layer can be prepared by dry mixing the components in powder, granular, or preferably granulated form. Such a mixture can also be processed to obtain a ready-to-use molding composition by melting and mixing the components in a molten state or by melting a dry premix of the components. This can be done, for example, in a single-screw or twin-screw extruder. The resulting extrudate can then be granulated. Conventional additives, auxiliaries, and / or fillers can be directly mixed or added subsequently by the end user as needed.

[0366] The multilayer film of the present invention can then be prepared by methods known per se, such as co-extrusion or lamination, or by extrusion lamination.

[0367] Applying the diaphragm to the substrate

[0368] The diaphragm of the present invention has a wide range of applications. A preferred use of the diaphragm is for coating plastic molded articles or metal articles. In particular, the substrate protected by the diaphragm can be melamine resin-impregnated paper, an optional fiber-reinforced polymer material, preferably polyvinyl chloride (PVC), polycarbonate (PC) or polypropylene (PP), or metal, preferably steel or aluminum, and the co-extruded diaphragm is applied directly to the substrate.

[0369] Particularly advantageous here is the coating of molded articles containing or composed of PVC. Advantageously, the protected substrate is, for example, a window profile composed of aluminum, wood, plastic, or composite materials, and the protected substrate may have a decorative film, preferably composed of PC, SAN, or PVC. Such articles are then protected from weathering by using the film of the present invention. Another preferred use of the film of the present invention is in the design of high-specification, durable surface finishing paints for substrate materials. Additionally, the film can be advantageously used in traffic control materials (TCM).

[0370] As will be readily apparent to those skilled in the art, the film of the present invention is applied to a substrate such that layer A faces the outer surface of the substrate to be coated. In other words, if the film of the present invention substantially consists of layers A and B, then layer B is located between layer A and the substrate. In embodiments where the film of the present invention further includes layer C, layer C is located between layer B and the surface of the substrate to be coated.

[0371] Another aspect of the invention is a method of manufacturing a coated article, the method comprising the step of applying a film to the surface of the substrate. Such a coated article comprises a substrate and has an outer surface, wherein the substrate is at least partially covered by the film, wherein the film has layers arranged in the following order starting from the outer surface of the coated article:

[0372] • If layer D exists,

[0373] • Layer A,

[0374] • If layer E exists,

[0375] • Layer B, and

[0376] • The layer C, if it exists.

[0377] In all cases, applying the film of the present invention to a substrate is relatively simple. Preferably, the film is applied to the material to be protected by means of co-extrusion. The film can also be applied to the material to be protected by means of film lamination. A further preferred application is characterized by applying the film to the material to be protected by means of extrusion lamination. Preferably, the extrusion lamination is carried out at a temperature greater than or equal to 120°C and under a mechanical pressure greater than or equal to 1 MPa, preferably greater than or equal to 2 MPa, more preferably greater than or equal to 4 MPa, more preferably greater than or equal to 6 MPa, and more preferably greater than or equal to 7 MPa.

[0378] In one embodiment of the invention, the article itself may be a film or sheet, which may be conveniently stored and / or handled in roll form.

[0379] In some embodiments, the coated article of the present invention may be a high-pressure laminate (HPL), a medium-pressure laminate (MPL), or a continuous-pressure laminate (CPL). In a particularly preferred embodiment, the multilayer material obtained using the diaphragm of the present invention is a decorative high-pressure laminate (HPL) according to EN 438-6, which consists of layers (e.g., paper) of a web of fibrous material impregnated with a curable resin, these layers being bonded to each other by means of a high-pressure method described below. The surface layer of the material (having a decorative color or pattern on one or both sides) is impregnated with an amino-based resin (e.g., melamine resin). Then, during the high-pressure process, amino or hydroxymethyl amino groups present in the decorative layer act as reaction participants for covalent bonding to the polymethacrylic acid-based layer (in this case, the diaphragm) for surface finishing. A corresponding high-pressure laminate is particularly described in US2017 / 0197391A1.

[0380] Therefore, one aspect of the present invention relates to a method for manufacturing high-pressure laminates using the diaphragm as described above.

[0381] The high-pressure method produces a durable bond between the decorative layer and the polymethacrylic layer applied according to the invention. The temperature set during the method and the associated interpenetration of the melamine-saturated decorative paper into the film ensure sufficient covalent bond formation and thus ensure a durable bond with the material.

[0382] The high-pressure method is defined as simultaneously using heat (temperature greater than or equal to 120°C) and high pressure (greater than or equal to 3 MPa), resulting in the curable resin flowing and subsequently hardening to produce a product with a relatively high density (at least 1.35 g / cm³). 3 A uniform non-porous material with the desired surface structure.

[0383] Typically, the coated article of the present invention has the following layer arrangement in the multilayer film:

[0384] If present, layer D forms the outer surface of the coated article;

[0385] Layer A is located between layer D and the substrate;

[0386] If layer E exists, it is located between layer A and layer B.

[0387] Layer B is located between layer A and the substrate; and

[0388] If present, layer C is located between layer B and the substrate. Detailed Implementation

[0389] The following embodiments will illustrate the invention in more detail, but are not intended to limit the invention.

[0390] Example

[0391] According to DIN EN ISO 4892-2 (2013), Method A, using the first cycle, climate aging tests were conducted under the following conditions in the wavelength range of 300 to 400 nm:

[0392]

[0393] Optical evaluation was performed at 0, 1,000, 2,000, 4,000, 6,000, 8,000, 10,000, 12,000, 14,000 and 16,000 hours.

[0394] Protective films are prepared by adapter co-extrusion using a 35mm diameter single-screw extruder and a 25mm diameter single-screw co-extruder at an extrusion speed of 7.3 m / min and at a melt temperature of 240-250°C, employing a cooling roller process. For three-layer films, a second 25mm diameter single-screw co-extruder is used. Alternatively, preparation can be achieved via manifold co-extrusion or a combination of adapter and manifold co-extrusion.

[0395] The adhesion promoter used is a copolymer formed from 75 wt% MMA, 15 wt% styrene, and 10 wt% maleic anhydride. The weight-average molar mass (Mw) of this copolymer is approximately 100,000 g / mol (determined by GPC relative to a PMMA standard).

[0396] As mentioned above, accelerated climate aging tests were conducted according to standard ISO 4892-2 (2013).

[0397] Preparation Example 1 (Comparative membrane according to WO 2007 / 0074138 A1)

[0398] Using a 35mm diameter single-screw extruder and a 25mm diameter single-screw co-extruder, at an extrusion speed of 7.3m / min and at a melt temperature of 240-250℃, a PMMA monolayer film with a total thickness of 53μm was prepared by extrusion.

[0399] The single-layer membrane has the following composition:

[0400] a) 85.7% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0401] 61.3% by weight of methyl methacrylate,

[0402] 38.0% by weight of butyl acrylate,

[0403] 0.7% by weight of allyl methacrylate,

[0404] b) 12.3% by weight 7H, can be obtained from

[0405] c) 1.0% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0406] d) 0.7% by weight 1600 (6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-idexyl]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-dien-1-one), available from BASF SE.

[0407] e) 0.3% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0408] Preparation Example 2 (Membrane according to the present invention)

[0409] Under the same conditions as in Example 1, a PMMA-based bilayer film with a thickness of 53 μm was prepared by co-extrusion.

[0410] Layer A has a thickness of 23 μm and the following composition:

[0411] a) 85.7% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0412] 61.3% by weight of methyl methacrylate,

[0413] 38.0% by weight of butyl acrylate,

[0414] 0.7% by weight of allyl methacrylate,

[0415] b) 12.3% by weight 7H, can be obtained from

[0416] c) 1.72% by weight 1600, obtained from BASF SE

[0417] d) 0.3% by weight stab UV 119, obtained from Sabo SpA.

[0418] The transmittance of layer A at a wavelength of 360 nm is 1.7%. Layer A has a transmittance of 1.7% at any wavelength λ. A The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ A ≤360nm.

[0419] Layer B has a thickness of 30 μm and the following composition:

[0420] a) 85.7% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0421] 61.3% by weight of methyl methacrylate,

[0422] 38.0% by weight of butyl acrylate,

[0423] 0.7% by weight of allyl methacrylate,

[0424] b) 12.3% by weight 7H, can be obtained from

[0425] c) 1.7% by weight 360, available from BASF SE

[0426] d) 0.3% by weight stab UV 119, obtained from Sabo SpA.

[0427] Layer B at any wavelength λ B The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ B ≤370nm.

[0428] Preparation Example 3 (Comparative Membrane)

[0429] Under the same conditions as in Example 1, a PMMA-based bilayer film with a thickness of 58 μm was prepared by co-extrusion.

[0430] The layer D has a thickness of 5 μm and the following composition:

[0431] a) 100.0% by weight of KF Polymer 850 PVDF, available from KUREHACORPORATION

[0432] Layer C has a thickness of 53 μm and the following composition:

[0433] a) 85.7% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0434] 61.3% by weight of methyl methacrylate,

[0435] 38.0% by weight of butyl acrylate,

[0436] 0.7% by weight of allyl methacrylate,

[0437] b) 12.3% by weight 7H, can be obtained from

[0438] c) 1.0% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0439] d) 0.7% by weight 1600 (6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-idexyl]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-dien-1-one), available from BASF SE.

[0440] e) 0.3% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0441] Preparation Example 4 (Membrane according to the present invention)

[0442] Under the same conditions as in Example 1, a PMMA-based three-layer film with a thickness of 58 μm was prepared by co-extrusion.

[0443] The layer D has a thickness of 5 μm and the following composition:

[0444] a) 100.0% by weight of KF Polymer 850 PVDF, available from KUREHACORPORATION

[0445] Layer A has a thickness of 23 μm and the following composition:

[0446] b) 85.7% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0447] 61.3% by weight of methyl methacrylate,

[0448] 38.0% by weight of butyl acrylate,

[0449] 0.7% by weight of allyl methacrylate,

[0450] b) 12.3% by weight 7H, can be obtained from

[0451] c) 1.72% by weight 1600, obtained from BASF SE

[0452] d) 0.3% by weight stab UV 119, obtained from Sabo SpA.

[0453] The transmittance of layer A at a wavelength of 360 nm is 1.7%. Layer A has a transmittance of 1.7% at any wavelength λ. A The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ A ≤360nm.

[0454] Layer B has a thickness of 30 μm and the following composition:

[0455] b) 85.35% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0456] 61.3% by weight of methyl methacrylate,

[0457] 38.0% by weight of butyl acrylate,

[0458] 0.7% by weight of allyl methacrylate,

[0459] b) 12.3% by weight 7H, can be obtained from

[0460] c) 2.05% by weight 360, available from BASF SE

[0461] d) 0.3% by weight stab UV 119, obtained from Sabo SpA.

[0462] Layer B at any wavelength λ B The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ B ≤370nm.

[0463] Preparation Example 5 (Comparative Membrane)

[0464] Under the same conditions as in Example 1, a PMMA-based bilayer film with a thickness of 58 μm was prepared by co-extrusion.

[0465] The layer D has a thickness of 5 μm and the following composition:

[0466] b) 100.0% by weight of KF Polymer 850 PVDF, available from KUREHACORPORATION

[0467] Layer C has a thickness of 53 μm and the following composition:

[0468] a) 83.0% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0469] 61.3% by weight of methyl methacrylate,

[0470] 38.0% by weight of butyl acrylate,

[0471] 0.7% by weight of allyl methacrylate,

[0472] b) 15.0% by weight of adhesion promoter,

[0473] c) 1.0% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0474] d) 0.7% by weight 1600 (6-[4,6-bis(4-phenylphenyl)-1,2-dihydro-1,3,5-triazine-2-idexyl]-3-[(2-ethylhexyl)oxy]cyclohexyl-2,4-dien-1-one), is available from BASF SE.

[0475] e) 0.3% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2”-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N”-dibutyl-N',N”-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0476] Preparation Example 6 (Membrane according to the present invention)

[0477] Under the same conditions as in Example 1, a PMMA-based three-layer film with a thickness of 58 μm was prepared by co-extrusion.

[0478] The layer D has a thickness of 5 μm and the following composition:

[0479] c) 100.0% by weight of KF Polymer 850 PVDF, available from KUREHACORPORATION

[0480] Layer A has a thickness of 23 μm and the following composition:

[0481] d) 85.7% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0482] 61.3% by weight of methyl methacrylate,

[0483] 38.0% by weight of butyl acrylate,

[0484] 0.7% by weight of allyl methacrylate,

[0485] b) 12.3% by weight 7H, can be obtained from

[0486] c) 1.72% by weight 1600, obtained from BASF SE

[0487] d) 0.3% by weight stab UV 119, obtained from Sabo SpA.

[0488] The transmittance of layer A at a wavelength of 360 nm is 1.7%. Layer A has a transmittance of 1.7% at any wavelength λ. A The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ A ≤360nm.

[0489] Layer B has a thickness of 30 μm and the following composition:

[0490] c) 82.65% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0491] 61.3% by weight of methyl methacrylate,

[0492] 38.0% by weight of butyl acrylate,

[0493] 0.7% by weight of allyl methacrylate,

[0494] b) 15.0% by weight of adhesion promoter,

[0495] c) 2.05% by weight 360, available from BASF SE

[0496] d) 0.3% by weight stab UV 119, obtained from Sabo SpA.

[0497] The transmittance of layer B at a wavelength of 370 nm is 0.7%. The transmittance of layer B at any wavelength λ... B The spectral transmittance at a certain point is no greater than 10%; where 270 nm ≤ λ B ≤370nm.

[0498] The films prepared in Examples 1, 2, 3, and 4 were then laminated onto the PVC decorative film, while the film prepared in Example 2 was laminated onto the PVC film with layer B (Example 2a). As a comparative example, the film prepared in Example 2 was laminated onto the PVC film with layer A (Example 2b). The films prepared in Examples 3 and 4 were laminated onto the PVC film with layer C, or, in the case of Example 4, with layer B (Examples 3 and 4).

[0499] The films prepared in Examples 5 and 6 were used to prepare HPL. The HPL was prepared by simultaneously laminating resin-impregnated paper layers and stacked protective films (Preparation Examples 5 and 6). The core layer consisted of paper impregnated with phenolic resin. Decorative paper impregnated with melamine resin was present between these layers and the protective films. Anthracite-colored HPL was prepared and used for subsequent testing.

[0500] Samples from Examples 1, 2a and 2b, 3, 4, 5 and 6 were subjected to accelerated weathering testing according to standard ISO 4892-2 (2013), Method 1. Subsequently, the color difference ΔECIELAB 1976(D) of each sample was determined according to standard DIN ENISO11664-4:2011-07. 65 ,10°).

[0501] The obtained data is summarized in Table 1 below:

[0502]

[0503] Table 1. Results of Accelerated Climate Aging Tests

[0504] In Examples 1, 2b, and 3 (Comparative Examples), the UV protection provided by the film at wavelengths below 360 nm was only moderate, and therefore a color difference greater than 2 was observed after approximately 10,000 hours, and a color difference greater than 3 was observed after approximately 15,000 hours. In Example 5 (Comparative Example), the UV protection provided by the film at wavelengths below 360 nm was only moderate, and therefore a color difference greater than 2.5 was observed after approximately 20,000 hours. Even with the naked eye, an observer could easily identify these values ​​as UV damage to the PVC decorative film, or to the ink on the HPL.

[0505] Conversely, in Examples 2a, 4, and 6 (embodiments of the present invention), the UV protection provided by the film offered significantly better UV protection. Even after 20,000 hours of exposure, the detected color difference was less than 2, i.e., almost invisible to the observer. No visible damage to the film occurred.

[0506] In Preparation Examples 7-16, protective films were prepared by extruding monolayer films using a 35mm diameter single-screw extruder at an extrusion speed of 7.3 m / min and at 240-250°C (melt temperature) using a cooling roller process. To compare different climate aging behaviors, monolayer films comprising all UV absorbers were compared with films made from laminated layers (each layer comprising one of the UV absorbers used). For example, a 90μm monolayer film with three UV absorbers was compared with a 90μm film composed of three layers (each layer comprising one of the UV absorbers used). The lamination was performed using a press at 140°C, where stacked monolayer films, each with a thickness of 30μm, were pressed together, with a maximum pressing time of 1 minute. The films were placed between two rubber sheets and a separator sheet to prevent adhesion to the rubber sheets, as shown. Figure 1 As shown.

[0507] Cut off a portion of the laminated membrane containing air bubbles and measure the thickness of the resulting multilayer membrane.

[0508] Alternatively, the preparation can be achieved by a manifold co-extrusion method or a combination of adapter and manifold co-extrusion.

[0509] Preparation Example 7 (Comparative Membrane)

[0510] Using a 35mm diameter single-screw extruder, at an extrusion speed of 7.3m / min and at a melt temperature of 240-250℃, a PMMA monolayer film with a total thickness of 90μm was prepared by extrusion.

[0511] The single-layer membrane has the following composition:

[0512] a) 85.69% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0513] 61.3% by weight of methyl methacrylate,

[0514] 38.0% by weight of butyl acrylate,

[0515] 0.7% by weight of allyl methacrylate,

[0516] b) 12.0% by weight 7H, can be obtained from (Darmstadt, Germany)

[0517] c) 0.67% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0518] d) 0.66% by weight 1577 (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol), available from BASF SE.

[0519] e) 0.66% by weight of nano-sized zinc oxide, obtained by using materials available from Croda GmbH (Nettal, Germany). UV 200F achieved,

[0520] f) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0521] Preparation Example 8 (Comparative Membrane)

[0522] Under the same conditions as in Example 7, a PMMA monolayer film with a total thickness of 60 μm was prepared by extrusion.

[0523] The single-layer membrane has the following composition:

[0524] a) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0525] 61.3% by weight of methyl methacrylate,

[0526] 38.0% by weight of butyl acrylate,

[0527] 0.7% by weight of allyl methacrylate,

[0528] b) 12.0% by weight 7H, can be obtained from

[0529] c) 1.00% by weight 1577 (2-[4,6-diphenyl-1,3,5-triazin-2-yl]-5-[(hexyl)oxy]-phenol), available from BASF SE.

[0530] d) 1.00% by weight of nano-sized zinc oxide, obtained by using materials available from Croda GmbH. UV200F is achieved.

[0531] e) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0532] Preparation Example 9 (Comparative Membrane)

[0533] Under the same conditions as in Example 7, a PMMA monolayer film with a total thickness of 90 μm was prepared by extrusion.

[0534] The single-layer membrane has the following composition:

[0535] a) 85.68% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0536] 61.3% by weight of methyl methacrylate,

[0537] 38.0% by weight of butyl acrylate,

[0538] 0.7% by weight of allyl methacrylate,

[0539] b) 12.0% by weight 7H, can be obtained from

[0540] c) 0.67% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0541] d) 0.66% by weight 1577 (2-[4,6-diphenyl-1,3,5-triazin-2-yl]-5-[(hexyl)oxy]-phenol), available from BASF SE.

[0542] e) 0.67% by weight BLA 4200M (included) 329 and B-CAP's commercial products are available from EUTEC CHEMICAL CO.,LTD.

[0543] f) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0544] Preparation Example 10 (Comparative Membrane)

[0545] Under the same conditions as in Example 7, a PMMA monolayer film with a total thickness of 90 μm was prepared by extrusion.

[0546] The single-layer membrane has the following composition:

[0547] a) 86.13% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0548] 61.3% by weight of methyl methacrylate,

[0549] 38.0% by weight of butyl acrylate,

[0550] 0.7% by weight of allyl methacrylate,

[0551] b) 12.193% by weight 7H, can be obtained from

[0552] c) 0.67% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0553] d) 0.66% by weight 1577 (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol), available from BASF SE.

[0554] e) 0.017 wt% of Orracet Yellow 180 (1,8-bis(phenylthio)anthraquinone; 1,8-bis(phenylthio)-9,10-anthradinone), available from BASF SE.

[0555] f) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0556] Preparation Example 11 (Comparative Membrane)

[0557] Under the same conditions as in Example 7, a PMMA monolayer film with a total thickness of 60 μm was prepared by extrusion.

[0558] The single-layer membrane has the following composition:

[0559] a) 86.3% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0560] 61.3% by weight of methyl methacrylate,

[0561] 38.0% by weight of butyl acrylate,

[0562] 0.7% by weight of allyl methacrylate,

[0563] b) 12.325% by weight 7H, can be obtained from

[0564] c) 1.02% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0565] d) 0.025% by weight of Orracet Yellow 180 (1,8-bis(phenylthio)anthraquinone; 1,8-bis(phenylthio)-9,10-anthradinone), available from BASF SE.

[0566] e) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2”-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0567] Preparation Example 12 (The Membrane of the Invention)

[0568] Based on the conditions given above, a PMMA three-layer film with a total thickness of 90 μm was prepared by laminating three 30 μm thick single-layer films.

[0569] The three-layer membrane has the following composition:

[0570] 1. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0571] a) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0572] 61.3% by weight of methyl methacrylate,

[0573] 38.0% by weight of butyl acrylate,

[0574] 0.7% by weight of allyl methacrylate,

[0575] b) 12.0% by weight 7H, can be obtained from

[0576] c) 2.00% by weight of nano-sized zinc oxide, obtained by using materials available from Croda GmbH. UV200F is achieved.

[0577] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0578] 2. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0579] a) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0580] 61.3% by weight of methyl methacrylate,

[0581] 38.0% by weight of butyl acrylate,

[0582] 0.7% by weight of allyl methacrylate,

[0583] b) 12.0% by weight 7H, can be obtained from

[0584] c) 2.00% by weight 1577 (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol), available from BASF SE.

[0585] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0586] 3. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0587] a) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0588] 61.3% by weight of methyl methacrylate,

[0589] 38.0% by weight of butyl acrylate,

[0590] 0.7% by weight of allyl methacrylate,

[0591] b) 12.0% by weight 7H, can be obtained from

[0592] c) 2.00% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0593] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0594] Preparation Example 13 (The Membrane of the Invention)

[0595] Based on the conditions given above, a PMMA bilayer membrane with a total thickness of 60 μm was prepared by laminating two 30 μm thick single membranes.

[0596] The double-layer membrane has the following composition:

[0597] 1. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0598] b) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0599] 61.3% by weight of methyl methacrylate,

[0600] 38.0% by weight of butyl acrylate,

[0601] 0.7% by weight of allyl methacrylate,

[0602] b) 12.0% by weight 7H, can be obtained from

[0603] c) 2.00% by weight of nano-sized zinc oxide, obtained by using materials available from Croda GmbH. UV200F is achieved.

[0604] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0605] 2. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0606] a) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0607] 61.3% by weight of methyl methacrylate,

[0608] 38.0% by weight of butyl acrylate,

[0609] 0.7% by weight of allyl methacrylate,

[0610] b) 12.0% by weight 7H, can be obtained from

[0611] c) 2.00% by weight 1577 (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol), available from BASF SE.

[0612] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0613] Preparation Example 14 (The Membrane of the Invention)

[0614] Based on the conditions given above, a PMMA three-layer film with a total thickness of 90 μm was prepared by laminating three 30 μm thick single-layer films.

[0615] The three-layer membrane has the following composition:

[0616] 1. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0617] a) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0618] 61.3% by weight of methyl methacrylate,

[0619] 38.0% by weight of butyl acrylate,

[0620] 0.7% by weight of allyl methacrylate,

[0621] b) 12.0% by weight 7H, can be obtained from

[0622] c) 2.00% by weight 1577 (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol), available from BASF SE.

[0623] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0624] 2. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0625] a) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0626] 61.3% by weight of methyl methacrylate,

[0627] 38.0% by weight of butyl acrylate,

[0628] 0.7% by weight of allyl methacrylate,

[0629] b) 12.0% by weight 7H, can be obtained from

[0630] c) 2.00% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0631] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0632] 3. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0633] a) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0634] 61.3% by weight of methyl methacrylate,

[0635] 38.0% by weight of butyl acrylate,

[0636] 0.7% by weight of allyl methacrylate,

[0637] b) 12.0% by weight 7H, can be obtained from

[0638] c) 2.00% by weight BLA 4200M (included) 329 and B-CAP's commercial products are available from Eutec Chemical Co., Ltd.

[0639] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0640] Preparation Example 15 (The Membrane of the Present Invention)

[0641] Based on the conditions given above, a PMMA three-layer film with a total thickness of 90 μm was prepared by laminating three 30 μm thick single-layer films.

[0642] The three-layer membrane has the following composition:

[0643] 1. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0644] d) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0645] 61.3% by weight of methyl methacrylate,

[0646] 38.0% by weight of butyl acrylate,

[0647] 0.7% by weight of allyl methacrylate,

[0648] b) 12.0% by weight 7H, can be obtained from

[0649] c) 2.00% by weight 1577 (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol), available from BASF SE.

[0650] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0651] 2. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0652] a) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0653] 61.3% by weight of methyl methacrylate,

[0654] 38.0% by weight of butyl acrylate,

[0655] 0.7% by weight of allyl methacrylate,

[0656] b) 12.0% by weight 7H, can be obtained from

[0657] c) 2.00% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0658] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis(N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0659] 3. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0660] a) 86.97% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0661] 61.3% by weight of methyl methacrylate,

[0662] 38.0% by weight of butyl acrylate,

[0663] 0.7% by weight of allyl methacrylate,

[0664] b) 12.65% by weight 7H, can be obtained from

[0665] c) 0.05% by weight of Orracet Yellow 180 (1,8-bis(phenylthio)anthraquinone; 1,8-bis(phenylthio)-9,10-anthradinone), available from BASF SE.

[0666] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0667] Preparation Example 16 (The Membrane of the Invention)

[0668] Based on the conditions given above, a PMMA bilayer membrane with a total thickness of 60 μm was prepared by laminating two 30 μm thick monolayer membranes.

[0669] The double-layer membrane has the following composition:

[0670] 1. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0671] a) 85.67% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0672] 61.3% by weight of methyl methacrylate,

[0673] 38.0% by weight of butyl acrylate,

[0674] 0.7% by weight of allyl methacrylate,

[0675] b) 12.0% by weight 7H, can be obtained from

[0676] c) 2.00% by weight 360 (phenol-2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))), is available from BASF SE (Ludwigshafen, Germany).

[0677] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis(N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

[0678] 2. A monolayer film with a thickness of 30 μm was prepared by extrusion under the same conditions as in Example 7, and the monolayer film had the following composition:

[0679] a) 86.97% by weight of a polymeric acrylic core-shell impact modifier, having the following composition:

[0680] 61.3% by weight of methyl methacrylate,

[0681] 38.0% by weight of butyl acrylate,

[0682] 0.7% by weight of allyl methacrylate,

[0683] b) 12.65% by weight 7H, can be obtained from

[0684] c) 0.05% by weight of Orracet Yellow 180 (1,8-bis(phenylthio)anthraquinone; 1,8-bis(phenylthio)-9,10-anthradinone), available from BASF SE.

[0685] d) 0.33% by weight stab UV 119 (1,3,5-triazine-2,4,6-triamine, N2,N2"-1,2-ethanediylbis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N',N"-dibutyl-N',N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)), is available from Sabo SpA (Levat, Italy).

Claims

1. A multilayer film comprising at least layer A and layer B, wherein Layer A includes a total weight meter based on layer A: 0.0 to 99.9% by weight of poly(meth)acrylate; 0.0 to 95.0% by weight of one or more impact modifiers; 0.0 to 30.0% by weight of fluoropolymers; 0.1 to 5.0% by weight of a first UV absorber, wherein the first UV absorber is a triazine compound; 0.0 to 5.0% by weight of one or more UV stabilizers; The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer A is at least 50% by weight and not more than 99.9% by weight based on the weight of layer A; and wherein Layer A at any wavelength λ A The spectral transmittance at that location is no greater than 10%; where 270 nm ≤ λ A ≤ 360 nm; and Layer B includes a total weight meter based on layer B: 0.0 to 99.9% by weight of poly(meth)acrylate; 0.0 to 85.0% by weight of one or more impact modifiers; 0.1 to 5.0% by weight of a second UV absorber that is different from the first UV absorber, wherein the second UV absorber is a benzotriazole type compound; 0.0 to 5.0% by weight of one or more UV stabilizers; and 0.0 to 20.0% by weight of an adhesion-promoting copolymer, the adhesion-promoting copolymer comprising: based on the weight of the adhesion-promoting copolymer: (i) 70.0 to 95.0% by weight of methyl methacrylate; (ii) 0.5 to 15.0% by weight of maleic anhydride; and (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers, which have no functional groups other than vinyl functional groups; and The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer B is at least 50% by weight and not more than 99.9% by weight based on the weight of layer B; and wherein Layer B at any wavelength λ B The spectral transmittance at that location is no greater than 10%; where 270 nm ≤ λ B ≤ 370 nm; and Layer A contains no more than 0.1% by weight of the second UV absorber, and Layer B contains no more than 0.1% by weight of the first UV absorber; The layer A has a thickness of 20.0 μm to 40.0 μm; and the layer B has a thickness of 20.0 μm to 40.0 μm; Layer B is located below layer A, and The one or more impact modifiers mentioned above are selected from cross-linked impact modifiers having a core-shell or core-shell-shell structure.

2. The membrane of claim 1, wherein the cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer A is at least 95% by weight and not more than 99.9% by weight based on the weight of layer A; and The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer B is at least 95% by weight and not more than 99.9% by weight based on the weight of layer B.

3. A multilayer film comprising at least layer A and layer B, wherein Layer A includes a total weight meter based on layer A: 0.0 to 99.0% by weight of poly(meth)acrylate; 0.0 to 95.0% by weight of one or more impact modifiers; 0.0 to 30.0% by weight of fluoropolymers; 1.0 to 30.0% by weight of a first UV absorber, wherein the first UV absorber is an inorganic particulate material selected from zinc oxide, titanium dioxide, cerium dioxide, tin dioxide, silicon dioxide, and glass; and 0.0 to 5.0% by weight of one or more UV stabilizers; The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer A is at least 50% by weight and not more than 97.0% by weight based on the weight of layer A. and among them Layer A at any wavelength λ A The spectral transmittance at that location is no greater than 20%; where 270 nm ≤ λ A ≤ 310 nm; and Layer B includes a total weight meter based on layer B: 0.0 to 99.9% by weight of poly(meth)acrylate; 0.0 to 85.0% by weight of one or more impact modifiers; 0.1 to 5.0% by weight of a second UV absorber that is different from the first UV absorber, wherein the second UV absorber is a benzotriazole type compound; 0.0 to 5.0% by weight of one or more UV stabilizers; and 0.0 to 20.0% by weight of an adhesion-promoting copolymer, the adhesion-promoting copolymer comprising: based on the weight of the adhesion-promoting copolymer: (i) 70.0 to 95.0% by weight of methyl methacrylate; (ii) 0.5 to 15.0% by weight of maleic anhydride; and (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers, which have no functional groups other than vinyl functional groups; and The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer B is at least 50% by weight and not more than 99.9% by weight based on the weight of layer B; and wherein Layer B at any wavelength λ B The spectral transmittance at that location is no greater than 10%; where 270 nm ≤ λ B ≤ 370 nm; and Layer A contains no more than 0.1% by weight of the second UV absorber, and Layer B contains no more than 0.1% by weight of the first UV absorber; The layer A thereon has a thickness of 20.0 μm to 40.0 μm; The layer B has a thickness of 20.0 μm to 40.0 μm.

4. The membrane of claim 3, wherein the cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer A is at least 95% by weight and not more than 97.0% by weight based on the weight of layer A; and wherein The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer B is at least 95% by weight and not more than 99.9% by weight based on the weight of layer B.

5. The membrane according to any one of claims 1-4, wherein the membrane further comprises an adhesion-promoting layer C, wherein the layer C comprises, based on the total weight of the layer C: 0.0 to 95.0% by weight of poly(meth)acrylate; 0.0 to 75.0% by weight of one or more impact modifiers; 0.0 to 5.0% by weight of UV absorber; 0.0 to 5.0% by weight of one or more UV stabilizers; and 5.0 to 80.0% by weight of an adhesion-promoting copolymer, wherein the adhesion-promoting copolymer comprises: based on the weight of the adhesion-promoting copolymer: (i) 70.0 to 95.0% by weight of methyl methacrylate; (ii) 0.5 to 15.0% by weight of maleic anhydride; and (iii) 0.0 to 25.0% by weight of other vinyl comonomers, which have no functional groups other than vinyl functional groups; and The cumulative content of the poly(meth)acrylate and one or more impact modifiers in layer C is at least 20.0% by weight and not more than 95.0% by weight based on the weight of layer C. and Layer B comprises less than 3.0% by weight of the adhesion-promoting copolymer based on the weight of layer B.

6. The film according to claim 5, wherein the UV absorber in layer C is the second UV absorber.

7. The membrane according to any one of claims 1 to 4, wherein the membrane further comprises a fluoropolymer-based layer D adjacent to layer A, the layer D comprising, by weight of the total weight of layer D: At least one fluoropolymer, comprising 40.0 to 100.0% by weight; 0.0 to 60.0% by weight of poly(meth)acrylate; and 0.0 to 30.0% by weight of substantially spherical glass beads.

8. The membrane according to any one of claims 1 to 4, wherein the fluoropolymer is selected from polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polyethylene-tetrafluoroethylene (ETFE), fluorinated ethylene-propylene (FEP), or mixtures or copolymers thereof.

9. The film according to any one of claims 1 to 4, wherein the film further comprises a layer E located between the layer A and the layer B and comprising a combination of the first UV absorber and the second UV absorber.

10. The membrane according to claim 1 or 2, wherein Layer A comprises 0.5 to 3.0% by weight of a triazine compound as a first UV absorber, based on the weight of layer A; and Layer B contains 0.5 to 4.0% by weight of a benzotriazole-type compound as a second UV absorber.

11. The film according to any one of claims 1 to 4, wherein the UV stabilizer is a hindered amine light stabilizer (HALS) or an antioxidant.

12. The membrane according to any one of claims 1 to 4, wherein the poly(meth)acrylate is a poly(meth)acrylate having an average molecular weight Mw of 80,000 g / mol to 220,000 g / mol, and is obtained by polymerizing a composition having a polymerizable component comprising, by weight, based on the polymerizable composition: (a) 50.0 to 99.9% by weight of methyl methacrylate, (b) 0.1 to 50.0% by weight of acrylates of C1-C4 alcohols, (c) 0.0 to 10.0% by weight of at least one other monomer capable of copolymerizing with said monomers (a) and (b).

13. The diaphragm according to claim 5, wherein Layer C has a thickness ranging from 1.0 μm to 20.0 μm.

14. The diaphragm according to claim 7, wherein Layer D has a thickness ranging from 1.0 μm to 40.0 μm.

15. The membrane according to claim 9, wherein Layer E has a thickness ranging from 10.0 μm to 80.0 μm.

16. The membrane according to any one of claims 1 to 4, wherein the membrane has an average transmittance of not more than 40% in a wavelength interval of 350 nm to 390 nm.

17. The membrane according to any one of claims 1 to 4, wherein, according to standard ISO 4892-2 (2013), method 1, 30 GJ / m 2 After 15,000 hours of accelerated climate aging testing with radiation exposure, the spectral transmittance of the membrane at any wavelength λ is no greater than 5%; where 270 nm ≤ λ ≤ 370 nm.

18. The membrane according to any one of claims 1 to 4, wherein the membrane has a light transmittance D greater than 60% for each wavelength from 400 nm to 800 nm, as measured according to standard DIN EN ISO 13468-2 (2006) prior to climate aging testing. 65 .

19. A coated article having an outer surface and comprising a substrate at least partially covered by a film according to any one of claims 1 to 18.

20. The coated article of claim 19, wherein the film is a co-extruded film and comprises the following layers arranged in the following order, starting from the outer surface: Optional layer D; Layer A; Optional layer E; Layer B; and Optional layer C.

21. The coated article according to claim 19 or 20, wherein the coated article is a high-pressure laminate (HPL), a medium-pressure laminate (MPL), or a continuous pressure laminate (CPL).

22. The coated article of claim 19 or 20, wherein the substrate is melamine resin impregnated paper, optionally fiber-reinforced polymer material, or metal, and the co-extruded film is applied directly to the substrate.

23. The coated article of claim 22, wherein the polymer material is polyvinyl chloride (PVC), polycarbonate, or polypropylene (PP).

24. The coated article of claim 22, wherein the metal is steel or aluminum.

25. Use of the film according to any one of claims 1 to 18 for coating a substrate.

26. The use according to claim 25, wherein the substrate is coated by a method selected from co-extrusion, lamination or extrusion lamination.

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