Highly weather-resistant acrylic multilayer foil with improved mechanical properties

Abstract

The present invention relates to an acrylic multilayer foil comprising at least one layer in which silica particles are uniformly distributed in an acrylic polymer matrix and at least one further layer. Due to the adhesion-promoting properties of the layer containing silica particles, the multilayer foil can be easily applied or laminated onto a substrate. The foil has high weathering resistance and excellent mechanical properties. Therefore, the multilayer foil of the present invention is highly suitable for use in surface protection of materials such as polyvinyl chloride (PVC) and high-pressure laminates (HPL).

Description

Technical Field

[0001] Field of the Invention The present invention relates to an acrylic multi-layer foil comprising at least one layer in which granular silica is uniformly distributed in an acrylic polymer matrix and further comprising at least one layer. This multi-layer foil has particularly high weather resistance and excellent mechanical properties. Therefore, the foils of the present invention are very suitable for surface protection of materials such as polyvinyl chloride (PVC) and for use in high-pressure laminates (HPL), particularly continuous pressure laminates (CPL).

[0002] Prior Art HPL is used in a wide range of applications such as table tops, doors, furniture, kitchen worktops, building wall, balcony or facade coating sheets. For example, European Patent Application Publication No. 3094493 and European Patent Application Publication No. 0166153 describe HPLs for indoor and outdoor applications.

[0003] For indoor applications, usually protection from ultraviolet rays is not required, but HPLs for outdoor applications necessarily have to have an ultraviolet protection top layer because the melamine resin of the HPL rapidly deteriorates even after short-term exposure to solar ultraviolet radiation. Recently, acrylic foils containing one of several types of ultraviolet absorbers have been widely used for this purpose as the top layer.

[0004] While acrylic foils possess excellent inherent resistance to solar ultraviolet radiation, their resistance to mechanical damage is only moderate, making them easily scratched. Furthermore, untreated acrylic materials such as polymethyl methacrylate (PMMA) exhibit poor adhesion to common scratch-resistant coatings, resulting in the lack of commercially available scratch-resistant HPL with UV protection. Consequently, the scratch resistance of HPL used for coating building walls, balconies, and facades is only moderate, and their vulnerability to vandalism has been a long-standing issue, particularly in socially problematic urban areas. Additionally, building walls, balconies, and facades are frequently exposed to corrosive substances such as bird droppings and urine; therefore, adequate chemical resistance is necessary.

[0005] Furthermore, simply physically bonding acrylic foil to the reactive resin-coated paper of HPL is insufficient to guarantee its stability over many years, and weathering can even cause the acrylic foil to partially or completely peel off from the HPL surface. To overcome this drawback, European Patent Application Publication No. 1664191 proposes laminating acrylic foil to melamine resin-impregnated paper on HPL using a copolymer containing an adhesion promoter, such as carboxylic acid anhydride units. During the HPL preparation procedure, the carboxylic acid anhydride units chemically react with the melamine resin. The combination of physical and chemical bonding of acrylic foil to the reactive resin-coated paper of HPL, along with the use of UV protection, enables the preparation of decorative HPL that remains stable for many years for outdoor use.

[0006] International Publication No. 2015 / 180995 discloses a three-layer foil having particularly strong adhesion to HPL substrates and excellent optical properties. In this foil, the outermost layer is a layer containing a fluoropolymer, the intermediate layer is a PMMA layer containing at least one UV absorber and / or UV stabilizer, and the innermost layer is a PMMA layer containing at least one adhesion promoter to improve adhesion to the substrate.

[0007] Nevertheless, the long-term weathering stability of copolymers described in International Publication No. 2015 / 180995 is often lower than that of pure PMMA. As a result, even if such copolymers are located beneath a UV-absorbing PMMA layer, delamination of HPL coated with such materials may occur after prolonged exposure to UV radiation. If these copolymers are located above a PMMA layer and directly exposed to solar UV radiation, the moderate weathering stability of these copolymers becomes an even greater problem. For this reason, these copolymers are generally not suitable for attaching scratch-resistant layers to acrylic foils for outdoor use.

[0008] Object of the invention Therefore, the object of the present invention was to provide a novel acrylic foil for finishing HPL that exhibits good initial and long-term adhesion when laminated to HPL. These HPLs should not show any signs of peeling even after long-term outdoor use and should have excellent mechanical properties, in particular, high scratch resistance.

[0009] Another objective of the present invention was to provide an acrylic foil that not only offers high inherent weather resistance but also ensures adequate protection of articles such as HPL from moisture, wind, solar ultraviolet radiation, and mechanical damage.

[0010] A further aspect of the present invention was to provide an HPL for outdoor use having the above-described features.

[0011] Finally, another objective of the present invention was to provide a cost-effective preparation method for producing HPL having desired properties.

[0012] Summary of the Invention This invention is based on the remarkable finding that substantially uniformly incorporating granular silica into the impact-resistant modified acrylic layer of a multilayer foil significantly improves the adhesive properties of the aforementioned layer. This layer can be directly coated with a liquid coating composition, such as a scratch-resistant coating or an anti-graffiti coating. Furthermore, this layer has significantly higher UV resistance than conventional adhesion-promoting layers with anhydrous copolymers. Therefore, HPL with such foil is very suitable for outdoor use in urban areas.

[0013] As will be readily apparent to those skilled in the art, the term “foil” as used herein refers to a sheet having a thickness of less than 5 mm, more preferably less than 1 mm. While the foils of the present invention can be advantageously used as protective coatings, the term “foil” as used herein should generally be distinguished from the term “film.” A film is typically the top layer of a multilayer substrate and cannot be handled separately from the aforementioned substrate. In contrast to a film, the foils of the present invention are not necessarily layers of a multilayer article, i.e., they are not necessarily attached to any substrate, and therefore can be handled separately and used for a variety of different purposes.

[0014] Although the silica particles are substantially uniformly dispersed in the molding composition of layer A, they produce an excellent adhesion-promoting effect. As used herein, the term “uniformly” means that the concentration of silica particles within the layer is substantially constant. This observation is quite surprising, as silica particles are often used to reduce adhesion, i.e., as anti-tack agents. For example, U.S. Patent Application Publication 2015 / 0044441 describes a multilayer PMMA foil that may contain 0.01 to 0.5% by weight of an anti-tack agent such as SiO2 particles. This document also describes the use of 0.5 to 20% by weight of a matting agent such as SiO2 particles in a PMMA layer.

[0015] The inventors have further found that during the preparation of the foil of the present invention, particularly by the co-extrusion method, silica particles remain visible on the surface of the resulting foil. In preferred embodiments, the silica particles protrude from the foil surface (see Figure 13). This phenomenon is thought to be responsible for the observed adhesion-enhancing effect. The material of layer A also has excellent heat resistance and can therefore be advantageously processed by thermoplastic methods such as co-extrusion to form a multilayer foil having layers A, B, and optionally C.

[0016] In its first embodiment, the present invention relates to a multilayer foil having at least layer A and layer B, wherein layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate 0.0-78.0% by weight, One or more types of impact-resistant modifiers, 20.0-98.0% by weight, Granular silica 2.0-40.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups 0.0 to 20.0% by weight of an adhesion-promoting copolymer containing, 0.0 to 38.0% by weight of fluoropolymer, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing, The cumulative content of polyalkyl (meth)acrylate and one or more impact resistance modifiers in the molding composition of 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, and particularly preferably at least 85% by weight, based on the weight of layer A.

[0017] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate 0.0-100.0% by weight, One or more types of impact-resistant modifiers, 0.0 to 95.0% by weight, 0.0 to 40.0% by weight of fluoropolymer, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0 to 5.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups Adhesion-promoting copolymer containing 0.0 to 20.0% by weight and It consists of a molding composition containing, The cumulative content of polyalkyl (meth)acrylate and one or more impact-resistant modifiers in the molding composition of 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, and particularly preferably at least 95% by weight, based on the weight of layer B. In this application, the cumulative content of polyalkyl (meth)acrylate and one or more impact-resistant modifiers will be referred to as the "content of impact-resistant polyalkyl (meth)acrylate".

[0018] In a further embodiment, the present invention relates to a multilayer foil having at least layer A and layer B, wherein layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate 0.0-78.0% by weight, One or more types of impact-resistant modifiers, 20.0-98.0% by weight, Granular silica 2.0-40.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups 0.0 to 20.0% by weight of an adhesion-promoting copolymer containing, 0.0 to 38.0% by weight of fluoropolymer, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing, The cumulative content of impact-resistant polyalkyl (meth)acrylate in the molding composition of 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, and particularly preferably at least 85% by weight, based on the weight of layer A.

[0019] Layer B is defined based on the total weight of layer B. 40.0-100.0% by weight of fluoropolymer, Polyalkyl (meth)acrylate 0.0-30.0% by weight, Glass beads 0.0-30.0% by weight and It consists of a molding composition containing the following:

[0020] The materials used in this invention have excellent thermal stability, making them very suitable for thermoplastic processing such as extrusion molding and injection molding, and foil molding methods such as chill-roll methods. Multilayer foils having layers A, B, and optionally C are usually manufactured by co-extrusion.

[0021] The multilayer foil of the present invention is superior to commercially available foils in terms of weather resistance and mechanical resistance, and has improved long-term stability, typically exceeding 10 years. As used herein, the term “stability” refers not only to the inherent stability of the foil against weathering and mechanical damage, but also to the duration of its protective effect.

[0022] Furthermore, the multilayer foil of the present invention offers the following advantages: - Multilayer foils can be used to laminate various substrates at various temperatures and using various lamination techniques. When a layer containing granular silica is directed toward the substrate, it provides excellent long-term adhesion between the foil and the substrate. In particular, the foil exhibits excellent adhesion to melamine resin-based and phenolic resin-based substrates such as HPL. - The layer containing granular silica can be directly and uniformly coated with a liquid coating composition, thereby providing excellent adhesion between the coating layer and the multilayer foil. This makes it possible to impart desired properties to the foil, such as improved scratch resistance, in a particularly cost-effective manner. - Foils having layers A, B, and optionally C can be manufactured in an extrusion plant in a cost-effective manner. Layer D can then be uniformly applied as a liquid coating on layer A, if necessary. - The foil has excellent weather resistance and is also resistant to chemicals. - When a fluoropolymer is used as the top layer, the foil is substantially impermeable to water vapor, has excellent stain-resistant properties, such as very good chemical resistance to commercially available cleaning compositions and alcoholic beverages, and can be easily cleaned.

[0023] In a further embodiment, the present invention relates to a method for producing a foil having a layer A made of a molding composition A, wherein the foil is produced in a foil molding method, preferably a chill-roll method. Polyalkyl (meth)acrylate 0.0-78.0% by weight, One or more types of impact-resistant modifiers, 20.0-98.0% by weight, Granular silica 2.0-40.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups 0.0 to 20.0% by weight of an adhesion-promoting copolymer containing, 0.0 to 38.0% by weight of fluoropolymer, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight Molded from a molding composition containing, The cumulative content of impact-resistant polyalkyl (meth)acrylate in the molding composition of 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, and particularly preferably at least 85% by weight, based on the weight of layer A.

[0024] Another aspect of the present invention relates to a multilayer article, preferably an HPL, comprising a substrate at least partially covered with foil as defined above, and having layers in the following order, starting from the outer surface: - Layer D that forms the outer surface of the multilayer article, - layer A, - Layer B and - Layer C, if present.

[0025] Yet another aspect of the present invention relates to a multilayer article, preferably a high-pressure laminate, comprising a substrate at least partially covered with foil as defined above, and having layers in the following order, starting from the outer surface: - If present, layer C - Layer B and - Tier A.

[0026] Finally, a further aspect of the present invention relates to a method for manufacturing a multilayer article as defined above, the method comprising the step of coating a substrate with the foil of the present invention by co-extrusion, lamination or extrusion lamination, wherein at least partially crosslinked material of the coating layer D preferably undergoes further crosslinking. [Brief explanation of the drawing]

[0027] [Figure 1] This figure shows the multilayer foil of the present invention, consisting of layers A and B. [Figure 2] This figure shows a multilayer foil having layers A, B, and C. [Figure 3] This figure shows a multilayer foil comprising layers A and B, coated with layer D. [Figure 4] This figure shows a multilayer foil comprising layers A, B, and C, coated with layer D. [Figure 5] This figure shows a multilayer foil having layers A, B, and C. [Figure 6] This figure shows a substrate coated with the multilayer foil of the present invention, comprising layers A and B and coated with layer D. [Figure 7] This figure shows a substrate coated with the multilayer foil of the present invention, comprising layers A, B, and C, and coated with layer D. [Figure 8] This figure shows a substrate coated with the multilayer foil of the present invention having layers A and B. [Figure 9] This figure shows a substrate coated with the multilayer foil of the present invention, comprising layers A, B, and C, and coated with layer D. [Figure 10] This figure shows a substrate coated with the multilayer foil of the present invention, comprising layers A, B, and C, and coated with layer D. [Figure 11] This figure shows a substrate coated with the multilayer foil of the present invention having layers A, B, and C. [Figure 12]This figure shows a substrate coated with the multilayer foil of the present invention having layers A, B, and C. [Figure 13] This figure shows a micrograph of the multilayer foil of the present invention obtained with a scanning electron microscope (SEM) JEOL JSM IT 3000. Magnification: 750x, 10kV, SED detector. The foil sample was frozen in liquid nitrogen, mechanically fractured, and the newly obtained surface was analyzed.

[0028] Detailed description of preferred embodiments Foils having layers A, B, and optionally C can be obtained by methods such as co-extrusion, where layer A is formed from a molding composition in which silica particles are substantially uniformly dispersed in an impact-resistant polyalkyl (meth)acrylate matrix. Layer D can then be applied on layer A as a liquid coating.

[0029] The following embodiments of the multilayer foil of the present invention exhibited particularly advantageous properties.

[0030] Foil embodiment 1 The multilayer foil consists of layers A, B, and C (see Figure 2). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 60.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0031] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate 0.0 to 99.9% by weight, preferably 10.0 to 89.9% by weight, One or more types of impact-resistant modifiers in an amount of 0.0 to 95.0% by weight, preferably 10.0 to 90.0% by weight, Triazine-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, One or more types of UV stabilizers in an amount of 0.0 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight. It consists of a molding composition containing the following:

[0032] Layer C is defined based on the total weight of layer C. 40.0 to 100.0% by weight of fluoropolymer, preferably 70.0 to 100.0% by weight, more preferably 85.0 to 100.0% by weight, Polyalkyl (meth)acrylate 0.0 to 60.0% by weight, preferably 0.0 to 30.0% by weight, more preferably 0.0 to 15.0% by weight It consists of a molding composition containing the following:

[0033] Foil Embodiment 2 The multilayer foil consists of layers A, B, and C (see Figure 2). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 60.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0034] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate 0.0 to 99.8% by weight, preferably 10.0 to 89.8% by weight, One or more impact modifiers in an amount of 0.0 to 95.0% by weight, preferably 10.0 to 90.0% by weight, Benzotriazole-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, Triazine-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, One or more types of UV stabilizers in an amount of 0.0 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight. It consists of a molding composition containing the following:

[0035] Layer C is defined based on the total weight of layer C. 40.0 to 100.0% by weight of fluoropolymer, preferably 70.0 to 100.0% by weight, more preferably 85.0 to 100.0% by weight, Polyalkyl (meth)acrylate 0.0 to 60.0% by weight, preferably 0.0 to 30.0% by weight, more preferably 0.0 to 15.0% by weight It consists of a molding composition containing the following:

[0036] Foil embodiment 3 The multilayer foil consists of layers A, B, and C (see Figure 2). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 60.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0037] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate 0.0 to 99.8% by weight, preferably 10.0 to 89.8% by weight, One or more impact modifiers in an amount of 0.0 to 95.0% by weight, preferably 10.0 to 90.0% by weight, Fluoropolymer 0.0 to 40.0% by weight, preferably 0.0 to 30.0% by weight, more preferably 0.0 to 20.0% by weight, Benzotriazole-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, Triazine-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, One or more types of UV stabilizers in an amount of 0.0 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, It consists of a molding composition containing the following:

[0038] Layer C is defined based on the total weight of layer C. 40.0 to 100.0% by weight of fluoropolymer, preferably 70.0 to 100.0% by weight, more preferably 85.0 to 100.0% by weight, Polyalkyl (meth)acrylate 0.0 to 60.0% by weight, preferably 0.0 to 30.0% by weight, more preferably 0.0 to 15.0% by weight It consists of a molding composition containing the following:

[0039] Foil embodiment 4 The multilayer foil consists of layers A, B, and C (see Figure 2). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 60.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0040] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate 0.0 to 99.8% by weight, preferably 10.0 to 89.8% by weight, One or more impact modifiers in an amount of 0.0 to 95.0% by weight, preferably 10.0 to 90.0% by weight, Fluoropolymer 0.0 to 40.0% by weight, preferably 0.0 to 30.0% by weight, more preferably 0.0 to 20.0% by weight, Benzotriazole-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, Triazine-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, One or more types of UV stabilizers in an amount of 0.0 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, It consists of a molding composition containing the following:

[0041] Layer C is defined based on the total weight of layer C. 40.0 to 97.0% by weight of fluoropolymer, preferably 85.0 to 97.0% by weight, Polyalkyl (meth)acrylate 0.0-30.0% by weight, Glass beads in a quantity of 3.0 to 30.0% by weight, preferably 3.0 to 15.0% by weight. It consists of a molding composition containing the following:

[0042] Foil embodiment 5 The multilayer foil consists of layers A and B (see Figure 1). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 40.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0 to 5.0% by weight, It consists of a molding composition containing the following:

[0043] Layer B is defined based on the total weight of layer B. 40.0 to 100.0% by weight of fluoropolymer, preferably 70.0 to 100.0% by weight, more preferably 85.0 to 100.0% by weight, Polyalkyl (meth)acrylate 0.0 to 60.0% by weight, preferably 0.0 to 30.0% by weight, more preferably 0.0 to 15.0% by weight It consists of a molding composition containing the following:

[0044] Foil Embodiment 6 The multilayer foil consists of layers A and B (see Figure 1). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 40.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0045] Layer B is defined based on the total weight of layer B. 40.0 to 97.0% by weight of fluoropolymer, preferably 85.0 to 97.0% by weight, Polyalkyl (meth)acrylate 0.0-30.0% by weight, Glass beads in a quantity of 3.0 to 30.0% by weight, preferably 3.0 to 15.0% by weight. It consists of a molding composition containing the following:

[0046] Foil embodiment 7 The multilayer foil consists of layers A and B (see Figure 1). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 76.0% by weight, preferably 0.0 to 62.0% by weight, more preferably 0.0 to 50.0% by weight, even more preferably 0.0 to 40.0% by weight, and particularly preferably 0.0 to 30.0% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 96.0% by weight, preferably 30.0 to 92.0% by weight, more preferably 40.0 to 90.0% by weight, even more preferably 50.0 to 90.0% by weight, and especially preferably 60.0 to 90.0% by weight, Granular silica 2.0 to 20.0% by weight, preferably 4.0 to 25.0% by weight, more preferably 5.0 to 20.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups A bonding-promoting copolymer containing 2.0 to 20.0% by weight, preferably 4.0 to 25.0% by weight, more preferably 5.0 to 20.0% by weight, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0047] Layer B is defined based on the total weight of layer B. 40.0 to 100.0% by weight of fluoropolymer, preferably 70.0 to 100.0% by weight, more preferably 85.0 to 100.0% by weight, Polyalkyl (meth)acrylate 0.0 to 60.0% by weight, preferably 0.0 to 30.0% by weight, more preferably 0.0 to 15.0% by weight It consists of a molding composition containing the following:

[0048] Foil embodiment 8 The multilayer foil consists of layers A and B (see Figure 1). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 76.0% by weight, preferably 0.0 to 62.0% by weight, more preferably 0.0 to 50.0% by weight, even more preferably 0.0 to 40.0% by weight, and particularly preferably 0.0 to 30.0% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 96.0% by weight, preferably 30.0 to 92.0% by weight, more preferably 40.0 to 90.0% by weight, even more preferably 50.0 to 90.0% by weight, and especially preferably 60.0 to 90.0% by weight, Granular silica 2.0 to 20.0% by weight, preferably 4.0 to 25.0% by weight, more preferably 5.0 to 20.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups A bonding-promoting copolymer containing 2.0 to 20.0% by weight, preferably 4.0 to 25.0% by weight, more preferably 5.0 to 20.0% by weight, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0049] Layer B is defined based on the total weight of layer B. 40.0 to 97.0% by weight of fluoropolymer, preferably 85.0 to 97.0% by weight, Polyalkyl (meth)acrylate 0.0-30.0% by weight, Glass beads in a quantity of 3.0 to 30.0% by weight, preferably 3.0 to 15.0% by weight. It consists of a molding composition containing the following:

[0050] Foil embodiment 9 The multilayer foil consists of layers A and B (see Figure 1). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 60.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0051] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate 0.0 to 99.9% by weight, preferably 10.0 to 89.9% by weight, One or more types of impact-resistant modifiers in an amount of 0.0 to 95.0% by weight, preferably 10.0 to 90.0% by weight, Triazine-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, One or more types of UV stabilizers in an amount of 0.0 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight. It consists of a molding composition containing the following:

[0052] Foil embodiment 10 The multilayer foil consists of layers A and B (see Figure 1). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 75.9% by weight, preferably 0.0 to 61.9% by weight, more preferably 0.0 to 49.9% by weight, even more preferably 0.0 to 39.9% by weight, and particularly preferably 0.0 to 29.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 96.0% by weight, preferably 30.0 to 92.0% by weight, more preferably 40.0 to 90.0% by weight, even more preferably 50.0 to 90.0% by weight, and especially preferably 60.0 to 92.9% by weight, Granular silica 2.0 to 20.0% by weight, preferably 4.0 to 25.0% by weight, more preferably 5.0 to 20.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups A bonding-promoting copolymer containing 2.0 to 20.0% by weight, preferably 4.0 to 25.0% by weight, more preferably 5.0 to 20.0% by weight, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0053] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate 0.0 to 99.9% by weight, preferably 10.0 to 89.9% by weight, One or more types of impact-resistant modifiers in an amount of 0.0 to 95.0% by weight, preferably 10.0 to 90.0% by weight, Triazine-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, One or more types of UV stabilizers in an amount of 0.0 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight. It consists of a molding composition containing the following:

[0054] Foil embodiment 11 The multilayer foil consists of layers A and B (see Figure 1). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 60.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Triazine-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0055] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.8% by weight, more preferably 0.0 to 52.7% by weight, even more preferably 0.0 to 42.7% by weight, and particularly preferably 0.0 to 33.0% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 98.0% by weight, preferably 30.0 to 95.0% by weight, more preferably 40.0 to 93.0% by weight, even more preferably 50.0 to 93.0% by weight, and especially preferably 60.0 to 93.0% by weight, Benzotriazole-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups Adhesion-promoting copolymer containing 2.0 to 40.0% by weight, preferably 5.0 to 35.0% by weight, more preferably 7.0 to 30.0% by weight and It consists of a molding composition containing the following:

[0056] Foil embodiment 12 The multilayer foil consists of layers A and B (see Figure 1). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 60.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Triazine-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0057] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate in an amount of 0.0 to 79.9% by weight, preferably 0.0 to 66.8% by weight, more preferably 0.0 to 54.7% by weight, even more preferably 0.0 to 44.7% by weight, and particularly preferably 0.0 to 35.0% by weight, One or more types of impact-resistant modifiers in an amount of 20.0 to 98.0% by weight, preferably 30.0 to 95.0% by weight, more preferably 40.0 to 93.0% by weight, even more preferably 50.0 to 93.0% by weight, and especially preferably 60.0 to 93.0% by weight, Benzotriazole-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight. It consists of a molding composition containing the following:

[0058] Foil embodiment 13 The multilayer foil consists of layers A, B, and C (see Figure 5). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 60.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Triazine-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0059] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate 0.0 to 99.8% by weight, preferably 10.0 to 89.8% by weight, One or more impact modifiers in an amount of 0.0 to 95.0% by weight, preferably 10.0 to 90.0% by weight, Benzotriazole-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, Triazine-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, One or more types of UV stabilizers in an amount of 0.0 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight. It consists of a molding composition containing the following:

[0060] Layer C is defined based on the total weight of layer C. Polyalkyl (meth)acrylate 0.0-77.9% by weight, One or more types of impact-resistant modifiers, 20.0-97.9% by weight, Granular silica 2.0-40.0% by weight, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0061] Foil embodiment 14 The multilayer foil consists of layers A, B, and C (see Figure 2). Layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.9% by weight, more preferably 0.0 to 52.9% by weight, even more preferably 0.0 to 42.9% by weight, and particularly preferably 0.0 to 32.9% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 97.9% by weight, preferably 30.0 to 94.9% by weight, more preferably 40.0 to 92.9% by weight, even more preferably 50.0 to 92.9% by weight, and especially preferably 60.0 to 92.9% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, Triazine-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0062] Layer B is defined based on the total weight of layer B. Polyalkyl (meth)acrylate 0.0 to 99.8% by weight, preferably 10.0 to 89.8% by weight, One or more impact modifiers in an amount of 0.0 to 95.0% by weight, preferably 10.0 to 90.0% by weight, Benzotriazole-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, Triazine-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, One or more types of UV stabilizers in an amount of 0.0 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight. It consists of a molding composition containing the following:

[0063] Layer C is defined based on the total weight of layer C. Polyalkyl (meth)acrylate in an amount of 0.0 to 77.9% by weight, preferably 0.0 to 64.8% by weight, more preferably 0.0 to 52.7% by weight, even more preferably 0.0 to 42.7% by weight, and particularly preferably 0.0 to 33.0% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 98.0% by weight, preferably 30.0 to 95.0% by weight, more preferably 40.0 to 93.0% by weight, even more preferably 50.0 to 93.0% by weight, and especially preferably 60.0 to 93.0% by weight, Benzotriazole-type UV absorber in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of maleic anhydride, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups Adhesion-promoting copolymer containing 2.0 to 40.0% by weight, preferably 5.0 to 35.0% by weight, more preferably 7.0 to 30.0% by weight and It consists of a molding composition containing the following:

[0064] Foil embodiment 15 The multilayer foil consists of layers D, A, and B (see Figure 3).

[0065] Layer D consists of at least partially crosslinked polyurethane (meth)acrylate.

[0066] Layers A and B correspond to those of the foil embodiment 11.

[0067] Foil embodiment 16 The multilayer foil consists of layers D, A, and B (see Figure 3).

[0068] Layer D consists of at least partially crosslinked polyurethane (meth)acrylate.

[0069] Layers A and B correspond to those of the foil embodiment 12.

[0070] Foil embodiment 17 The multilayer foil consists of layers D, A, B, and C (see Figure 4).

[0071] Layer D consists of at least partially crosslinked polyurethane (meth)acrylate.

[0072] Layers A, B, and C correspond to those of the foil embodiment 14.

[0073] Foil embodiment 18 The multilayer foil consists of layers D, A, B, and C (see Figure 4).

[0074] Layer D consists of at least partially crosslinked polyurethane (meth)acrylate.

[0075] Layers A, B, and C correspond to those of the foil embodiment 13.

[0076] The compositions of layers A, B, C, and D will be described in more detail below.

[0077] Layer A The foil of the present invention has a layer A comprising a molding composition in which silica particles are substantially uniformly dispersed in an impact-resistant polyalkyl (meth)acrylate matrix. The content of impact-resistant polyalkyl (meth)acrylate 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, and particularly preferably at least 85% by weight, based on the weight of layer A. Typically, the polymer matrix does not contain any fluoropolymers.

[0078] According to the present invention, the presence of one or more impact-resistant modifiers in the molding composition of layer A is essential to ensure the foil's good tear resistance and excellent adhesive properties. Therefore, layer A contains 20.0 to 98.0% by weight, preferably 30.0 to 95.0% by weight, more preferably 40.0 to 93.0% by weight, even more preferably 50.0 to 93.0% by weight, and particularly preferably 60.0 to 93.0% by weight, of one or more impact-resistant modifiers, based on the weight of layer A. Preferably, the amount of rubber in the one or more impact-resistant modifiers in the molding composition of layer A is 6.0 to 35.0% by weight, preferably 10.0 to 30.0% by weight, more preferably 12.0 to 25.0% by weight, even more preferably 15.0 to 20.0% by weight, and particularly preferably 60.0 to 93.0% by weight, of one or more impact-resistant modifiers, based on the weight of layer A. Therefore, the polyalkyl (meth)acrylate content in the molding composition for layer A may be in the range of 0.0 to 78.0% by weight, preferably 0.0 to 65.0% by weight, more preferably 0.0 to 53.0% by weight, even more preferably 0.0 to 43.0% by weight, and particularly preferably 0.0 to 33.0% by weight, based on the weight of layer A.

[0079] The molding composition for layer A is based on the total weight of layer A. Polyalkyl (meth)acrylate 0.0-78.0% by weight, One or more types of impact-resistant modifiers, 20.0-98.0% by weight, Granular silica 2.0-40.0% by weight, 0.0 to 38.0% by weight of fluoropolymer, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0 to 5.0% by weight, Preferably, Polyalkyl (meth)acrylate 0.0-65.0% by weight, One or more types of impact-resistant modifiers, 30.0-95.0% by weight, Granular silica 5.0-30.0% by weight, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0 to 5.0% by weight, more, Polyalkyl (meth)acrylate 0.0-53.0% by weight, One or more types of impact-resistant modifiers, 40.0-93.0% by weight, Granular silica 7.0-20.0% by weight, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0 to 5.0% by weight, Furthermore, Polyalkyl (meth)acrylate 0.0-43.0% by weight, 50.0-93.0% by weight of one or more types of impact-resistant modifiers, Granular silica 7.0-20.0% by weight, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0 to 5.0% by weight, Particularly preferred, Polyalkyl (meth)acrylate 0.0-33.0% by weight, One or more types of impact-resistant modifiers, 60.0-93.0% by weight, Granular silica 7.0-20.0% by weight, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It may include.

[0080] The inventors have further found that the adhesion-enhancing effect of granular silica in layer A can be further enhanced by using granular silica in combination with an adhesion-promoting copolymer. In this embodiment, the molding composition for layer A is based on the total weight of layer A, Polyalkyl (meth)acrylate 0.0-76.0% by weight, One or more types of impact-resistant modifiers, 20.0-96.0% by weight, Granular silica 2.0-20.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups 2.0 to 20.0% by weight of an adhesion-promoting copolymer containing, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0 to 5.0% by weight, Preferably, Polyalkyl (meth)acrylate 0.0-62.0% by weight, One or more types of impact-resistant modifiers, 30.0-92.0% by weight, Granular silica 4.0-25.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups 4.0-25.0% by weight of an adhesion-promoting copolymer containing, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0 to 5.0% by weight, more, Polyalkyl (meth)acrylate 0.0-50.0% by weight, One or more types of impact-resistant modifiers, 40.0-90.0% by weight, Granular silica 5.0-20.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups 5.0 to 20.0% by weight of an adhesion-promoting copolymer containing, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0 to 5.0% by weight, Furthermore, Polyalkyl (meth)acrylate 0.0-40.0% by weight, 50.0-90.0% by weight of one or more impact modifiers, Granular silica 5.0-20.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups 5.0 to 20.0% by weight of an adhesion-promoting copolymer containing, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0 to 5.0% by weight, Particularly preferred, Polyalkyl (meth)acrylate 0.0-30.0% by weight, 60.0-90.0% by weight of one or more types of impact-resistant modifiers, Granular silica 5.0-20.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups 5.0 to 20.0% by weight of an adhesion-promoting copolymer containing, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It may include.

[0081] Furthermore, if layer A contains an additional small amount of fluoropolymer, the chemical resistance and impact resistance of layer A can be further improved. Therefore, in some embodiments, the polymer matrix of layer A may contain at least one fluoropolymer, such as PVDF, and the fluoropolymer content is typically 0.0 to 38.0% by weight, preferably 0.0 to 28.0% by weight, and more preferably 0.0 to 18.0% by weight, based on the weight of layer A.

[0082] Layer B The foil of the present invention typically further comprises a layer B directly adjacent to layer A (see Figure 1). The content of impact-resistant polyalkyl (meth)acrylate 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, and particularly preferably at least 95% by weight, based on the weight of layer B. Layer B may optionally contain at least one fluoropolymer such as PVDF, but the composition of layer B is typically different from the composition of layer A. Furthermore, layer B may contain a small amount of granular silica, although granular silica is usually not present in layer B.

[0083] In one aspect of the present invention, the composition of layer B is as follows, based on the total weight of layer B: Polyalkyl (meth)acrylate 0.0 to 100.0% by weight, preferably 10.0 to 90.0% by weight, One or more types of impact-resistant modifiers in an amount of 0.0 to 95.0% by weight, preferably 10.0 to 90.0% by weight, Fluoropolymer 0.0 to 40.0% by weight, preferably 0.0 to 30.0% by weight, more preferably 0.0 to 20.0% by weight, One or more types of UV absorbers in an amount of 0.0 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, One or more types of UV stabilizers in an amount of 0.0 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.3 to 3.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups Adhesion-promoting copolymer containing 0.0 to 20.0% by weight, preferably 0.0 to 10.0% by weight and That is the case.

[0084] Preferably, the polyalkyl (meth)acrylate in layer B is PMMA as described later, and the fluoropolymer is PVDF. Furthermore, depending on the substrate to which the foil is applied, layer B may not substantially contain the adhesion-promoting copolymer.

[0085] In yet another aspect of the present invention, layer B is based on the total weight of layer B, 40.0-100.0% by weight of fluoropolymer, Polyalkyl (meth)acrylate 0.0-30.0% by weight, Glass beads 0.0-30.0% by weight and It consists of a molding composition containing the following:

[0086] The composition of layer B can be further adjusted to meet the requirements for the desired final appearance of the foil.

[0087] If a foil with a non-glossy appearance is desired, layer B is calculated based on the total weight of layer B. 40.0 to 97.0% by weight of fluoropolymer, preferably 85.0 to 97.0% by weight, Polyalkyl (meth)acrylate 0.0-30.0% by weight, Glass beads in a quantity of 3.0 to 30.0% by weight, preferably 3.0 to 15.0% by weight. It may consist of a molding composition containing the following.

[0088] To obtain a foil with a glossy appearance, layer B is based on the total weight of layer B, 40.0 to 100.0% by weight of fluoropolymer, preferably 70.0 to 100.0% by weight, more preferably 85.0 to 100.0% by weight, Polyalkyl (meth)acrylate 0.0 to 60.0% by weight, preferably 0.0 to 30.0% by weight, more preferably 0.0 to 15.0% by weight It may consist of a molding composition containing the following.

[0089] Furthermore, in both embodiments described above, the fact that layer B is substantially free of polyalkyl (meth)acrylate is advantageous in terms of the chemical resistance of the foil.

[0090] This composition of layer B is particularly advantageous when the foil of the present invention is used to protect a substrate, such that layer A is directly adjacent to layer B, and layer B, which is based on a fluoropolymer, forms the outer surface of the substrate, thereby facing the environment. Layer A is located beneath layer B, i.e., closer to the surface of the substrate. Therefore, layer A functions as an adhesion-promoting layer.

[0091] In this embodiment, the glass beads are substantially uniformly dispersed in the polymer matrix of layer B. In one embodiment, the polymer matrix comprises a combination of a fluoropolymer, such as PVDF, and at least one further polymer, such as a polyalkyl (meth)acrylate such as PMMA. In this embodiment, the fluoropolymer content is typically 40.0 to 100.0% by weight, based on the total weight of layer B, and the polyalkyl (meth)acrylate content is 0.0 to 30.0% by weight. This corresponds to a fluoropolymer:polyalkyl (meth)acrylate weight ratio of about 1:1 to about 1:0. As those skilled in the art will readily understand, the exact composition of the polymer matrix in layer A can be adjusted according to the intended use of the foil. When the weight ratio of PVDF to PMMA is 1.0:0.0 to 1:1 (w / w), more preferably 1.0:0.0 to 1.0:0.40 (w / w), and particularly preferably 1.0:0.0 to 1.0:0.30 (w / w), a particularly weather-resistant foil can be obtained by using the PMMA / PVDF combination.

[0092] Layer C Adhesion promotion layer C In addition to layers A and B described above, the multilayer foil of the present invention may optionally include an adhesion-promoting layer C such that layer B is located between layers A and C. In this embodiment, layer C acts as an adhesion-promoting layer and therefore necessarily contains granular silica, an adhesion-promoting copolymer, or a combination thereof. Generally, when the multilayer foil has layer C, 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.

[0093] To achieve excellent adhesion of the foil to a substrate such as HPL, the cumulative content of granular silica and adhesion-promoting copolymer in layer C is selected to be at least 2.0% by weight, preferably at least 4.0% by weight, more preferably at least 6.0% by weight, and even more preferably at least 8.0% by weight, based on the weight of layer C, and the content of impact-resistant polyalkyl (meth)acrylate in layer C is at least 60% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, and even more preferably at least 80% by weight, based on the weight of layer C.

[0094] Generally, layer C is Polyalkyl (meth)acrylate 0.0-78.0% by weight, One or more types of impact-resistant modifiers, 20.0-98.0% by weight, 0.0 to 40.0% by weight of fluoropolymer, Granular silica 0.0 to 40.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups 0.0 to 40.0% by weight of an adhesion-promoting copolymer containing, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0095] In one embodiment, layer C contains granular silica and does not contain adhesion-promoting copolymer. Therefore, in this embodiment, the composition of layer C substantially corresponds to the composition of layer A. Layer C is Polyalkyl (meth)acrylate in an amount of 0.0 to 78.0% by weight, preferably 0.0 to 65.0% by weight, more preferably 0.0 to 53.0% by weight, even more preferably 0.0 to 43.0% by weight, and particularly preferably 0.0 to 33.0% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 98.0% by weight, preferably 30.0 to 95.0% by weight, more preferably 40.0 to 93.0% by weight, even more preferably 50.0 to 93.0% by weight, and especially preferably 60.0 to 93.0% by weight, Granular silica in a quantity of 2.0 to 40.0% by weight, preferably 5.0 to 30.0% by weight, more preferably 7.0 to 20.0% by weight, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0096] In yet another embodiment, layer C comprises an adhesion-promoting copolymer and does not contain granular silica. Therefore, in this embodiment, layer C is Polyalkyl (meth)acrylate in an amount of 0.0 to 78.0% by weight, preferably 0.0 to 65.0% by weight, more preferably 0.0 to 53.0% by weight, even more preferably 0.0 to 43.0% by weight, and particularly preferably 0.0 to 33.0% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 98.0% by weight, preferably 30.0 to 95.0% by weight, more preferably 40.0 to 93.0% by weight, even more preferably 50.0 to 93.0% by weight, and especially preferably 60.0 to 93.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups A bonding-promoting copolymer containing 2.0 to 40.0% by weight, preferably 5.0 to 35.0% by weight, more preferably 7.0 to 30.0% by weight, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0097] In this embodiment, layer C contains 2.0 to 40.0% by weight, preferably 5.0 to 35.0% by weight, and more preferably 7.0 to 30.0% by weight, of the adhesion-promoting copolymer based on the weight of layer C. Therefore, the amount of adhesion-promoting monomer in the molding composition of layer C is typically 0.1 to 10.0% by weight, preferably 0.5 to 8.0% by weight, and more preferably 1.0 to 5.0% by weight, based on the weight of layer C.

[0098] In yet another embodiment, layer C includes an adhesion-promoting copolymer in combination with granular silica. Therefore, in this embodiment, layer C is Polyalkyl (meth)acrylate in an amount of 0.0 to 78.0% by weight, preferably 0.0 to 65.0% by weight, more preferably 0.0 to 53.0% by weight, even more preferably 0.0 to 43.0% by weight, and particularly preferably 0.0 to 33.0% by weight. One or more types of impact-resistant modifiers in an amount of 20.0 to 98.0% by weight, preferably 30.0 to 95.0% by weight, more preferably 40.0 to 93.0% by weight, even more preferably 50.0 to 93.0% by weight, and especially preferably 60.0 to 93.0% by weight, Granular silica 1.0 to 20.0% by weight, preferably 2.0 to 17.0% by weight, more preferably 4.0 to 15.0% by weight, Adhesion-promoting copolymer, wherein the weight of the adhesion-promoting copolymer is used as a basis. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups Adhesion-promoting copolymer containing 1.0 to 20.0% by weight, preferably 3.0 to 20.0% by weight, more preferably 7.0 to 15.0% by weight, One or more types of UV absorbers, 0.0 to 5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It consists of a molding composition containing the following:

[0099] In this embodiment, layer C contains 1.0 to 20.0% by weight, preferably 3.0 to 20.0% by weight, and more preferably 7.0 to 15.0% by weight, of the adhesion-promoting copolymer based on the weight of layer C. Therefore, the amount of adhesion-promoting monomer in the molding composition of layer C is typically 0.05 to 5.0% by weight, preferably 0.25 to 4.0% by weight, and more preferably 0.5 to 2.5% by weight, based on the weight of layer C.

[0100] The presence of one or more impact-resistant modifiers in the molding composition of layer C is essential to ensure the good tear resistance and excellent adhesion of the foil. Therefore, layer C contains 20.0 to 98.0% by weight, preferably 30.0 to 95.0% by weight, more preferably 40.0 to 93.0% by weight, even more preferably 50.0 to 93.0% by weight, and particularly preferably 60.0 to 93.0% by weight, of one or more impact-resistant modifiers, based on the weight of layer C. Preferably, the amount of rubber in one or more impact-resistant modifiers in the molding composition of layer C is 6.0 to 35.0% by weight, preferably 10.0 to 30.0% by weight, more preferably 12.0 to 25.0% by weight, even more preferably 15.0 to 20.0% by weight, and particularly preferably 60.0 to 93.0% by weight, of one or more impact-resistant modifiers, based on the weight of layer C.

[0101] Fluoropolymer-based layer C In a further embodiment of the present invention, layer C, based on the total weight of the layer C, comprises 40.0 to 100.0% by weight of a fluoropolymer and 0.0 to 30.0% by weight of a polyalkyl (meth) acrylate and 0.0 to 30.0% by weight of glass beads to form a molding composition.

[0102] The composition of layer C can be further adjusted to meet the requirements regarding the desired final appearance of the multilayer foil.

[0103] If a foil with a non-glossy appearance is desired, layer C, based on the total weight of the layer C, comprises 40.0 to 97.0% by weight, preferably 85.0 to 97.0% by weight of a fluoropolymer and 0.0 to 30.0% by weight of a polyalkyl (meth) acrylate and 3.0 to 30.0% by weight, preferably 3.0 to 15.0% by weight of glass beads to form a molding composition.

[0104] To obtain a foil with a glossy appearance, layer C, based on the total weight of the layer C, comprises 40.0 to 100.0% by weight, preferably 70.0 to 100.0% by weight, more preferably 85.0 to 100.0% by weight of a fluoropolymer and 0.0 to 60.0% by weight, preferably 0.0 to 30.0% by weight, more preferably 0.0 to 15.0% by weight of a polyalkyl (meth) acrylate to form a molding composition.

[0105] Furthermore, in both of the above embodiments, it is advantageous in terms of the chemical resistance of the foil that layer C substantially does not contain polyalkyl (meth) acrylate.

[0106] This composition of layer C is particularly advantageous when the foil of the present invention is used to protect a substrate, such that layer C, which is based on a fluoropolymer, forms the outer surface of the substrate and thus faces the environment. Layer A is located beneath layers C and B, i.e., in direct contact with the surface of the substrate. Therefore, in this embodiment, layer A functions as an adhesion-promoting layer.

[0107] Layer D The multilayer foil of the present invention may further comprise a coating layer D adjacent to layer A. Based on the adhesion-promoting effect of silica particles in layer A, the coating layer D can be advantageously applied uniformly as a liquid coating composition and preferably subsequently cured at least partially. The coating layer D may comprise at least partially crosslinked material selected from crosslinked polyurethane, crosslinked polyurethane (meth)acrylate, crosslinked poly(meth)acrylate, or mixtures thereof.

[0108] The coating layer D can be applied as a coating on layer A by known methods, such as by a roller. Preferably, the coating layer D is applied so that a closed film of the coating composition is formed on layer A, and the application amount is preferably 20 to 150 g / m². 2 The range is particularly preferably 50-100 g / m². 2 It is within the range.

[0109] The composition of layer D will be described in detail below.

[0110] Explanation of each component in layers A to D Silica particles The content of granular silica dispersed in the polymer matrix of the layer is typically 2.0 to 40.0% by weight, more preferably 5.0 to 30.0% by weight, and particularly preferably 7.0 to 20.0% by weight, based on the total weight of the corresponding layer.

[0111] The presence of granular silica in the multilayer foil of the present invention serves several purposes. Layer A of the foil has a rough and hydrophilic surface and can be easily coated with a liquid coating composition based on the presence of a specified amount of silica particles. The coating can be applied substantially on the surface of the layer by any method known in the prior art, such as dip coating, spray coating, doctor knife coating, flow coating, and application by roller or roll. The coating can be applied on the foil in a particularly easy and cost-effective manner by using roll-to-roll processing. Roll-to-roll manufacturing technology is well known to those skilled in the art and includes continuous processing while the foil is continuously transferred between two moving rolls. In a preferred embodiment, the coating of the foil by the intermediate layer is carried out at a temperature in the range of 60°C to 90°C at a speed of 1 m / min to 70 m / min, more preferably 10 m / min to 30 m / min.

[0112] Furthermore, the layer containing granular silica has surprisingly high adhesion to materials such as melamine resin-based HPL. Therefore, the multilayer foil of the present invention can be directly used for laminating various substrates such as HPL by applying the layer facing the substrate. Importantly, in this embodiment, the presence of a copolymer containing an acid anhydride copolymer is no longer essential.

[0113] To achieve an optimal balance between the good handling properties of the multilayer foil and the good adhesion properties of the layer, it has been shown to be advantageous to ensure that the content (weight %) of one or several impact modifiers n im in the layer follows the following relationship: 0.01 * n im ≦n si ≦0.4 * n im n si is the content (weight %) of granular silica in the layer.

[0114] The granular silica n in the layer siThe content is 0.01 * n im If the pressure is lower than this, multilayer foils will, in principle, still be suitable for the desired purpose. However, the adhesion of various liquid coatings to the layers, and the adhesion of the layers to some substrates, may be somewhat reduced.

[0115] On the other hand, granular silica n in the layer si The content is 0.4 * n im If the value is higher than this, the brittleness of the layers increases. As a result, the multilayer foil of the present invention becomes more difficult to handle.

[0116] Furthermore, in order to achieve an even better balance between the adhesive properties of the layer and its brittleness, one or more impact-resistant modifiers n are added to the layer. im It is particularly advantageous if the content (by weight %) follows the following relationship: 0.03 * n im ≤n si ≤0.3 * n im In the formula, one or more impact-resistant modifiers n in the layer im It is particularly advantageous if the content (by weight) follows the following relationship: 0.05 * n im ≤n si ≤0.2 * n im n si This represents the granular silica content (weight %) in the layer.

[0117] The choice of granular silica for use in this invention is not particularly limited, and calcined silica can also be advantageously used, as can precipitated silica. Nevertheless, the specific surface area measured by the BET method, standard ISO 9277, is 200 m². 2 More than / g, preferably 300m 2 / g or more, more preferably 400m 2 / g or more, even more efficiently 500m 2It was shown that selecting granular silica with a density exceeding 1 / g is particularly advantageous in terms of adhesion-promoting properties. The specific surface area of ​​the granular silica is preferably 850 m². 2 It is less than / g.

[0118] Furthermore, the high dibutyl phthalate (DBP) absorption of silica used in the present invention has been found to be beneficial in terms of its adhesion-promoting properties. The silica used in the present invention preferably has a DBP absorption of 100 to 500 g / 100 g. More preferably, it has a DBP absorption in the range of 150 to 450 g / 100 g, and even more preferably, 150 to 400 g / 100 g. The DBP absorption can be determined according to method ASTM D6854-12a.

[0119] In preferred embodiments, the silica particles have a weight-average particle diameter d in the range of 1.0 μm to 20.0 μm, more preferably 2.0 μm to 15.0 μm. 50 It has a weight-average particle diameter d. 50 This can be determined by a laser diffraction method in accordance with standard DIN ISO 13320-1, using commercially available equipment such as the LS 13 320 laser diffraction particle size distribution analyzer from Beckman Coulter Inc., for example.

[0120] Preferably, the silica particles have a 45 μm sieve residue of 0.1% by weight or less, more preferably 0.01% by weight or less, as measured according to ISO 3262-19, indicating that there are substantially no agglomerates with particle sizes larger than 45 μm. This allows the silica particles to be dispersed in the matrix of the poly(meth)acrylate foil in a particularly homogeneous manner, without the presence of large filler agglomerates, so that the resulting foil exhibits a substantially uniform appearance and excellent mechanical properties. The presence of a substantial amount of larger agglomerates from silica particles in the layer is undesirable because such agglomerates tend to cause foil cracking, thereby reducing the initial tear strength at random locations in the foil.

[0121] The granular silica for use in the present invention typically has a SiO2 content of 95% by weight or more, more preferably 96% by weight or more, and even more preferably 97% by weight or more based on ISO 3262-19. Furthermore, it has been shown that the use of hydrophilic silica is particularly advantageous in terms of adhesion promoting properties. "Hydrophilic" silica means that when stirred and incorporated into water, its surface exhibits hydrophilic behavior, that is, the surface is completely wetted by water, and thus the contact angle with water at 23 ± 2 °C is less than 90°. A simple way to determine whether silica is "hydrophilic" is to stir the silica in water. For example, add 0.5 g of silica to a beaker containing 200 ml of pure water, and stir the mixture vigorously (stir at about 100 rpm using an impeller with a diameter of 3 cm) at a temperature of about 23 ± 2 °C. If the silica is dispersed in water, that is, the silica is not floating on the surface, the silica can be said to be "hydrophilic", which can be evaluated with the naked eye.

[0122] Hydrophilic precipitated silica and hydrophilic fumed silica are also known as non-modified silica. Hydrophilic silica has less than 10%, typically less than 5%, of the silanol groups on their surfaces substituted with hydrophobic functional groups such as alkoxy groups. In contrast, hydrophobic silica is obtained by treating hydrophilic silica with a halogenated silane, alkoxysilane or silazane to make it hydrophobic. Different from hydrophilic silica, hydrophobic silica has a low silanol group density and a low water vapor adsorption amount.

[0123] The inventors have found that the silanol group density has a strong influence on the adhesion promoting properties of granular silica. Although not wishing to be bound by theory, the inventors believe that the silanol groups on the surface of granular silica can chemically interact with the material of the coating layer D, particularly the isocyanate type curing agent. Also, when the layer containing granular silica is used as an adhesion promoting layer, the silanol groups on the surface of granular silica are expected to interact with various substrates. Typically, the silanol group density is 0.5 SiOH / nm 2 or more, more preferably 0.5 - 20.0 SiOH / nm 2More preferably 1.0 to 15.0 SiOH / nm 2 More preferably 1.5 to 10.0 SiOH / nm 2 It is desirable that this be the case.

[0124] To determine the silanol group concentration, the number of silanol groups on the silica surface is first determined by lithium aluminum hydride. However, hydrophilic precipitated silica, which generally has a larger surface area, has a greater absolute number of silanol groups than hydrophilic precipitated silica, which has a smaller surface area, so silanol group concentration alone is meaningless. As a result, it is necessary to relate the number of silanol groups to the surface area of ​​the silica. The surface area suitable for this purpose is the BET surface area, because it represents a surface area that is usable even for relatively small molecules such as water.

[0125] The silanol group density can be determined by following these steps: First, the moisture content of the silica sample is measured by drying it at 105°C for 2 hours according to ISO 787-2. Then, 2-4 g (1 mg accuracy) of the sample is transferred to a pressure-resistant glass apparatus (glass flask with dropping funnel) equipped with a pressure measuring device. In this apparatus, the sample is dried under reduced pressure (less than 1 hPa) at 120°C for 1 hour. At room temperature, approximately 40 ml of a 2 wt% diglyme solution of degassed lithium aluminum hydride is added dropwise from the dropping funnel. Further solution is added dropwise, if necessary, until no further pressure increase is observed. The pressure increase resulting from the hydrogen generated when lithium aluminum hydride reacts with the silanol groups of silica is determined by pressure measurement (using the volume known as a result of the calibration of the apparatus before measurement) with an accuracy of ≤1 hPa. From this pressure increase, it is possible to calculate the silica silanol group concentration, taking into account the silica's moisture content, using a general gas equation. The effect of the solvent's vapor pressure must be corrected accordingly. The silanol group concentration is calculated as follows: Silanol group density = Silanol group concentration / BET specific surface area.

[0126] Generally, the tap density of the granular silica used affects the adhesion-promoting properties of the corresponding layer. For this reason, foils with particularly advantageous adhesion-promoting properties are obtained with granular silica having a tap density of 10 g / l to 800 g / l, more preferably 40 g / l to 500 g / l, and even more preferably 80 g / l to 300 g / l, as measured according to DIN EN ISO 787-11.

[0127] For example, it is particularly preferable to use precipitated silica as described in Ullmann's Encyclopaedia of Industrial Chemistry, 5th edition, vol. A23, pp. 642-647. The precipitated silica has a specific surface area of ​​850 m² as measured by the BET method. 2 It may be up to / g and is obtained by reacting at least one silicate, preferably an alkali metal silicate and / or an alkaline earth metal silicate, with at least one acidifying agent, preferably at least one mineral acid. In contrast to silica gel (see Ullmann's Encyclopaedia of Industrial Chemistry, 5th edition, vol. A23, pp. 629-635), precipitated silica is not composed of a homogeneous three-dimensional SiO2 network, but rather of individual aggregates and agglomerates. A special characteristic of precipitated silica is its high proportion of so-called internal surface area, which is reflected in its highly porous structure with micropores and mesopores.

[0128] In particular, the precipitated silica used in this invention includes SIPERNAT® 160, SIPERNAT® 310, SIPERNAT® 320, SIPERNAT® 320DS, SIPERNAT® 325C, SIPERNAT® 350, SIPERNAT® 360, SIPERNAT® 383DS, SIPERNAT® 500LS, SIPERNAT® 570, SIPERNAT® 700, SIPERNAT® 22, S IPERNAT(registered trademark) 22S, SIPERNAT(registered trademark) 50LOS, SIPERNAT(registered trademark) 22, Tixosil(registered trademark) 38, Tixosil(registered trademark) 38A, Tixosil(registered trademark) 38D, Tixosil(registered trademark) 38D, Tixosil(registered trademark) 38X, Tixosil(registered trademark) 38AB, Tixosil(registered trademark) 39, Tixosil(registered trademark) 43, Tixosil(registered trademark) 331, Tixosil(registered trademark) 365, Zeoosil(registered trademark) 175BB, Zeoosil( (Registered Trademark) 39, Zeosil (Registered Trademark) 39AB, Zeosil (Registered Trademark) 45, Flo-Gard (Trademark) FF320, Flo-Gard (Trademark) FF330, Flo-Gard (Trademark) FF350, Flo-Gard (Trademark) FF370, Flo-Gard (Trademark) FF390, Flo-Gard (Trademark) SP, Flo-Gard (Trademark) SP-D, Hi-Sil (Trademark) 213, Hi-Sil (Trademark) ABS, Hi-Sil (Trademark) HOA, Hi-Sil (Trademark) HOA-D, Hi-Sil (Trademark) SC50-D, Hi-Sil (Trademark) 6 0-M, Hi-Sil(trademark)72, Hi-Sil(trademark)T-600, Hi-Sil(trademark)T650, Hi-Sil(trademark)700, Hubersil(registered trademark)5170, Hubersorb(registered trademark)250, Hubersorb(registered trademark)250NF, Hubersorb(registered trademark)5121, Hubersorb(registered trademark)600, Hubersorb(registered trademark)E, ZEOFREE(registered trademark)110SD, ZEOFREE(registered trademark)153, ZEOFREE(registered trademark)153B, ZEOFREE(registered trademark)182,Examples include ZEOFREE(registered trademark) 51, ZEOFREE(registered trademark) 5111, ZEOFREE(registered trademark) 5112, ZEOFREE(registered trademark) 5161, ZEOFREE(registered trademark) 5161A, ZEOFREE(registered trademark) 5161S, ZEOFREE(registered trademark) 5175B, ZEOFREE(registered trademark) 5181, ZEOFREE(registered trademark) 5183, ZEOFREE(registered trademark) 80, and ZEOFREE(registered trademark) 684.

[0129] Unlike calcined silica, precipitated silica can be used in layers A and C and is known as AEROSIL® (see Ullmann's Encyclopaedia of Industrial Chemistry, 5th edition, vol. A23, pp. 635-642). Calcined silica is obtained from silicon tetrachloride by flame hydrolysis. Due to its completely different preparation method, calcined silica has surface properties that differ from precipitated silica, among other properties. This is evident, for example, in its low density of silanol groups on the surface. Furthermore, no polyvalent anions are generated during the production of calcined silica.

[0130] Suitable calcined silica of the AEROSIL® type from Evonik Industries AG include, for example, AEROSIL® 90, AEROSIL® 130, AEROSIL® 150, AEROSIL® 200, AEROSIL® 300, AEROSIL® 380, and AEROSIL® Ox50, but Cab-O-Sil® M5, Cab-O-Sil® EH5, Cab-O-Sil® S17, HDK T40, HDK N20, and HDK N20E can also be used.

[0131] Polyalkyl (meth)acrylate Polyalkyl (meth)acrylates are typically obtained by free radical polymerization of a mixture containing an alkyl (meth)acrylate, typically methyl methacrylate (a), and at least one further (meth)acrylate (b). These mixtures generally contain at least 50% 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 (a), based on the weight of the monomer. The amount of methyl methacrylate (a) commonly used is 50.0% to 99.9% by weight, preferably 80.0% to 99.0% by weight, and particularly preferably 90.0% to 99.0% by weight, based on the weight of the monomer.

[0132] These mixtures for producing polyalkyl (meth)acrylates may include other (meth)acrylates (b) copolymerizable with methyl methacrylate (a). The term "(meth)acrylate" as used herein means encompassing methacrylates, acrylates, and mixtures thereof. (Meth)acrylates can be derived from saturated alcohols, e.g., methyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, pentile (meth)acrylate, and 2-ethylhexyl (meth)acrylate, or from unsaturated alcohols, e.g., oleyl (meth)acrylate, 2-propynyl (meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, and similarly aryl (meth)acrylates, e.g., benzyl (meth)acrylate or phenyl (meth)acrylate, cycloalkyl (meth)acrylate. These can be derived from acrylates, such as 3-vinylcyclohexyl (meth)acrylate, bornyl (meth)acrylate, hydroxyalkyl (meth)acrylates, such as 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycol di(meth)acrylates, such as 1,4-butanediol (meth)acrylate, ether alcohol (meth)acrylates, such as tetrahydrofurfuryl (meth)acrylate, vinyloxyethoxyethyl (meth)acrylate, and amides and nitriles of (meth)acrylic acid.

[0133] The amount of (meth)acrylic comonomer (b) commonly used is 0.1% to 50.0% by weight, preferably 1.0% to 20.0% by weight, and particularly preferably 1.0% to 10.0% by weight, based on the weight of the monomer, and the compound can be used alone or in mixture form.

[0134] Polymerization reactions are generally initiated by known free radical initiators. Among preferred initiators, particularly well known to those skilled in the art are azo initiators, e.g., AIBN and 1,1-azobiscyclohexanecarbonitride, as well as peroxy compounds, e.g., methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl 2-ethyl perhexanoate, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl isopropyl carbonate, 2,5-bis( These are 2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-butyl 2-ethylperoxyhexanoate, 3,5,5-trimethylperoxyhexanoate, dicumylperoxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, cumylhydroperoxide, tert-butylhydroperoxide, bis(4-tert-butylcyclohexyl)peroxydicarbonate, or mixtures thereof.

[0135] The polymerized composition may include not only the methyl methacrylate (a) and (meth)acrylate (b) described above, but also other unsaturated monomers copolymerizable with methyl methacrylate and the (meth)acrylate described above. Among these, in particular, are 1-alkenes, e.g., 1-hexene, 1-heptene; branched alkenes, e.g., vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methyl-1-pentene; acrylonitrile; vinyl esters, e.g., vinyl acetate; styrene; substituted styrenes having alkyl substituents in the side chains, e.g., α-methylstyrene and α-ethylstyrene; maleic acid derivatives, e.g., maleic anhydride, methyl maleic anhydride, maleimide, methyl maleimide; and dienes, e.g., divinylbenzene.

[0136] The amounts of these comonomers (c) commonly used are 0.0% to 10.0% by weight, preferably 0.0% to 5.0% by weight, and particularly preferably 0.0% to 2.0% by weight, based on the weight of the monomer, and the compounds herein can be used individually or in the form of mixtures.

[0137] Even more preferable are polymerizable components, (a) Methyl methacrylate 50.0% to 99.9% by weight, (b) 0.1% to 50.0% by weight of acrylic acid esters of C1-C4 alcohols, (c) 0.0% to 10.0% by weight of monomers copolymerizable with the monomers of (a) and (b) This is a polyalkyl (meth)acrylate that can be obtained by polymerization of a composition having [a certain characteristic].

[0138] In yet another embodiment, a polyalkyl (meth)acrylate composed of 85.0% to 99.5% by weight of methyl methacrylate and 0.5% to 15.0% by weight of methyl acrylate is preferred, where the amounts are based on 100% by weight of the polymerizable component. Particularly advantageous copolymers can be obtained by copolymerization of 90.0% to 99.5% by weight of methyl methacrylate and 0.5% to 10.0% by weight of methyl acrylate, where the amounts are based on 100% by weight of the polymerizable component. For example, the polyalkyl (meth)acrylate may contain 91.0% by weight of methyl methacrylate and 9.0% by weight of methyl acrylate, 96.0% by weight of methyl methacrylate and 4.0% by weight of methyl acrylate, or 99.0% by weight of methyl methacrylate and 1.0% by weight of methyl acrylate. The Vicat softening point (VSP) of the aforementioned polyalkyl (meth)acrylate (ISO 306:2013, Method B50) is typically at least 90°C, preferably 95°C to 112°C.

[0139] The weight-average molar mass Mw of polyalkyl (meth)acrylate is generally in the range of 50,000 g / mol to 300,000 g / mol. Particularly advantageous mechanical properties are obtained from foils containing polyalkyl (meth)acrylate having an average molar mass Mw in the range of 50,000 g / mol to 180,000 g / mol, preferably 80,000 g / mol to 160,000 g / mol, in each case determined by GPC against a PMMA calibration standard and THF as the eluent. Furthermore, the polyalkyl (meth)acrylate preferably contains oligomer PMMA having a weight-average molar mass of 300 to 1500 g / m as measured by SEC against a PMMA standard, in amounts of less than 20 wt%, more preferably less than 10 wt%, even more preferably less than 5 wt%, even more preferably less than 3 wt%, and even more preferably less than 1.5 wt%.

[0140] In a particularly preferred embodiment, the polyalkyl (meth)acrylate is a polymerizable component based on the weight of the polymerizable composition. (a) Methyl methacrylate 80.0% to 99.0% by weight, (b) Acrylates of C1-C4 alcohols in amounts of 1.0% to 20.0% by weight It can be obtained by polymerization of a composition containing [the specified element].

[0141] Impact resistance modifier Impact modifiers for use by themselves in the present invention are well known and may have different chemical compositions and different polymer structures. Impact modifiers may be crosslinked or thermoplastic. Furthermore, impact modifiers may be in granular form as core-shell or core-shell-shell particles. Typically, granular impact modifiers have an average particle size of 20 nm to 500 nm, preferably 50 nm to 450 nm, more preferably 100 nm to 400 nm, and most preferably 150 nm to 350 nm. Here, “granular impact modifier” generally means a crosslinked impact modifier having a core, core-shell, core-shell-shell, or core-shell-shell-shell structure. The average particle size of a granular impact modifier can be determined by methods known to those skilled in the art, for example, by photon correlation spectroscopy according to standard DIN ISO 13321:1996.

[0142] In its simplest form, the granular impact modifier is a crosslinked particle obtained by emulsion polymerization, having an average particle size in the range of 10 nm to 150 nm, preferably 20 nm to 100 nm, and particularly 30 nm to 90 nm. These generally consist of at least 20.0% by weight, preferably 20.0% to 99.0% by weight, of butyl acrylate, particularly preferably 30.0% to 98.0% by weight, 0.1% to 2.0% by weight, preferably 0.5% to 1.0% by weight, of a crosslinkable monomer, such as a polyfunctional (meth)acrylate, such as allyl methacrylate, and optionally other monomers, such as C1-C4 alkyl methacrylate, such as ethyl acrylate or butyl methacrylate, preferably methyl acrylate, or other vinyl polymerizable monomers, such as styrene, 0.0% to 10.0% by weight, preferably 0.5% to 5.0% by weight.

[0143] A more preferred impact resistance modifier is polymer particles that have a core-shell or core-shell-shell structure and are obtained by emulsion polymerization (see, for example, European Patent Publication No. 0113924, European Patent Publication No. 0522351, European Patent Publication No. 0465049 and European Patent Publication No. 0683028). In the present invention, it is typically required that the appropriate average particle size of these emulsion polymers is in the range of 20 nm to 500 nm, preferably 50 nm to 450 nm, more preferably 150 nm to 400 nm, and most preferably 200 nm to 350 nm.

[0144] A three-layer or three-phase structure having a core and two shells can be prepared as follows: The innermost (hard) shell may consist, for example, of methyl methacrylate, a small proportion of a comonomer, such as ethyl acrylate, and a certain proportion of a crosslinking agent, such as allyl methacrylate. The intermediate (soft) shell may consist of a copolymer containing, for example, butyl acrylate and optionally styrene, while the outermost (hard) shell is the same as the matrix polymer, thus resulting in compatibility and good bonding to the matrix.

[0145] The proportion of polybutyl acrylate in the core or shell of a two- or three-layer core-shell impact modifier is critically important for the impact modifier's effect, and is preferably in the range of 20.0% to 99.0% by weight, particularly preferably 30.0% to 98.0% by weight, and even more preferably 40.0% to 97.0% by weight, based on the total weight of the impact modifier.

[0146] In addition to granular impact modifiers containing polybutyl acrylate or polybutadiene copolymers, impact modifiers containing siloxanes can also be used. However, the use of such modifiers is not very advantageous because their presence in polyalkyl (meth)acrylate foils tends to negatively affect the printability of the foil.

[0147] Thermoplastic impact modifiers have a different mechanism of action than granular impact modifiers. They are generally mixed with a matrix material. When domains are formed, for example, when block copolymers are used, the preferred size of these domains (which can be determined, for example, by electron microscopy) corresponds to the preferred size of the core-shell particles.

[0148] There are various classes of thermoplastic impact modifiers. One example is aliphatic thermoplastic polyurethane (TPU), such as the Desmopan® products commercially available from Covestro AG. For example, Desmopan® WDP 85784A, WDP 85092A, WDP 89085A, and WDP 89051D TPUs all have refractive indices of 1.490 to 1.500 and are particularly suitable as impact modifiers.

[0149] A further class of thermoplastic polymers for use in accordance with the foil of the present invention as impact resistance modifiers are methacrylate-acrylate block copolymers, particularly acrylic TPEs, which include PMMA-poly-n-butyl acrylate-PMMA triblock copolymers, commercially available from Kuraray under the product name Kurarity®. The poly-n-butyl acrylate blocks form nanodomains of 10 nm to 20 nm in size within the polymer matrix.

[0150] In addition to the thermoplastic impact modifiers mentioned above, thermoplastic impact modifiers containing PVDF can also be used. However, using such modifiers in layers A and C tends to impair the adhesion-promoting properties of the layers and is therefore not very advantageous.

[0151] Fluoropolymer Depending on the intended use of the foil of the present invention, the fluoropolymer may be selected from polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polyethylene tetrafluoroethylene (ETFE), fluoroethylene-propylene (FEP), or mixtures thereof.

[0152] The PVDF polymer used in foils is generally a transparent, semi-crystalline thermoplastic fluoropolymer. Advantageously, PVDF has a high crystalline melting point. When the crystalline melting point of PVDF is at least 150°C, more preferably at least 160°C, the heat resistance of the foil becomes particularly high. The upper limit of the crystalline melting point is preferably around 175°C, which is equal to the crystalline melting point of PVDF. More preferably, the weight-average molecular weight Mw of PVDF, as determined by GPC, 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.

[0153] 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 to obtain PVDF. Vinylidene fluoride can be obtained, for example, by using hydrogen fluoride and methyl chloroform as starting materials and chlorodifluoroethane as a precursor. In principle, any commercially available grade of PVDF, such as Kynar® grade from Arkema, Dyneon® grade from Dyneon, and Solvay® grade from Solvay, is suitable for use in this invention. For example, the following commercially available products can be used: Arkema's Kynar® 720 (vinylidene fluoride content: 100% by weight, crystal melting point: 169°C) and Kynar® 710 (vinylidene fluoride content: 100% by weight, crystal melting point: 169°C); Kureha Corporation's T850 (vinylidene fluoride content: 100% by weight, crystal melting point: 173°C); Solvay Solexis's Solef® 1006 (vinylidene fluoride content: 100% by weight, crystal melting point: 174°C) and Solef® 1008 (product name) (vinylidene fluoride content: 100% by weight, crystal melting point: 174°C).

[0154] PVDF has three types of monomer bonding: head-to-head, tail-to-tail, and head-to-tail. Of these, head-to-head and tail-to-tail bonding are called "heterobonding." The chemical resistance of layer A is particularly high when the "proportion of heterobonding" in PVDF is 10 mol% or less. From the viewpoint of lowering the proportion of heterobonding, PVDF is preferably a resin produced by suspension polymerization. The proportion of heterobonding is specified in European Patent Application Publication No. 2756950 for PVDF. 19 This can be determined from the peaks of the F-NMR spectrum. Typically, fluoropolymers are not crosslinked and are therefore suitable for thermoplastic processing. PVDF may contain a matting agent to an extent that does not degrade the transparency of layer A. Organic and inorganic matting agents can be used.

[0155] In one embodiment, the fluoropolymer is a predominantly amorphous or microcrystalline PVDF with a haze value less than 5. For this purpose, the haze value is measured on a 30 μm thick pure fluoropolymer (PVDF) foil at 23°C according to ASTM D1003. Examples of PVDF types with sufficiently low haze values ​​and particularly good suitability include Solvay's Solef® 9009, Kureha's T850, and Arkema's Kynar® 9000HD.

[0156] UV absorbers and UV stabilizers Light stabilizers are well known and are described in detail as examples in Hans Zweifel, Plastics Additives Handbook, Hanser Verlag, 5th Edition, 2001, p. 141 ff. Light stabilizers are understood to include UV absorbers, UV stabilizers, and free radical scavengers.

[0157] UV absorbers may be derived, for example, from the group of substituted benzophenones, salicylates, cinnamate esters, oxanilides, benzoxazinones, hydroxyphenylbenzotriazoles, triazines, or benzylidene malonates. The most well-known representative examples of UV stabilizers / free radical scavengers are provided by the group of sterically hindered amines (hindered amine light stabilizers, HALS).

[0158] Preferably, the combination of UV absorber and UV stabilizer consists of the following components: - Benzotriazole-type UV absorbers, - Triazine-type UV absorber, - UV stabilizer (HALS compound).

[0159] These components can be used in the form of individual substances or in the form of mixtures.

[0160] Benzotriazole-type UV absorbers are known in the prior art and are typically 2-(2'-hydroxyphenyl)benzotriazole. Corresponding 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, and 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)- 5-Chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2' -Hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; transesterification product of 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'-2 Examples of benzotriazole-type UV absorbers that can be used include H-benzotriazole-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole; and 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]benzotriazole. Further examples of benzotriazole-type UV absorbers that can be used include 2-(2-hydroxy-5-methylphenyl)benzotriazole, and 2-[2-hydroxy-3,5-di(α,These are α-dimethylbenzyl)phenyl]benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)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, and 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)]. These compounds are commercially available from BASF SE (Ludwigshafen, Germany) as, for example, Tinuvin® 360 and Tinuvin® 234.

[0161] Benzotriazole-type UV absorbers can also be used in combination with other UV absorbers, such as bismalonate-type UV absorbers. An example of such a combination is Eusorb® BLA 4200M (a commercially available product containing Tinuvin® 329 and Hostavin® B-CAP) from Eutec Chemical Co. Ltd.

[0162] The amount of 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 preferably 0.5 to 3.0% by weight, based on the weight of layer B which is PMMA-based. It is also possible to use a mixture of different benzotriazole-type UV absorbers.

[0163] Triazine-type UV absorbers are typically 2-(2-hydroxyphenyl)-1,3,5-triazine derivatives. Preferably used 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, and 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-( 2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyl [poxy)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,Examples include 5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 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 are commercially available, for example, from BASF SE (Ludwigshafen, Germany) under the trademarks Tinuvin® 1600, Tinuvin® 1577, or Tinuvin® 1545.

[0164] The amount of triazine-type UV absorber is in the range of 0.1 to 5.0% by weight, preferably 0.2 to 3.0% by weight, and very preferably 0.5 to 2.0% by weight, based on the weight of the layer. It is also possible to use a mixture of different triazine-type UV absorbers.

[0165] Sterihed amines, or HALS (hindered amine light stabilizers) UV stabilizers, are known in themselves. They can be used to suppress aging in paints and plastics, particularly polyolefin plastics (Kunststoffe, 74 (1984) 10, pp. 620-623; Farbe + Lack, Volume 96, 9 / 1990, pp. 689-693). The tetramethylpiperidine group present in HALS compounds is responsible for the stabilizing effect. Compounds in this class either have no substituents on the piperidine nitrogen or may have substituents on the piperidine nitrogen by alkyl or acyl groups. Sterihed amines are not absorbed in the ultraviolet region. Sterihed amines can capture formed free radicals, whereas UV absorbers cannot. Examples of HALS compounds that have a stabilizing effect and can also be used in the form of a mixture include bis(2,2,6,6-tetramethyl-4-piperidyl) 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-piperidyl) succinate, poly(N-β-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine succinate) or bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate.

[0166] The amount of HALS compound used in each of layers A, B, and C is typically 0.0 to 5.0% by weight, preferably 0.1 to 3.0% by weight, and very preferably 0.2 to 2.0% by weight, based on the weight of layer B. It is also possible to use mixtures of different HALS compounds.

[0167] Other co-stabilizers that may be used include the HALS compounds mentioned above, sulfites such as sodium disulfite, and sterically hindered phenols and phosphates. Such co-stabilizers may be present at a concentration of 0.1 to 5.0% by weight, based on the weight of the layer.

[0168] Sterically hindered phenols are particularly suitable for use in the foil of the present invention. Preferred sterically hindered phenols include, in particular, 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, styrenelated phenols, 2,6-di-tert-butyl-4-methylphenol, and n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propyl Examples include pioneates, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenyl), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), stearyl-β(3,5-di-4-butyl-4-hydroxyphenyl)propionate, 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, and tetrakis-[methylene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane.Commercially available sterically hindered phenols include SUMILIZER BHT BP-76, WXR, GA-80 and BP-101 (Sumitomo Chemical Co., Ltd.), IRGANOX® 1076, IRGANOX® 565, IRGANOX® 1035, IRGANOX® 1425WL, IRGANOX® 3114, IRGANOX® 1330 and IRGANOX® 1010 (BASF SE), MARK AO-50, -80, -30, -20, -330 and -60 (ADEKA ARGUS), as well as TOMINOX SS, TT (Yoshitomi Pharmaceutical Co., Ltd.), IONOX WSP (ICI), SANTONOX® (MONSANTO), ANTAGE CRYSTAL (Kawaguchi Chemical Industry Co., Ltd.), and NOCLIZER Examples include NS-6 (Ouchi Shinko Chemical Industry Co., Ltd.), TOPANOL® CA (ICI Corporation), and CYANOX® 1790 (ACC Corporation).

[0169] Typically, layers A, B, or C are measured relative to the total weight of layer B. The first UV absorber is a benzotriazole-type compound in an amount of 0.5-4.0% by weight, As a second UV absorber, 0.5 to 3.0% by weight of a triazine-type compound, As a UV stabilizer, 0.2-2.0% by weight of a HALS-type compound It may include.

[0170] In embodiments of the present invention in which the multilayer foil has two or more layers containing polymethyl (meth)acrylate, it has been shown that it is advantageous in terms of enhanced weather resistance and UV protection if the layer facing the environment contains at least one triazine-type UV absorber and the layer below it contains at least one benzotriazole-type UV absorber. Furthermore, the inventors have found that the triazine-type UV absorbers can be replaced with inorganic UV absorbers such as titanium dioxide, tin dioxide, or glass in the form of glass beads or glass powder without affecting the long-term stability of the resulting multilayer foil.

[0171] For example, if a multilayer foil is intended to be used such that layer A faces the substrate and thereby acts as an adhesion-promoting layer, the molding composition of layer A is based on the weight of the molding composition, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight Includes, The molding composition of layer B is, based on the weight of the molding composition, Triazine-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It is advantageous to include it.

[0172] In an embodiment in which layer A is coated with layer D, the molding composition of layer A is, based on the weight of the molding composition, Triazine-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight Includes, The molding composition of layer B is, based on the weight of the molding composition, Benzotriazole-type UV absorber 0.1-5.0% by weight, One or more types of UV stabilizers, 0.0-5.0% by weight It is advantageous to include it.

[0173] Adhesion promoting copolymer Typically, the adhesion-promoting copolymer is measured based on the weight of the adhesion-promoting copolymer. (i) Methyl methacrylate 70.0-99.5% by weight, (ii) 0.5 to 15.0% by weight of adhesion-promoting monomer, (iii) 0.0 to 25.0% by weight of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups Includes.

[0174] The vinyl copolymerizable monomer (iii) can be selected from the group of vinyl aromatic monomers, such as α-halogenated styrene, p-methylstyrene, p-tert-butylstyrene, and vinylnaphthalene, and preferably from α-methylstyrene and styrene, with styrene being particularly preferred.

[0175] As used herein, the term "adhesion-promoting monomer" (ii) refers to a monomer having a polymerizable double bond and a reactive functional group that can react with an amino group or a methylol group. Therefore, the adhesion-promoting copolymer can be chemically interacted with the melamine resin of HPL by carrying out a heating reaction in contact with a material containing methylolmelamine and its derivatives, specifically a melamine resin or its precursor. The reaction temperature of the reactive functional group varies depending on the presence or absence of a catalyst, the pH value, etc., but is preferably 50 to 200°C, more preferably 110 to 170°C. Since HPL is generally manufactured at 110 to 170°C, when the reaction temperature is 110 to 170°C, the adhesion-promoting copolymer chemically reacts with the melamine resin of HPL.

[0176] Examples of reactive functional groups for amino or methylol groups include, but are not limited to, hydroxyl groups, carboxyl groups, amino groups, amide groups, acid anhydride groups, imide groups, and epoxy groups, with acid anhydride groups and carboxyl groups being particularly useful. Therefore, examples of adhesion-promoting monomers particularly suitable for use in the present invention include, but are not limited to, unsaturated carboxylic acid anhydrides, unsaturated dicarboxylic acid anhydrides, and unsaturated dicarboxylic acid imides. It has been shown that the use of maleic anhydride, methacrylic anhydride, maleic anhydride or itaconic anhydride, N-phenylmaleimide, and N-cyclohexylmaleimide provides particularly advantageous adhesion-promoting properties. It is particularly advantageous to use GMA (glycidyl methacrylate), maleic acid derivatives, such as maleic acid, maleic acid anhydride (MA), methyl maleic acid anhydride, maleimide, methyl maleimide, maleamide (MA), phenylmaleimide, and cyclohexylmaleimide, fumaric acid derivatives, methacrylic anhydride, and acrylic anhydride. The most promising results were observed with maleic anhydride and methacrylic anhydride.

[0177] In a preferred embodiment, the adhesion-promoting copolymer is (i) Methyl methacrylate in an amount of 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. (ii) Maleic anhydride 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, (iii) 0.0 to 25.0% by weight, preferably 2.0 to 15.0% by weight, of other vinyl copolymerizable monomers that do not have functional groups other than vinyl functional groups. Includes.

[0178] In the most preferred embodiment, the adhesion-promoting copolymer is a copolymer of MMA, styrene, and maleic anhydride.

[0179] glass beads In some embodiments, glass beads may be used in the fluoropolymer matrix to give the foil an aesthetically pleasing matte appearance. Depending on the desired gloss of the foil, the content of glass beads dispersed in the polymer matrix is ​​typically 3.0 to 30.0% by weight, more preferably 5.0 to 20.0% by weight, and particularly preferably 10.0 to 15.0% by weight, based on the total weight of the corresponding layer.

[0180] 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., have an aspect ratio of about 1:1.

[0181] Glass beads have an advantageous narrow size distribution. This size distribution can be measured using conventional instruments such as Malvern particle size analyzers, e.g., the Mastersizer 2000. Typically, glass beads are solid (i.e., non-hollow) glass beads, not limited to any particular chemical composition, and can have either a smooth or etched surface. Surface etching can be conveniently performed by contacting the glass beads with nitric acid for a sufficient time to give the desired degree of etching. To achieve optimal adhesion between the glass beads and the fluoropolymer matrix, the glass beads may have a siloxane layer.

[0182] Depending on the desired optical properties and surface roughness of the foil, the size of the glass beads (average diameter, weight average) is typically selected to be between 2.0 μm and 30.0 μm, preferably between 5.0 μm and 20.0 μm, and more preferably between 8.0 μm and 15.0 μm. Typically, when glass beads with an average diameter of less than 2.0 μm are used, the surface of the resulting foil will no longer appear without gloss. On the other hand, using glass beads with an average diameter greater than 30.0 μm results in a relatively large surface roughness, which is undesirable in many applications.

[0183] Glass bead size - so-called d 50 The size (i.e., 50 volume percent of the particles having a particle size smaller than the specified average particle size) can be measured according to the standard ISO 13320 (2009) for laser diffraction measurements. Typically, the size of glass beads is determined in each case (dispersion refractive index of particles in butyl acetate: 1,462) by laser light scattering (room temperature 23°C) using a Malvern Mastersizer 2000 from Malvern Instruments equipped with a mini-disperser MS1 at 2000 rpm, and evaluated by Fraunhofer diffraction. A more equally suitable instrument for this purpose is the Beckman Coulter LS 13 320 laser diffraction particle size analyzer.

[0184] The inventors have found that both the foil of the present invention and the substrate laminated using the aforementioned foil exhibit a particularly uniform matte appearance when, based on the weight of the glass beads used, at least 20% by weight, more preferably at least 40% by weight, even more preferably at least 60% by weight, and in some cases at least 80% by weight of glass beads have a diameter greater than the average thickness of the layer in which they are located. While we do not wish to be bound by theory, in such embodiments, the ability of the glass beads to resist external mechanical pressure at the elevated temperature during the lamination method is considered to be particularly high.

[0185] The average thickness of the foil and the average thickness of individual layers are advantageously determined using micrographs obtained with a scanning electron microscope such as the JEOL JSM-IT300 (commercially available from JEOL GmbH, Freising, Germany). A sample of a suitable size for measurement can be obtained by freezing the foil in liquid nitrogen and mechanically breaking it. The newly obtained fracture surface is then photographed using a scanning electron microscope.

[0186] To achieve good mechanical properties of the foil, the glass beads are preferably non-hollow, i.e., solid. The refractive index of the glass beads, measured for the Na-D line (589 nm) at 20°C, is selected to differ from the refractive index of the polymer material matrix in layer B, which is based on a fluoropolymer, by 0.01 to 0.2 units.

[0187] The chemical composition of the glass beads is not particularly limited, and virtually any type of commercially available glass can be used. Examples of such glasses 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.

[0188] The refractive index of soda-lime silica glass is typically 1.51 to 1.52. In a particularly preferred embodiment, the glass beads have the following composition: SiO2 70.0~75.0% by weight, Na2O 12.0~15.0% by weight, K2O 0.0~1.5% by weight, CaO 7.0~12.0% by weight, MgO 0.0~5.0% by weight, Al2O30.1~2.5% by weight, Fe2O30.0~0.5wt% It has.

[0189] Suitable glass beads include Spheriglass® products available from Potters Industries LLC., such as Spheriglass® 7025 and Spheriglass® 5000, or Omicron® glass beads Omicron® NP3 and Omicron® NP5 available from Sovitec Mondial SA.

[0190] In some embodiments, the polymer matrix of the fluoropolymer-based layer is substantially composed of one or more fluoropolymers, such as PVDF. In these embodiments, the fluoropolymer content is typically 85.0–97.0% by weight, more preferably 88.0–95.0% by weight, and particularly preferably 90.0–92.0% by weight, based on the total weight of the fluoropolymer-based layer. Thus, the fluoropolymer-based layer contains typically 4.0–15.0% by weight, preferably 5.0–12.0% by weight, and particularly preferably 8.0–10.0% by weight of glass beads, based on the total weight of the fluoropolymer-based layer B.

[0191] Coating layer D In one embodiment of the present invention, the foil further comprises a coating layer D adjacent to layer A. Based on the adhesion-promoting effect of silica particles in layer A, the coating layer D can be advantageously and uniformly applied as a liquid coating composition and preferably subsequently cured at least partially. Furthermore, the coating layer D exhibits excellent adhesion to layer A, characterized in a cross-hatch test by a value of 3 or less, preferably 2 or less, and more preferably 1 or less.

[0192] The coating layer D may contain at least partially crosslinked material selected from crosslinked polyurethane, crosslinked polyurethane (meth)acrylate, crosslinked poly(meth)acrylate, or mixtures thereof.

[0193] Cross-linked polyurethane The use of crosslinked polyurethane as a scratch-resistant coating is known in prior art, for example, as described in U.S. Patent Application Publication No. 2009 / 0085235. These materials are very suitable for forming highly weather-resistant nano- or microstructured surfaces. Furthermore, layer D, based on crosslinked polyurethane, exhibits good adhesion to layer A as described above.

[0194] Cross-linked polyurethane (meth)acrylate In further embodiments, the coating layer D may include at least partially crosslinked polyurethane (meth)acrylate. Crosslinked polyurethane (meth)acrylate is known in the prior art and is described, for example, in International Publication No. 2017 / 109118 and International Publication No. 97 / 49746. The coating composition forming layer D includes a resin component, a curing agent component, and optionally further additives such as a radical initiator. The resin component and the curing agent component are present in stoichiometric amounts.

[0195] These materials are applied to layer A in the form of a liquid coating composition and can be dried under clearly defined temperature conditions. Under these conditions, free hydroxyl groups in the resin component react with isocyanate groups in the curing agent component to form a urethane (meth)acrylate prepolymer coating. Importantly, the reactivity of the (meth)acrylic double bonds in the resin component is maintained at this stage. This provides a flexible, non-sticky coated multilayer foil that is easy to handle and can be stored in roll form at room temperature for a sufficient period of time. Importantly, undesirable blocking of the roll does not occur, and the coated multilayer foil can be easily unwound for application onto a substrate.

[0196] In the second reaction step, typically, when the coated foil is applied onto the substrate, polymerization of (meth)acrylic double bonds in the resin component of layer D occurs, which is induced by high temperature and pressure. This polymerization reaction is promoted in the presence of a radical initiator.

[0197] Therefore, coatings containing cross-linked polyurethane (meth)acrylate typically cure in two separate steps. However, depending on the application, it may be more advantageous to use cross-linked polyurethane (meth)acrylate that can be cured in three or more separate steps.

[0198] Typically, the resin component contains a free reactive (meth)acrylic double bond and at least two reactive hydroxyl groups per molecule. Most preferably, the resin component has the following general formula (I): [ka] (In the formula, R 1 R is an alkylene, aliphatic polyether, or polyester group. 2 and R 3 (i is an aliphatic or alicyclic group, i = 2 to 6, preferably 3 to 5).

[0199] The resin component of general formula (I) is preferably general formula (II): [ka] (In the formula, i = 2 to 6, preferably 3 to 5, R 1 The urethane group is formed from a polyfunctional (meth)acrylate monomer having at least one free hydroxyl group, which is an alkyl or aliphatic polyether or polyester group and reacts with a diisocyanate in a stoichiometric excess of 2 times the reactive hydroxyl group in the (meth)acrylate monomer to form a urethane group. The free isocyanate group then reacts with three, preferably polyfunctional, alcohols to form a second urethane group containing both a free reactive (meth)acrylic double bond and at least two reactive hydroxyl groups per molecule.

[0200] The hardening agent component is general formula (III): R 3 -[N=C=] j (III) (In the formula, j is at least 2, preferably 3, R 3 It is a trifunctional isocyanate of an aliphatic or alicyclic residue, which is usually blocked from reactivity at room temperature.

[0201] The coating composition further includes a radical-forming agent that is stable at room temperature, along with an inhibitor to prevent premature crosslinking of (meth)acrylic double bonds. Further optional additives in the composition are typically fillers, coloring pigments, flame retardants, UV absorbers, and free radical scavengers.

[0202] In the first method step, the coating composition is applied to layer A of the multilayer foil and partially cured, preferably at a temperature below 100°C. At this stage, the free hydroxyl groups in the resin component react with the isocyanate groups of the curing agent component to form a urethane acrylate prepolymer coating containing reactive (meth)acrylic double bonds. The premature reaction of these (meth)acrylic double bonds can be further advantageously prevented by adding appropriate inhibitors. Based on careful control of the reaction temperature during this method step, the polyaddition reaction occurs only between the free hydroxyl groups of the resin component and the functional groups of the curing agent component, while the reactivity of the (meth)acrylic double bonds of the resin component remains unaffected. This produces a flexible multilayer foil containing a partially coated layer D. This foil is easy to handle and can be stored for a sufficiently long period without developing undesirable curling.

[0203] In another method step, a multilayer foil containing a urethane acrylate prepolymer coating with reactive (meth)acrylic double bonds in layer D is laminated onto a substrate which may be, for example, wood, plastic, or metal, and a plastic or metal film. Preferably, the substrate is a high-pressure laminate (HPL). The press stack typically consists of multiple substrate materials impregnated with synthetic resin, which is its outermost layer on at least one multilayer foil having a partially cured layer D. This press stack is pressed under high pressure and at a temperature above the drying temperature, preferably above 140°C, so that additional crosslinking reactions occur in the reactive (meth)acrylic double bonds in layer D to form a urethane acrylate polymer. Thus, the cured layer D forms a scratch-resistant polyurethane (meth)acrylate-based coating.

[0204] In further embodiments, the coating composition may contain a mixture of components A to C and optionally D, in which case, - Component A is a polymerizable (meth)acrylate compound having at least two groups with (meth)acrylic double bonds and no hydroxyl groups per molecule. - Component B is a polymerizable (meth)acrylate compound having one or more groups with (meth)acrylic double bonds and at least two hydroxyl groups per molecule. - Component C is a polyurethane prepolymer having at least two hydroxyl groups per molecule and no isocyanate groups. - Component D, if present, is a resin having an aminoplast structure with at least two hydroxyl groups per molecule.

[0205] Component A typically comprises a compound selected from formulas (A1) and (A2), more preferably a mixture of compounds of formulas (A1) and (A2). In particular, it is preferable that component A consists of compounds of formulas (A1) and (A2): [ka] (In the formula, R 4 and R 6 Each is independently selected from an aliphatic hydrocarbon group, an aliphatic polyether group, and an aliphatic polyester group, R 5 ( is an aliphatic group or alicyclic hydrocarbon group, n = 2 to 9, preferably 2 to 4, and m = 2 to 9, preferably 2 to 4). The m acrylic acid ester groups H2C=CH-C(O)-O- are each group R 4 It is bonded to the group R via an ester group, 6 It has n acrylic acid ester groups bonded to it.

[0206] Preferably, R 4 and R 6R is independently selected from linear or branched alkyl groups, preferably branched alkyl groups, and particularly preferably selected from alkyl groups having 3 to 10, more preferably 3 to 6 C atoms. 5 Preferably, R is an alkyl group that is open-chain (i.e., linear or branched) or cyclic, or can be a combination of open-chain or branched units, particularly preferably an alkyl group having 3 to 20, more preferably 6 to 12 C atoms. A preferred form of R as the alkyl group in formula (A1) 4 For example, it provides m+1 valencies for bonding to adjacent groups. This applies similarly to the other components of the coating system.

[0207] [ka] (In the formula, R 7 is an aliphatic hydrocarbon group, with o = 2 to 6, preferably 3 to 5. Preferably, R 7 (The alkyl group is linear or branched, preferably branched, and is particularly preferably an alkyl group having 3 to 10, more preferably 3 to 6 C atoms.)

[0208] Component B preferably comprises a compound of formula (B1), and more preferably consists of a compound of formula (B1): [ka] (In the formula, R 8 R is selected from an aliphatic hydrocarbon group, an aliphatic polyether group, or an aliphatic polyester group. 9 and R 10 These are independently aliphatic or alicyclic hydrocarbon groups, with p = 2 to 9, preferably 2 to 4. Each of the p acrylic acid ester groups H2C=CH-C(O)-O- is a group R 8 It is bonded to the group R via an ester group, 10 Two hydroxyl groups are bonded to it.

[0209] R 8The alkyl group is preferably linear or branched, preferably branched, and particularly preferably an alkyl group having 3 to 10, more preferably 3 to 6 carbon atoms. 9 Preferably, the alkyl group is open-chain (i.e., linear or branched) or cyclic, or can be a combination of open-chain or branched units, particularly preferably an alkyl group having 3 to 20, more preferably 6 to 12 C atoms. 10 Preferably, the alkyl group is open-chain (i.e., linear or branched) or cyclic, or can be a combination of open-chain or branched units, and particularly preferably a linear or branched alkyl group having 3 to 20, more preferably 3 to 10 C atoms.

[0210] Component C is a polyurethane prepolymer having at least two hydroxyl groups per molecule and no isocyanate groups, and the hydroxyl groups are generally alcoholic hydroxyl groups. The polyurethane prepolymer may be linear or branched. Preferably, it is formed from a polyisocyanate having 2 to 4 isocyanate groups, preferably 2, and a polyalcohol having 2 to 4 alcoholic hydroxyl groups, preferably 2 or 3. The polyisocyanate and polyhydric alcohol are preferably aliphatic compounds. The number of subunits formed from the polyisocyanate and the number of subunits formed from the polyalcohol in the polyurethane prepolymer is preferably 2 to 20, more preferably 2 to 9. The number of hydroxyl groups per molecule of the polyurethane prepolymer is preferably 2 to 9, more preferably 2 to 5.

[0211] Preferred for component C is a polyurethane prepolymer that contains at least two hydroxyl groups and no other reactive groups. The term "reactive groups" refers to possible reactions between components of the coating system, i.e., in these particularly preferred polyurethane prepolymers of component C, at least two hydroxyl groups are the only groups that can react with other components of the coating system to form covalent bonds.

[0212] Component C preferably comprises a polyurethane prepolymer selected from formulas (C1) and (C2), i.e., component C comprises a compound of formula (C1) and / or a compound of formula (C2). In particular, it is preferable that component C is composed of a polyurethane prepolymer selected from compounds of formulas (C1) and (C2). A combination of compounds of (C1) and (C2) is also preferred.

[0213] [ka] (In the formula, R 11 Each instance is independently selected from an aliphatic hydrocarbon group, an aliphatic polyether group, and an aliphatic polyester group, which may be substituted with one or more hydroxyl groups, and R 12 Each instance is independently selected from either an aliphatic group or an alicyclic hydrocarbon group, and q is between 2 and 9.

[0214] All base R 11 The same and all base R 12 It is preferable that they are the same.

[0215] Preferably, R 11 The alkyl group is linear or branched, preferably branched, and is particularly preferably an alkyl group having 3 to 10, more preferably 3 to 6 C atoms. 11 It may be substituted with one or more hydroxyl groups. Preferably, there are 0, 1, or 2 such hydroxyl substituents. 12Preferably, the alkyl group is open-chain (i.e., linear or branched) or cyclic, or can be a combination of open-chain or branched units, and particularly preferably, it is a linear or branched alkyl group having 3 to 20, more preferably 6 to 12 C atoms.

[0216] [ka] (In the formula, R 11 and R 11a Each instance is independently selected from an aliphatic hydrocarbon group, an aliphatic polyether group, and an aliphatic polyester group, which may be substituted with one or more OH groups, and R 12 Each instance is independently selected from either an aliphatic group or an alicyclic hydrocarbon group, and q is between 2 and 9.

[0217] For formula (C2), all base R 11 and R 11a The same and all base R 12 It is preferable that they are the same. Preferably, R 11 and R 11a Each of these is a linear or branched alkyl group, preferably a branched alkyl group, and particularly preferably an alkyl group having 3 to 10, more preferably 3 to 6 C atoms. Also, alkyl group R 11 and R 11a It may be substituted with one or more hydroxyl groups. Preferably, R 11 It has one or two hydroxy substituents, R 11a It has 0 or 1 hydroxyl substituent. 12 This is an alkyl group that is open-chain (i.e., linear or branched) or cyclic, or can be a combination of open-chain or branched units, and is particularly preferably a linear or branched alkyl group having 3 to 20, more preferably 6 to 12 C atoms.

[0218] The optional component D is a resin having an aminoplast structure with at least two hydroxyl groups per molecule, and the hydroxyl groups are generally alcoholic hydroxyl groups. The basic structure of the resin of component D can also have groups formed by the reaction of hydroxyl groups, such as ester groups or urethane groups. Preferably, there are 2 to 30 hydroxyl groups per molecule, more preferably 10 to 30. The resin having an aminoplast structure is preferably a cured resin in powder form. The average molecular weight (Mn) of the resin of optional component D is preferably 1,000 g / mol to 1,000,000 g / mol. The resin having an aminoplast structure is preferably a resin having a urea-formaldehyde resin structure that can be obtained by polymerization (especially polycondensation) of formaldehyde and urea, and more preferably a cured resin in powder form having a urea-formaldehyde resin structure.

[0219] The coating composition for forming layer D is optionally present in the solvent as a mixture of components A, B, C and optionally D. Examples of solvents include esters such as ethyl acetate, butyl acetate, and 2-butoxyethyl acetate, aliphatic, alicyclic, and aromatic hydrocarbons, alcohols, glycols, glycol ethers, or ketones. The concentrations of components A-C and, if present, D in the solvent can be, for example, 65% to 95% by weight based on the total weight of the solution.

[0220] For the preparation of the resin component of the coating composition, components A to C and, if present, D can be provided and mixed. Alternatively, for the provision of components A (e.g., a compound of formula (A1)), B, and C, starting products such as mixed functional compounds such as polyols, polyisocyanates, and / or polyacrylates can be mixed with one or more hydroxyl groups prepared during the synthesis of the resin component by components A, B, and C. For example, the resin component can be prepared by single-step or multi-step synthesis at a temperature of 30 to 130°C. Preferably, during the synthesis of the resin component, the resin having an aminoplast structure as component D is present in the synthesis mixture from the start of the synthesis.

[0221] During the preparation of the resin components, the mixture is thermally heated to a temperature of preferably 30 to 130°C after the addition of the resin having aminoplast structure D.

[0222] In the resin components, component A is preferably present in an amount of 40.0 to 80.0% by weight, with the total weight of components A to C, and optionally A to D, being 100% by weight; component B is present in an amount of 19.0 to 55.0% by weight; component C is present in an amount of 0.5 to 5.0% by weight; and optional component D is present in an amount of 0.5 to 7.0% by weight. In a more preferred embodiment, the resin component contains the component of formula (A1) in an amount of 15.0 to 45.0% by weight, the component of formula (A2) in an amount of 15.0 to 45.0% by weight (where the total amount of (A1) and (A2) is 40.0 to 80.0% by weight), the component of formula (B1) in an amount of 19.0 to 55.0% by weight, the components (C1) and (C2) in a total amount of 0.5 to 5.0% by weight, and an optional component D in an amount of 0.5 to 7.0% by weight. Here again, the total amount of the components is 100% by weight.

[0223] In a more preferred embodiment, the resin component contains the component of formula (A1) in an amount of 20.0 to 40.0% by weight, the component of formula (A2) in an amount of 20.0 to 40.0% by weight (where the total amount of (A1) and (A2) is 40.0 to 80.0% by weight), the component of formula (B1) in an amount of 25.0 to 47.0% by weight, the components (C1) and (C2) in a total amount of 0.6 to 3.0% by weight, and the component D in an amount of 1.0 to 5.0% by weight. Here again, the total amount of the components is 100% by weight.

[0224] In a particularly preferred embodiment, the resin component contains the component of formula (A1) in an amount of 25.0 to 35.0% by weight, the component of formula (A2) in an amount of 25.0 to 35.0% by weight (where the total amount of (A1) and (A2) is 50.0 to 70.0% by weight), the component of formula (B1) in an amount of 30.0 to 42.0% by weight, the components (C1) and (C2) in a total amount of 0.8 to 2.0% by weight, and the component D in an amount of 2.0 to 4.5% by weight. Here again, the total amount of the components is 100% by weight.

[0225] Cross-linked poly(meth)acrylate Crosslinked poly(meth)acrylates are also suitable for forming layer D. Corresponding coating compositions are known in the prior art, particularly described in International Publication No. 2008 / 155149. The aforementioned coating compositions typically comprise at least 40% by weight of (meth)acrylate having at least two double bonds, and two different polymerization initiators, preferably at least one photoinitiator and at least one thermal initiator. The use of two different thermal initiators acting at different temperatures is also possible. The (meth)acrylate may preferably be selected from 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, and pentaerythrityl tetraacrylate or mixtures thereof.

[0226] The coating composition may further contain lubricants, colorants, metallic pigments, UV stabilizers, fillers, or nanomaterials.

[0227] Similar to compositions containing polyurethane (meth)acrylate, coatings based on crosslinked poly(meth)acrylate can also be cured in several different method steps. Therefore, after applying the coating to layer A, pre-curing is performed. The resulting material is relatively flexible, which is advantageous in terms of handling multilayer foils. After the coated multilayer foil is applied to the substrate, the final curing of the coating is performed in a second method step. The resulting layer D has high scratch resistance due to its high degree of crosslinking.

[0228] Further additives The molding compositions forming any of the layers of the present invention may further optionally contain additional additives selected from colorants, dispersants, flow improvers, lubricants, fillers, and heat stabilizers, provided that the properties of the composition are not adversely affected by these additives. These compounds are well known to those skilled in the art and do not need to be described in detail here.

[0229] Foil properties Depending on the intended purpose, the foil 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 5.0 μm and 100.0 μm.

[0230] The thickness of the foil and its layers according to the present invention can be determined by mechanical scanning in accordance with the standard ISO 4593-1993. Furthermore, the thickness of the foil and its individual layers according to the present invention can be determined using a scanning electron microscope. For this purpose, the foil sample can be frozen in liquid nitrogen and mechanically crushed, and the newly obtained surface can be analyzed.

[0231] Layer A typically has a thickness of 1.0 μm to 30.0 μm, preferably 5.0 μm to 20.0 μm.

[0232] Layer B typically has a thickness of 10.0 μm to 200.0 μm, preferably 15.0 μm to 150.0 μm.

[0233] If present, the adhesion promoting layer C typically has a thickness of 1.0 μm to 30.0 μm, preferably 2.0 μm to 20.0 μm.

[0234] Based on the presence of protruding silica particles in layer A, the outer surface of layer A of the multilayer foil typically has a roughness value Rz in accordance with DIN 4768, at least 0.7 μm, preferably 1.0 to 50.0 μm, more preferably 2.0 to 40.0 μm, and even more preferably 5.0 to 30.0 μm. Roughness can be measured using commercially available equipment such as the Form Talysurf 50 manufactured by Rank Taylor Hobson GmbH.

[0235] The gloss (R60°) of the outer surface of layer A, according to DIN 67530 (01 / 1982), is typically at most 40, preferably at most 30, and particularly 15-30. The gloss can be measured using an RL laboratory reflectometer, such as a reflectometer from Fa. Dr. Hach-Lange.

[0236] Foil manufacturing method Depending on the intended application, the foil of the present invention can be manufactured to any desired thickness. The remarkable factors here are its ability to maintain a uniform degree of matiness even under mechanical pressure at elevated temperatures during lamination, for example, the exceptional weather resistance and mechanical stability, and the very high weather resistance and mechanical protection provided to the substrate. However, for the purposes of the present invention, relatively thin plastic molded articles, i.e., films or foils, characterized by thicknesses 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, are preferred.

[0237] The mixtures of the individual components of layers A, B, and C can be prepared via dry blends of the components, which are in powder, granular, or preferably pelletized form. Such mixtures can also be processed via melting and mixing of the individual components in a molten state, or via melting a dry premix of the individual components, to give a ready-to-use molding composition. For example, this can be done in a single-screw or twin-screw extruder. The resulting extruded material can then be pelletized. Conventional additives, auxiliaries, and / or fillers may be mixed in directly or added later by the end-user as needed.

[0238] The multilayer foil of the present invention can then be manufactured by methods known to the present, for example, by co-extrusion or lamination, or by extrusion lamination.

[0239] One particular manufacturing variation of the present invention relates to a method comprising the step of forming the foil using a foil forming method, preferably a chill-roll method.

[0240] Application of multilayer foils to substrates The foil according to the present invention can be used in a wide range of applications. One preferred application of the foil is coating plastic molded articles or metal articles. In particular, the substrate to be protected by the foil may be melamine resin-impregnated paper, optionally fiber-reinforced polymer materials, preferably polyvinyl chloride (PVC), polycarbonate (PC), or polypropylene (PP), or metal, preferably steel or aluminum, and the co-extruded foil is applied directly to the substrate.

[0241] In this case, it is particularly advantageous to coat plastic molded articles that contain or are composed of PVC. The protected substrate is advantageously, for example, a window profile made of aluminum, wood, plastic or composite material, to which a decorative foil, preferably made of PC, SAN or PVC, can be attached. This article is then protected from weathering by using the foil according to the present invention. Another preferred application of the foil according to the present invention is the design of high-spec, durable surface finishes for substrate materials. Furthermore, the foil according to the present invention can be advantageously used in traffic control materials (TCM).

[0242] As described above, the foil of the present invention can be applied to a substrate such that layer A is in direct contact with the surface of the substrate, thereby acting as an adhesion-promoting layer. In this embodiment, when the foil of the present invention is substantially composed of layers A and B, layer B faces the environment and layer A is located between layer B and the substrate. When the foil of the present invention further includes layer C, layer B faces the environment and layer B is located between layer C and layer A. Thus, the layers are arranged in the following order: - Layer C (if it exists) - Layer B - Layer A - Base material.

[0243] Furthermore, if the multilayer foil of the present invention includes a coating layer D, the coating layer D faces the environment, and the layers are in the following order: - Layer D - Layer A - Layer B - Layer C (if it exists) - Base material.

[0244] A further aspect of the present invention is a method for manufacturing a coated article, comprising the step of applying foil onto the surface of a substrate. The coated article comprises a substrate and has an outer surface, the substrate being at least partially covered by foil, the foil having layers arranged in the following order, starting from the outer surface of the coated article: - Layer C (if it exists) - Layer B - Layer A - Base material Or, instead, - Layer D - Layer A - Layer B - Layer C (if it exists) - Base material.

[0245] The application of the foil to the substrate according to the present invention is relatively simple in all cases. The foil is preferably applied to the substrate to be protected by co-extrusion. Application of the foil by foil lamination to the material to be protected is also possible. Use characterized by the application of foil to the material to be protected by extrusion lamination is also preferred. Preferably, extrusion lamination is performed at a temperature of 120°C or higher and under a mechanical pressure of 1 MPa or higher, preferably 2 MPa or higher, more preferably 4 MPa or higher, more preferably 6 MPa or higher, and more preferably 7 MPa or higher.

[0246] In one embodiment of the present invention, the article itself may be a foil or sheet that can be conveniently stored and / or handled in a roll.

[0247] In preferred embodiments, the coated articles of the present invention may be high-pressure laminates (HPL), medium-pressure laminates (MPL), or continuous-pressure laminates (CPL). Accordingly, one aspect of the present invention relates to a method for manufacturing high-pressure laminates using the foil as described above. In particularly preferred embodiments, the multilayer material that can be obtained using the foil of the present invention is a decorative high-pressure laminate (HPL) according to standards EN 438-2 and EN 438-6, which consists of layers of webs of fibrous material (e.g., paper) impregnated with a curable resin, which are bonded together by the high-pressure method described later. The surface layer of the material having a decorative color or pattern on one or both sides is impregnated with an aminoplastic-based resin, such as melamine resin. The amino groups or methylolamino groups present in the decorative layer during the high-pressure method then function as reaction partners for covalent bonding to the polymethacrylate layer (in this case, the foil) for surface finishing. The corresponding high-pressure laminate is described in particular in U.S. Patent Application Publication No. 2017 / 0197391.

[0248] The HPL is typically prepared in batches at a pressure of 1 MPa to 20 MPa, preferably 4 MPa to 15 MPa, more preferably 6 MPa to 10 MPa, and a temperature of 120°C to 220°C. Under these conditions, if a coating layer D is present, it typically undergoes final crosslinking, thereby forming a coating with high scratch resistance.

[0249] The high-pressure method creates a long-lasting bond between the decorative layer and the polymethacrylate layer applied according to the present invention. The temperature set during the method and the resulting interpenetration of the melamine resin-saturated decorative paper into the foil ensure sufficient covalent bonding and, consequently, long-lasting bonding to the material.

[0250] The high-pressure method is defined as the simultaneous use of heat (120°C or higher) and high pressure (3 MPa or higher), resulting in the curable resin flowing and then curing to achieve a relatively high density (at least 1.35 g / cm³) with the required surface structure. 3This produces a homogeneous, non-porous material. The high-pressure method can be performed in batch or roll-to-roll, i.e., continuously. The latter product is usually called continuously pressed laminate (CPL).

[0251] A method for manufacturing CPL includes the step of providing a curable resin-based support, for example, a phenol resin-based support structure or a melamine resin-based support structure. The support structure may include several individual layers, which are typically paper layers. The paper layers can be used as cardboard layers. One or all of these layers preferably contain a phenol resin or a melamine resin. The support structure typically has a thickness of 0.1 mm to 2 mm, more preferably 0.2 mm to 1.5 mm, more preferably 0.3 mm to 1.2 mm, more preferably 0.4 mm to 1.0 mm, and more preferably 0.5 mm to 0.8 mm. The CPL method includes pressing the multilayer foil of the present invention together with the support. The time the material is exposed to pressure and temperature is usually significantly shorter than in the HPL batch method. In the CPL method, the layers can be pressed in a continuous manner to form a kind of endless plate, for example by using a double-sided heated double-belt press. The double-belt press may include a structured belt (i.e., a belt with a structured / embossed surface). The pressing pressure can be lower than in the case of HPL manufacturing. Preferably, in the CPL method, pressing is performed at a pressure of 1.0 MPa to 10 MPa, more preferably 1.5 MPa to 8.0 MPa, even more preferably 2.0 MPa to 6.0 MPa, even more preferably 2.5 MPa to 4.5 MPa, and most preferably 3.0 MPa to 3.5 MPa. The temperature during this step is usually maintained in the range of 120°C to 200°C, more preferably 140°C to 180°C, and even more preferably 150°C to 170°C. Under these conditions, the coating layer D, if present, typically undergoes final crosslinking, thereby forming a coating with high scratch resistance.

[0252] Table 1 below lists embodiments of the multilayer article of the present invention having particularly advantageous properties. The multilayer article comprises a substrate coated with the multilayer foil of preferred embodiments 1 to 18 above, and optionally a coating layer D. Embodiments are schematically shown in Figures 6 to 12.

[0253] [Table 1]

[0254] SEM image SEM images were obtained using a commercially available scanning electron microscope, the JEOL JSM IT300, manufactured by JEOL Ltd. Foil samples were frozen in liquid nitrogen, mechanically fractured, and the newly obtained surfaces were analyzed.

[0255] The measurement parameters were as follows: Variable flow of electrons from a tungsten filament (cathode) Vacuum systems: Rotary pumps / Oil diffusion pumps XYZ rotation and tilt: Fully motorized Working distance (WD): 5-70mm (common: 10mm) Sample rotation: 360° Sample tilt: -5 to a maximum of 90° (depending on WD) Magnification: 750x Maximum resolution: approx. 3nm Detector: Secondary electron detector (SED) Backscattered electrons (BSE, 5 divisions) Energy-dispersive X-ray spectroscopy (EDS)

[0256] Sample preparation To measure the foil thickness, the sample was frozen using liquid nitrogen and mechanically fractured. Brittle fracture was induced for this purpose. The resulting fracture surfaces were analyzed.

[0257] conductive layer All standard samples were sputtered with gold to obtain a conductive surface.

[0258] Measurement using images The average thickness of the foil and the average thickness of the individual layers were measured from SEM images. To enable the measurement of existing images at a later time, all images were saved in an SEM image database, similar to the relevant measurement parameters.

[0259] The following examples illustrate the invention in more detail without limitation.

[0260] Examples The multilayer foils were produced by adapter coextrusion using the chill roll method at 240 - 250 °C (melt temperature at the extrusion die) and an extrusion speed of 7.3 m / min using a single screw extruder with a diameter of 35 mm and a single screw coextruder with a diameter of 25 mm. For the 3 - layer foils, a second 25 - mm diameter single screw coextruder was used. Alternatively, production can be achieved by a plurality of manifold coextrusion methods or a combination of adapter and plurality of manifold coextrusion.

[0261] The adhesion promoter used was a copolymer of 75 wt% MMA, 15 wt% styrene, and 10 wt% maleic anhydride. The weight - average molar mass Mw of this copolymer was about 100,000 g / mol (determined by GPC relative to PMMA standards).

[0262] As the granular silica, precipitated hydrophilic silica with a specific surface area of about 700 m 2 / g (measured by the BET method according to ISO 9277) available from Evonik Industries AG (Hanau) was used.

[0263] PMMA1 referred to in the following examples is a copolymer of 96 wt% methyl methacrylate and 4 wt% methyl acrylate with a mass - average molecular weight Mw of 155,000 g / mol (determined by GPC relative to PMMA standards) and is available from Roehm GmbH (Darmstadt).

[0264] The PMMA2 referred to in the following examples is a copolymer of 99% by weight methyl methacrylate and 1% by weight methyl acrylate, with a mass-average molecular weight Mw of 110,000 g / mol (determined by GPC relative to PMMA standard), and is available from Roehm GmbH (Darmstadt).

[0265] The PMMA3 mentioned in the following examples is a copolymer of 96% by weight methyl methacrylate and 4% by weight methyl acrylate, with a mass-average molecular weight Mw of 115,000 g / mol (determined by GPC relative to PMMA standard), and is available from Roehm GmbH (Darmstadt).

[0266] The impact-resistant modifiers 1, 3, and 4 mentioned in the examples described later are butyl acrylate-based acrylic core-shell type impact-resistant modifiers.

[0267] The impact resistance modifier 2 mentioned in the examples described later is an ashel-type core-shell impact resistance modifier based on butyl acrylate.

[0268] Tinuvin® 360 (benzotriazole-type UV absorber) and Tinuvin® 1600 (triazine-type UV absorber) are commercially available from BASF SE (Ludwigshafen).

[0269] Chimassorb® 119 is a hindered amine light stabilizer (HALS) and is commercially available from BASF SE (Ludwigshafen).

[0270] Manufacturing Example 1 (According to the present invention) A molding compound for forming layer A was prepared using a twin-screw extruder. A three-layer foil with a total thickness of 75 μm was prepared by extruding at 240-250°C (melting temperature) and an extrusion speed of 7.3 m / min using a 35 mm diameter single-screw extruder and a 25 mm diameter single-screw co-extruder.

[0271] This foil had the following composition: Layer A had a thickness of 10 μm and the following composition: a) 87.0% by weight of impact-resistant additive 1 b) 10.0% by weight granular silica c) 2.0% by weight of Tinuvin® 1600 d) 1.0% by weight of a dispersant.

[0272] Layer B had a thickness of 60 μm and the following composition: a) 19.7% by weight of impact-resistant additive 2 b) 55.3% by weight of PMMA1 c) 22.2% by weight of PMMA3 d) A 2.7% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0273] Layer C had a thickness of 5 μm and had the following composition: a) 78.5% by weight of impact-resistant additive 1 b) 20.0% by weight of an adhesion promoter c) 1.3% by weight of Tinuvin® 360 d) 0.2% by weight of Chimassorb® 119.

[0274] Manufacturing Example 2 (Comparative Example) A three-layer foil with a total thickness of 75 μm was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: Layer A had a thickness of 10 μm and the following composition: a) 16.8% by weight of impact-resistant additive 2 b) 67.6% by weight of PMMA2 c) 10.0% by weight granular silica d) 0.5% by weight of Tinuvin® 360 e) A mixture of 5.1% by weight of Irganox® 1076 and several dispersants.

[0275] Layer B had a thickness of 60 μm and had the following composition: a) 19.7% by weight of impact-resistant additive 2 b) 55.3% by weight of PMMA1 c) 22.2% by weight of PMMA3 d) A 2.7% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0276] Layer C had a thickness of 5 μm and the following composition: a) 78.5% by weight of impact-resistant additive 1 b) 20.0% by weight of an adhesion promoter c) 1.3% by weight of Tinuvin® 360 d) 0.2% by weight of Chimassorb® 119.

[0277] Manufacturing Example 3 (According to the present invention) A three-layer foil with a total thickness of 75 μm was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: Layer A had a thickness of 10 μm and the following composition: a) 65.6% by weight of impact-resistant additive 1 b) 11.3% by weight of impact-resistant additive 3 c) 11.3% by weight of PMMA1 d) 10.0% by weight granular silica e) A 1.9% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0278] Layer B had a thickness of 60 μm and had the following composition: a) 19.7% by weight of impact-resistant additive 2 b) 55.3% by weight of PMMA1 c) 22.2% by weight of PMMA3 d) A 2.7% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0279] Layer C had a thickness of 5 μm and had the following composition: a) 78.5% by weight of impact-resistant additive 1 b) 20.0% by weight of an adhesion promoter c) 1.3% by weight of Tinuvin® 360 d) 0.2% by weight of Chimassorb® 119.

[0280] Manufacturing Example 4 (According to the present invention) A three-layer foil with a total thickness of 75 μm was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: Layer A had a thickness of 10 μm and the following composition: a) 92.5% by weight of impact-resistant additive 1 b) 7.5% by weight of granular silica.

[0281] Layer B had a thickness of 60 μm and had the following composition: a) 19.7% by weight of impact-resistant additive 2 b) 55.3% by weight of PMMA1 c) 22.2% by weight of PMMA3 d) A 2.7% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0282] Layer C had a thickness of 5 μm and had the following composition: a) 78.5% by weight of impact-resistant additive 1 b) 20.0% by weight of an adhesion promoter c) 1.3% by weight of Tinuvin® 360 d) 0.2% by weight of Chimassorb® 119.

[0283] Manufacturing Example 5 (According to the present invention) A three-layer foil with a total thickness of 75 μm was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: Layer A had a thickness of 10 μm and the following composition: a) 62.0% by weight of impact-resistant additive 1 b) 10.6% by weight of impact-resistant additive 3 c) 10.6% by weight of PMMA1 d) 15.0% by weight granular silica e) A prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119 in a 1.8% by weight concentration.

[0284] Layer B had a thickness of 60 μm and had the following composition: a) 19.7% by weight of impact-resistant additive 2 b) 55.3% by weight of PMMA1 c) 22.2% by weight of PMMA3 d) A 2.7% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0285] Layer C had a thickness of 5 μm and had the following composition: a) 78.5% by weight of impact-resistant additive 1 b) 20.0% by weight of an adhesion promoter c) 1.3% by weight of Tinuvin® 360 d) 0.2% by weight of Chimassorb® 119.

[0286] Manufacturing Example 6 (Comparative Example) A two-layer foil with a total thickness of 45 μm was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: Layer A had a thickness of 40 μm and had the following composition: a) 18.6% by weight of impact-resistant additive 2 b) 75.1% by weight of PMMA2 c) 0.5% by weight of Tinuvin® 360 d) A mixture of 5.8% by weight of Irganox® 1076 and a dispersant.

[0287] Layer B had a thickness of 5 μm and had the following composition: a) 78.5% by weight of impact-resistant additive 1 b) 20.0% by weight of an adhesion promoter c) 1.3% by weight of Tinuvin® 360 d) 0.2% by weight of Chimassorb® 119.

[0288] Manufacturing Example 7 (Comparative Example) A two-layer hydrophilic coating was applied to layer A of the foil in manufacturing example 6 according to the following procedure: Preparation of the intermediate layer A first copolymer consisting of 88% by weight of methyl methacrylate and 12% by weight of γ-methacryloyloxypropyltrimethoxysilane, and a second copolymer consisting of 20% by weight of methyl methacrylate and 80% by weight of butyl methacrylate were dissolved in butyl acetate in a 1:1 ratio and applied as a thin film to foil. After pouring, the coated foil was dried in an 80°C oven for 20 minutes.

[0289] Preparation of hydrophilic coatings 25% by weight (30% by weight solids) of anionic silica sol was mixed with 0.1% by weight of potassium salt of 3-sulfopropyl ester of O-ethyldithiocarboxylic acid and 0.4% by weight of ethoxylated fatty alcohol. This mixture was diluted to 100 parts with deionized water and applied as a thin film onto a foil with an intermediate layer. After air drying, the foil with the intermediate layer and hydrophilic coating was dried in an 80°C convection oven for 20 minutes.

[0290] Manufacturing Example 8 (Comparative Example) Layer A of the foil from manufacturing example 6 was subjected to corona treatment.

[0291] Manufacturing Example 9 (According to the present invention) A two-layer foil with a total thickness of 75 μm was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: Layer A had a thickness of 5 μm and the following composition: a) 82.8% by weight of impact-resistant additive 1 b) 10.0% by weight of an adhesion promoter c) 5.0% by weight granular silica d) A 1.8% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119. e) 0.5% by weight of a dispersant.

[0292] Layer B had a thickness of 70 μm and had the following composition: a) 10.3% by weight of impact-resistant additive 2 b) 89.5% by weight of PMMA2 c) 0.2% by weight of Chimassorb® 119.

[0293] Manufacturing Example 10 (Comparative Example) Under the same conditions as in Manufacturing Example 1, a single-layer foil was prepared consisting of a single layer A and having a mechanically textured surface (created with a textured embossing roller). This foil had the following composition: a) 30.0% by weight of impact-resistant additive 1 b) 10.0% by weight of impact-resistant additive 2 c) 45.3% by weight of PMMA2 d) 12.5% ​​by weight of PMMA3 e) A prepared mixture of Tinuvin® 360 and Chimassorb® 119 in a concentration of 2.2% by weight.

[0294] Manufacturing Example 11 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 100.0% by weight of PMMA1.

[0295] Manufacturing Example 12 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 74.8% by weight of impact-resistant additive 4 b) 10.0% by weight of Degacryl® 6615 (acrylic bead polymer) available from Evonik Industries AG. c) 13.3% by weight of PMMA1 d) A prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119 in a 1.9% by weight concentration.

[0296] Manufacturing Example 13 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 66.5% by weight of impact-resistant additive 4 b) 20.0% by weight of Degacryl® 6615 (acrylic bead polymer) available from Evonik Industries AG. c) 11.8% by weight of PMMA1 d) A prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119 in a 1.7% by weight concentration.

[0297] Manufacturing Example 14 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 78.1% by weight of impact-resistant additive 4 b) 6.0% by weight of Spheriglass® Potters 5000 CP-01 (glass beads) available from Potters Industries LLC. c) 13.9% by weight of PMMA1 d) A 2.0% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0298] Manufacturing Example 15 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 70.6% by weight of impact-resistant additive 4 b) 15.0% by weight of Spheriglass® Potters 5000 CP-01 (glass beads) available from Potters Industries LLC. c) 12.6% by weight of PMMA1 d) A prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119 in a 1.8% by weight concentration.

[0299] Manufacturing Example 16 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 70.6% by weight of impact-resistant additive 4 b) 15.0 wt% Omicron® NP3 (glass beads) with P1 coating, available from Sovitec Mondial SA. c) 12.6% by weight of PMMA1 d) 1.8% by weight of a prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0300] Manufacturing Example 17 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 70.6% by weight of impact-resistant additive 4 b) 15.0% by weight of SIPENNAT® 44MS (zeolite) available from Evonik Industries AG. c) 12.6% by weight of PMMA1 d) A prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119 in a 1.8% by weight concentration.

[0301] Manufacturing Example 18 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 70.6% by weight of impact-resistant additive 4 b) 15.0% by weight granular silica c) 12.6% by weight of PMMA1 d) A prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119 in a 1.8% by weight concentration.

[0302] Therefore, the composition of the single-layer foil corresponds to the composition of layer A of the multilayer foil of the present invention.

[0303] Manufacturing Example 19 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 70.6% by weight of impact-resistant additive 4 b) 15.0% by weight of SILBOND® 600 MST (silane-treated quartz filler) available from Quarzwerke GmbH. c) 12.6% by weight of PMMA1 d) A prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119 in a 1.8% by weight concentration.

[0304] Manufacturing Example 20 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 70.6% by weight of impact-resistant additive 4 b) 15.0% by weight of SILBOND® 600 VST (silane-treated quartz filler) available from Quarzwerke GmbH. c) 12.6% by weight of PMMA1 d) A prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119 in a 1.8% by weight concentration.

[0305] Manufacturing Example 21 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 62.3% by weight of impact-resistant additive 4 b) 25.0% by weight of Spheriglass® Potters 7010 CP-01 (glass beads) available from Potters Industries LLC. c) 11.1% by weight of PMMA1 d) A 1.6% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0306] Manufacturing Example 22 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 62.3% by weight of impact-resistant additive 4 b) 25.0% by weight of SpheriWhite® 5000 CP-01 (glass beads) available from PQ Corporation. c) 11.1% by weight of PMMA1 d) A 1.6% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0307] Manufacturing Example 23 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 62.3% by weight of impact-resistant additive 4 b) 25.0% by weight of SpheriWhite® 3000 CP-01 (glass beads) available from PQ Corporation. c) 11.1% by weight of PMMA1 d) A 1.6% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0308] Manufacturing Example 24 (Comparative Example) A single-layer foil consisting of single layer A was prepared under the same conditions as in Manufacturing Example 1. This foil had the following composition: a) 62.3% by weight of impact-resistant additive 4 b) 25.0% by weight of SpheriWhite® 3000 CP-01 (glass beads) available from PQ Corporation. c) 11.1% by weight of PMMA1 d) A 1.6% by weight prepared mixture of Tinuvin® 360, Tinuvin® 1600, and Chimassorb® 119.

[0309] Preparation of polyurethane-(meth)acrylate coating compositions Preparation of prepolymer solutions Preparation was carried out according to the procedure of Example 1 in Austrian Patent No. 404241. A glass reactor equipped with stirring blades was used. The empty reactor was heated to 70°C for 1 hour to dry the internal reactor surface area. Dry air was supplied into the reactor below the liquid level during the reaction. Subsequently, 591.3 g of dipentaerythritetraacrylate, 250.1 g of isophorone diisocyanate, 118.3 g of n-butyl acetate, 0.96 g of dibutyltin dilaurate as a catalyst, and 5.41 g of 4-methoxyphenol as a polymerization inhibitor were added to the reactor.

[0310] The reaction mixture was stirred at 60°C for approximately 4 hours until the content of free isocyanate groups was reduced to half of the initial value due to the formation of urethane bonds (determined according to DIN 53185). Next, 150.8 g of 2-ethyl-2-(hydroxymethyl)-1,3-propanediol was added to the reaction mixture, and the reaction was stirred for a further 3 hours until the isocyanate content was reduced to less than 0.5% due to the formation of further urethane bonds. The reaction mixture was cooled to room temperature, and 6.97 g of 4-methoxyphenol dissolved in 150.5 g of n-butyl acetate was added.

[0311] Preparation of the coating system 60.00 parts by weight of the above resin component solution was mixed with the following: The curing agent component is 20.00 parts by weight of Tolonate® HDT LV2 (an aliphatic polyisocyanate based on a hexamethylene diisocyanate trimer, available from Worlee-Chemie GmbH (Hamburg)). 1.20 parts by weight of tert-butylperoxybenzoate as a radical-forming agent 0.14 parts by weight of Kosmos® T12N (dibutyltin dilaurate, available from Evonik Industries AG) as a catalyst. 18.66 parts by weight of n-butyl acetate as a diluent.

[0312] Foil coating with scratch-resistant composition Test Series (a) - Application of a 60 μm thick coating layer A polyurethane (meth)acrylate coating system was applied to layer A of the foils from Production Examples 1 and 6. The thickness of coating layer D was approximately 60 μm. The resulting foils were dried at a temperature of 90°C for 4 minutes, thereby partially curing the coating.

[0313] Test Series (b) - Application of a 20-30 μm thick coating layer Further samples of the polyurethane (meth)acrylate coating composition were applied to layer A of the foils from Production Examples 1-24 and to layer B of the foil from Production Example 6. The thickness of coating layer D was approximately 20-30 μm. The resulting foils were dried at a temperature below 100°C, thereby partially curing the coating.

[0314] Preparation and testing of HPL Foils from Production Examples 1 and 6 of Test Series (a), and foils from Production Examples 1 to 24 of Test Series (b), coated as described above, were used for the preparation of HPL. HPL was prepared by co-lamination of a protective foil with a phenol resin-impregnated paper layer according to the conditions described in the specification. Layer C, if present, was in direct contact with the resin-impregnated paper layer and thereby acted as an adhesion-promoting layer. Layer A, coated with a partially cured polyurethane (meth)acrylate coating composition (layer D), formed the outer surface of the coated HPL. The core of the HPL consisted of phenol resin-impregnated paper. Melamine resin-impregnated decorative paper was placed between these and the protective foil. Anthracite-colored HPL was prepared and used for subsequent tests.

[0315] HPL samples were stored in 100°C hot water for 2 hours, or alternatively, at 65°C for 48 hours. Adhesion was then tested using a single cutting hand tool with a cross-hatch test according to ISO EN 2409 (2013).

[0316] The results of the cross-hatch test were evaluated as follows: 0 The cut edges are perfectly smooth, and not a single square in the grid is missing. 1. At the intersection of the grid lines, a small fragment of the coating is missing. The area of ​​the missing fragment does not exceed 5% of the grid area. 2. The coating is peeling off along the cutting edge and / or the intersection of the grid lines. The area of ​​peeling is greater than 5% but less than or equal to 15% of the grid area. 3. The coating is partially or completely peeled off in a wide band along the cutting edge, and / or some squares are partially or completely peeled off. The peeled area is greater than 15% but less than or equal to 35% of the cross-cut area. 4. The coating is chipped off along the edges of the cut surface in a wide strip, and / or some squares are completely or partially chipped off. The delamination area is greater than 35% but less than or equal to 65% of the cross-cut area. 5. There is some kind of delamination that can no longer be classified as characteristic 4 of the grid-like section.

[0317] The results of test series (a) are summarized in Table 2.

[0318] [Table 2]

[0319] The multilayer foil of Example 1 (an example according to the present invention) showed excellent initial adhesion and long-term durability in a humid environment. In contrast, the multilayer foil of Example 6 (a comparative example) had insufficient initial adhesion and was not used in the long-term test.

[0320] The results of test series (b) are summarized in Table 3.

[0321] [Table 3]

[0322] The multilayer foils of Examples 1, 3-5, and 9 (examples according to the present invention) and the single-layer foil of Example 18 (comparative example) showed excellent initial adhesion and long-term resistance in humid environments. However, the foil of Example 18 was brittle and difficult to handle.

[0323] The foils in Examples 11-13, 15, 16, and 21-24 (comparative examples) also exhibited excellent initial adhesion, although their long-term resistance in humid environments was insufficient.

[0324] Further testing The HPL obtained using the foil from Production Example 1 of Test Series (b) was subjected to further testing. The test results are summarized in Table 4.

[0325] [Table 4]

[0326] Therefore, multilayer foils, or Example 1, exhibited excellent chemical resistance, long-term durability in high-temperature and humid environments, and high tensile strength. [Explanation of symbols]

[0327] 1 layer A 2. Impact-resistant polyalkyl (meth)acrylate matrix 3. Silica particles 4 layer B 5 layer C 6. Coating layer D 7 Impact-resistant polyalkyl (meth)acrylate matrix 8 Adhesion promoting layer C having silica particles 9 Base material 10 Silica particles

Claims

1. A multi-layer foil having at least a layer A and a layer B, The layer A is, based on the total weight of the layer A, 0.0 to 78.0% by weight of a polyalkyl(meth)acrylate, which is a polyalkyl methacrylate, a polyalkyl acrylate, or a mixture thereof; 20.0 to 98.0% by weight of one or more particulate impact modifiers selected from core, core-shell, core-shell-shell and core-shell-shell-shell impact modifiers; 2.0 to 40.0% by weight of granular silica; an adhesion promoting copolymer, comprising, based on the weight of the adhesion promoting copolymer: (i) 70.0 to 99.5% by weight of methyl methacrylate; (ii) 0.5 to 15.0 weight percent of an adhesion promoting monomer; and (iii) 0.0 to 25.0 wt. % of a vinyl copolymerizable monomer having no functional group other than a vinyl functional group and selected from the group of vinyl aromatic monomers; 0.0 to 20.0 wt. % of an adhesion promoting copolymer comprising 0.0 to 38.0 wt.% of a fluoropolymer; 0.0 to 5.0% by weight of one or more ultraviolet absorbents; 0.0 to 5.0% by weight of one or more ultraviolet stabilizers; A molding composition comprising: the cumulative content of the polyalkyl(meth)acrylate and one or more impact modifiers in the molding composition of the layer A is at least 50% by weight, based on the weight of the layer A; The layer B is, based on the total weight of the layer B, 0.0 to 100.0% by weight of a polyalkyl(meth)acrylate, which is a polyalkyl methacrylate, a polyalkyl acrylate, or a mixture thereof; 0.0 to 95.0% by weight of one or more particulate impact modifiers selected from core, core-shell, core-shell-shell and core-shell-shell-shell impact modifiers; 0.0 to 40.0 wt.% of a fluoropolymer; 0.0 to 5.0% by weight of one or more ultraviolet absorbents; 0.0 to 5.0% by weight of one or more ultraviolet stabilizers; an adhesion promoting copolymer, comprising, based on the weight of the adhesion promoting copolymer: (i) 70.0 to 99.5% by weight of methyl methacrylate; (ii) 0.5 to 15.0 weight percent of an adhesion promoting monomer; and (iii) 0.0 to 25.0 wt. % of a vinyl copolymerizable monomer having no functional group other than a vinyl functional group and selected from the group of vinyl aromatic monomers; 0.0 to 20.0 wt. % of an adhesion promoting copolymer comprising A molding composition comprising: the cumulative content of polyalkyl (meth)acrylate and one or more impact modifiers in the molding composition of layer B is at least 50% by weight, based on the weight of layer B; The particulate silica is a precipitated silica or a pyrogenic silica; Multi-layer foil.

2. A multi-layer foil having at least a layer A and a layer B, The layer A is, based on the total weight of the layer A, 0.0 to 78.0% by weight of a polyalkyl(meth)acrylate, which is a polyalkyl methacrylate, a polyalkyl acrylate, or a mixture thereof; 20.0 to 98.0% by weight of one or more particulate impact modifiers selected from core, core-shell, core-shell-shell and core-shell-shell-shell impact modifiers; 2.0 to 40.0% by weight of granular silica; an adhesion promoting copolymer, comprising, based on the weight of the adhesion promoting copolymer: (i) 70.0 to 99.5% by weight of methyl methacrylate; (ii) 0.5 to 15.0 weight percent of an adhesion promoting monomer; and (iii) 0.0 to 25.0 wt. % of a vinyl copolymerizable monomer having no functional group other than a vinyl functional group and selected from the group of vinyl aromatic monomers; 0.0 to 20.0 wt. % of an adhesion promoting copolymer comprising 0.0 to 38.0 wt.% of a fluoropolymer; 0.0 to 5.0% by weight of one or more ultraviolet absorbents; 0.0 to 5.0% by weight of one or more ultraviolet stabilizers; A molding composition comprising: the cumulative content of the polyalkyl(meth)acrylate and one or more impact modifiers in the molding composition of the layer A is at least 50% by weight, based on the weight of the layer A; The layer B is, based on the total weight of the layer B, 40.0 to 100.0% by weight of a fluoropolymer; 0.0 to 30.0% by weight of a polyalkyl(meth)acrylate, which is a polyalkyl methacrylate, a polyalkyl acrylate, or a mixture thereof; Glass beads 0.0 to 30.0% by weight A molding composition comprising: The particulate silica is a precipitated silica or a pyrogenic silica; Multi-layer foil.

3. The content n im (wt %) of one or more impact modifiers in the foil, based on the total weight of the layer A, satisfies the following relationship: 0.01 ＊ n ｉｍ ≦n ｓｉ ≦0.4 ＊ n ｉｍ [In the formula, n ｓｉ 3. The foil according to claim 1, wherein x is the content (in %) by weight of granular silica in the foil.

4. The granular silica has a viscosity of 200 mm as measured by the BET method according to ISO 9277. ２ 4. The foil according to claim 1, having a specific surface area of ​​more than 1.0 x 10 / g.

5. 5. The foil according to claim 1, wherein the particulate silica is a hydrophilic precipitated silica or a hydrophilic pyrogenic silica.

6. The granular silica has a weight average particle diameter d of 1.0 μm to 20.0 μm as measured by a laser diffraction method in accordance with ISO 13320. ５０ 6. The foil according to claim 1, which is a precipitated silica having the formula:

7. The granular silica has a density of 0.5 SiOH / nm ２ 7. The foil according to claim 1, having a silanol group density of at least 100 .mu.m.sup.2 or more.

8. 8. The foil of claim 1, wherein the particulate silica has a DBP absorption of 100 to 500 g / 100 g, as measured according to ASTM D6854-12a.

9. 9. The foil according to claim 1, wherein the granular silica has a tap density, determined according to DIN EN ISO 787-11, of 10 g / l to 800 g / l.

10. The polyalkyl(meth)acrylate is a polymethyl methacrylate having a mass average molar mass Mw of 50,000 g / mol to 180,000 g / mol, and the polymerizable component is, based on the weight of the polymerizable composition, (a) 50.0 to 99.9% by weight of methyl methacrylate; (b) 0.1 to 50.0% by weight of an acrylic acid ester of a C1 to C4 alcohol; (c) 0.0 to 10.0% by weight of at least one further monomer copolymerizable with said monomers (a) and (b); 10. The foil according to claim 1 , which is obtainable by polymerization of a composition comprising:

11. The layer B has, based on the total weight of the layer B, 0.5 to 4.0% by weight of a benzotriazole type compound as a first ultraviolet absorber; 0.5 to 3.0% by weight of a triazine type compound as a second ultraviolet absorber; 0.2 to 2.0% by weight of a HALS type compound as an ultraviolet stabilizer 11. The foil according to claim 1, comprising:

12. the foil further comprises a layer C, the layer B being located between the layers A and C; The layer B is, based on the total weight of the layer B, 0.0 to 100.0% by weight of a polyalkyl(meth)acrylate, which is a polyalkyl methacrylate, a polyalkyl acrylate, or a mixture thereof; 0.0 to 95.0% by weight of one or more particulate impact modifiers selected from core, core-shell, core-shell-shell and core-shell-shell-shell impact modifiers; 0.0 to 40.0 wt.% of a fluoropolymer; 0.0 to 5.0% by weight of one or more ultraviolet absorbents; 0.0 to 5.0% by weight of one or more ultraviolet stabilizers; A molding composition comprising: The layer C is 0.0 to 78.0% by weight of a polyalkyl(meth)acrylate, which is a polyalkyl methacrylate, a polyalkyl acrylate, or a mixture thereof; 20.0 to 98.0% by weight of one or more particulate impact modifiers selected from core, core-shell, core-shell-shell and core-shell-shell-shell impact modifiers; 0.0 to 40.0% by weight of granular silica; an adhesion promoting copolymer, comprising, based on the weight of the adhesion promoting copolymer: (i) 70.0 to 99.5% by weight of methyl methacrylate; (ii) 0.5 to 15.0 weight percent of an adhesion promoting monomer; and (iii) 0.0 to 25.0 wt. % of a vinyl copolymerizable monomer having no functional group other than a vinyl functional group and selected from the group of vinyl aromatic monomers; 0.0 to 40.0 wt. % of an adhesion promoting copolymer comprising 0.0 to 5.0% by weight of one or more ultraviolet absorbents; 0.0 to 5.0% by weight of one or more ultraviolet stabilizers; A molding composition comprising: the cumulative content of the polyalkyl(meth)acrylate and one or more impact modifiers in the molding composition of layer C is at least 50% by weight, based on the weight of layer C; 12. The foil of claim 1, wherein the cumulative content of said particulate silica and said adhesion-promoting copolymer is at least 2.0% by weight, based on the weight of said layer C, and said particulate silica is precipitated silica or pyrogenic silica.

13. The foil further comprises a layer C, the layer C comprising, based on the total weight of the layer C: 40.0 to 100.0% by weight of a fluoropolymer; 0.0 to 30.0% by weight of polyalkyl(meth)acrylate; Glass beads 0.0 to 30.0% by weight 12. The foil according to claim 1, which consists of a molding composition comprising:

14. The layer A has a thickness of 1.0 μm to 30.0 μm, The layer B has a thickness of 15.0 μm to 150.0 μm, The foil of any one of claims 1 and 3 to 13, wherein layer C, if present, has a thickness of 1.0 μm to 30.0 μm.

15. 15. The foil according to any one of claims 1, 3 to 12 and 14, further comprising a coating layer D adjacent to layer A, said coating layer D comprising an at least partially crosslinked material selected from crosslinked polyurethanes, crosslinked polyurethane (meth)acrylates, crosslinked poly(meth)acrylates or mixtures thereof.

16. 16. A multi-layer article having an outer surface comprising a substrate at least partially covered by a foil according to any one of claims 1, 3 to 12, 14 and 15, comprising, starting from the outer surface of said multi-layer article, a process for applying, in the following order: - layer D, if present, forming the outer surface of said multi-layer article - Layer A layer B; and Layer C, if present A multi-layer article comprising:

17. A multi-layer article comprising a substrate at least partially covered by a foil according to any one of claims 1 to 15, the multi-layer article being characterized in that, starting from the outer surface, the foil is applied in the following order: - Optionally layer C layer B; and - Layer A A multi-layer article comprising:

18. 18. A method for producing a multilayer article according to claim 16 or 17, comprising the step of coating a substrate with a foil according to any one of claims 1 to 15 by coextrusion, lamination or extrusion lamination, wherein the at least partially crosslinked material of the coating layer D, if present, is subjected to further crosslinking.

19. The method of claim 18, wherein the multilayer article is a high pressure laminate and the step of coating a substrate with the foil of any one of claims 1 to 15 is carried out at a pressure of 1 MPa to 20 MPa and at a temperature of 120°C to 220°C.

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