Film, film-coated object and method for producing a film-coated object

Abstract

The invention relates to a film, a film-coated object and a method for producing a film-coated object. The film comprises at least one adhesion-promoting layer. The film also comprises a protective layer (14) and / or a carrier layer (11). The adhesion-promoting layer (16) is designed for the application of polyurethane. The film-coated object also comprises a polyurethane layer (P) overmoulded onto the adhesion-promoting layer (16).

Description

[0001] LEONHARD KURZ Foundation & Co. KG, Schwabacher Str. 482, 90763 Fürth

[0002] Film, film-coated article and method for producing a film-coated article

[0003] The invention relates to a film, a film-coated article and a method for producing a film-coated article.

[0004] Film-coated articles are known in the art as injection-molded articles.

[0005] For example, DE 10221482 C1 discloses a device for producing a molded part from a curing injection-molding material, which is decorated during injection molding using the IMD process (IMD = In-Mold Decoration) with an embossed foil comprising a carrier film and a decorative layer that can be detached from the carrier layer. The embossed foil is inserted into an open injection mold, with the decorative layer of the embossed foil facing an upper mold part. The injection mold is closed, and liquid injection-molding material is injected through an injection channel into the cavity of the injection mold, with the embossed foil adhering to the visible side of the molded part. The embossed foil, with its decorative layer, bonds with the injection-molding material, which is removed from the injection mold after curing. After the carrier film is removed from the decorative layer, the decorated molded part is finished.Such decorated injection-molded articles are used in particular for automotive interior parts such as door strips, strips in instrument panels, gear lever covers and center console covers, for automotive exterior parts such as door sill protection strips and covers on A, B and C pillars, in the audio and video sector for decorative strips on the housings of radio and television sets, and in the telecommunications sector for housing shells of mobile devices such as cell phones or navigation devices.

[0006] Insert molding (IM) is a combined process of hot stamping, vacuum forming, and casting, particularly injection molding. Compared to the IMD process, insert molding offers the possibility of more pronounced deformation of the film. This is advantageous when, for example, highly profiled and shaped parts are required. First, a vacuum-formable, thin hot stamping film is hot stamped onto a carrier, e.g., an ABS film (thickness approximately between 200 μm and 750 μm) (ABS = acrylonitrile butadiene styrene). This hot-stamped carrier is vacuum-formed under heat. The vacuum-formed layers of hot stamping foil and carrier form the so-called "insert" and are cut or punched to precise contours. The insert is positioned in an injection mold, the mold is filled with plastic (the insert is back-injected), then the decorated injection-molded article is removed from the injection mold.

[0007] The flooding of objects, such as injection-molded articles, using polyurethane (PU) is also known from the prior art. For this purpose, an object to be coated is positioned in a tool that has two tool halves. A first tool half accommodates the object to be coated, and a second tool half forms a slightly larger cavity than the object to be coated. PU is introduced into this space, and the object to be coated is flooded with PU. Two-component PU systems (2K-PU) are also known; they cure within seconds of the components being mixed before and / or immediately during flooding. When the tool opens, the PU is already sufficiently hard.The international patent application WO 2019 / 034361 A2 discloses a film-coated article produced by injection molding with a thermoplastic material, in which a surface protection is additionally applied to the film coating by flooding with polyurethane.

[0008] The production of the familiar foil-coated article requires two separate production units. This makes production relatively complex, time-consuming, and expensive.

[0009] The invention is based on the object of eliminating the disadvantages of the prior art. In particular, it is intended to provide a simple and inexpensive process for producing a film-coated article, as well as a film suitable for this process and a corresponding film-coated article. The film-coated article should, in particular, exhibit high quality and surface finish.

[0010] According to the invention, this object is achieved by a film according to the subject matter of claim 1, by a film-coated article according to the subject matter of claim 14, and by a method according to the subject matter of claim 26. Advantageous embodiments of the invention are specified in the dependent claims.

[0011] According to the invention, a film for coating with polyurethane, in particular for flooding with polyurethane, is claimed. The film comprises at least one adhesion promoter layer. Additionally, the film comprises a protective layer and / or a carrier layer. The adhesion promoter layer is designed for the deposition of polyurethane.

[0012] The film preferably comprises several adhesion promoter layers, particularly preferably two or three adhesion promoter layers. The several adhesion promoter layers preferably follow one another directly. In other words, the adhesion promoter layer is preferably composed of several layers.

[0013] The adhesion promoter layer can be single-layered or multi-layered. Particularly preferably, the adhesion promoter layer is two-layered or three-layered.

[0014] For linguistic simplicity, the term "adhesion promoter layer" is used in the present application, particularly in the singular. The term "adhesion promoter layer" can also be interpreted to mean that there are actually several adhesion promoter layers or that the adhesion promoter layer is multilayered.

[0015] In the present application, the term "protective layer" refers in particular to a layer that protects against chemical and / or mechanical influences, particularly external influences. A protective layer preferably forms an outer layer of the film and / or the transfer layer.

[0016] According to an advantageous embodiment of the invention, the film comprises at least one decorative layer. The adhesion promoter layer is arranged on the side of the at least one decorative layer facing away from the protective layer and / or the carrier layer.

[0017] According to a further advantageous embodiment of the invention, the film is a transfer film. The transfer film comprises a carrier layer and a transfer layer arranged on the carrier layer. The transfer layer comprises the at least one decorative layer, the protective layer, and the adhesion promoter layer. The carrier layer is arranged on the side of the at least one decorative layer facing away from the adhesion promoter layer. The carrier layer comprises the carrier layer.

[0018] The carrier layer preferably has a layer thickness of between 10 pm and 100 pm, preferably from 23 pm to 75 pm.

[0019] The carrier layer can preferably be formed as a continuous film or as a single film sheet or as a film sheet. Such a film sheet or film sheet can be obtained from a previously existing continuous film by separating it.

[0020] Preferably, when the film is designed as a transfer film, the carrier layer is removed again during the production of the film-coated article.

[0021] The protective layer can be formed from a protective lacquer. The protective layer preferably has a layer thickness of between 0.1 μm and 20 μm, preferably between 1 μm and 3 μm.

[0022] According to a further advantageous embodiment of the invention, the carrier layer additionally comprises a release layer. The release layer preferably has a layer thickness of 0.1 nm to 50 nm. The release layer is arranged on the side of the carrier layer facing the transfer layer. The release layer preferably comprises or consists of at least one wax. The release layer can additionally or alternatively comprise or consist of one or more polymers. After removal of the carrier layer from the film, the release layer can be arranged completely or partially on the transfer layer and / or completely or partially on the carrier layer. According to the invention, the film-coated article comprises a film according to the invention, or the transfer layer of the film according to the invention configured as a transfer film, and a polyurethane layer cast onto the adhesion promoter layer.Preferably, the polyurethane layer is cast or flooded by flooding the film with polyurethane.

[0023] The polyurethane layer may be a solvent-containing and polyurethane-containing composition and in particular comprises several components, individually or in combination selected from polyol, isocyanate, catalyst, release agent, additive.

[0024] The film-coated article is preferably dimensionally stable.

[0025] According to the invention, the method for producing a film-coated article, preferably for producing the film-coated article according to the invention, comprises the following steps, in particular in the following order: a) providing a film according to the invention, b) providing a mold cavity, c) introducing the film into the mold cavity, d) providing a polyurethane-forming mixture at a mixing head, e) injecting the mixture into the mold cavity so that the film is at least partially flooded and / or poured over by the mixture on its side delimited by the adhesion promoter layer, f) obtaining the film-coated article.

[0026] In the present application, the term "region" is understood in particular to mean a defined area of ​​a layer or film or ply in the plane formed by the respective layer and / or film and / or ply. For example, the polyurethane layer has at least a first region and at least one second region, wherein each of the two or more regions occupies a defined area in the plane formed by the polyurethane layer. Accordingly, the adhesion promoter layer can have at least a first region and at least one second region, wherein each of the two or more regions occupies a defined area in the plane formed by the adhesion promoter layer.Accordingly, the at least one decorative layer can have at least one first region and at least one second region, wherein each of the two or more regions occupies a defined area in the plane formed by the at least one decorative layer. The respective layers, films, or plies preferably extend parallel to one another. In particular, the adhesion promoter layer preferably extends parallel to the at least one decorative layer. The adhesion promoter layer preferably extends parallel to the polyurethane layer.

[0027] In the present application, the term “regionally” is preferably understood in the same way as described above for the term “region”.

[0028] In the present application, the areal extent of a layer, film, or ply is preferably understood to mean the extent of the plane formed by the respective layer, film, and / or ply. The areal extent of the respective layer, film, and / or ply includes, in particular, a longitudinal and / or transverse extent of the respective layer, film, and / or ply.

[0029] The term “mold cavity 1can be understood in two different ways in the present application. A mold cavity can be designed as a tool or formed in a tool in order to form a cavity or a cavity corresponding to a desired shape of the film-coated article. This cavity is filled by flooding or flooding with the polyurethane-forming mixture. After crosslinking of the polyurethane, the desired shape of the film-coated article is formed in a mechanically stable manner and the film-coated article can be removed from the cavity. If the term "mold cavity" is to be understood specifically in one of the two ways, reference is made, for example, to the "tool forming the mold cavity" or to the "cavity formed by the mold cavity".

[0030] The term “curing” or “hardening” preferably refers to the transition from a liquid or plastically deformable state to a solid state of a substance or mixture of substances under standard conditions (temperature: 25°C, pressure: 1013 mbar).

[0031] The process of curing or hardening can preferably be carried out by cooling, ie by reducing the temperature below the freezing point and / or below the glass transition temperature of a substance or mixture of substances and / or by physical drying, ie by removing at least one liquid component, for example solvent, and / or by chemical reaction, for example by chain polymerization, polyaddition and / or polycondensation.

[0032] The term “polymeric component and / or precursor thereof” is preferably understood to mean a substance or mixture of substances which comprises at least one, preferably organic, polymer and / or at least one precursor thereof.

[0033] The term "polymer" preferably refers to a substance composed of preferably at least 10 structural units, so-called constitutional repeating units, which may be identical or different from one another and which form at least one organic polymer through chemical reaction, preferably chain polymerization, polyaddition, and / or polycondensation. A constitutional repeating unit (CRU) is preferably the smallest repeating group of atoms within a polymer.

[0034] A polymer within the meaning of the invention can be unbranched or branched.

[0035] The term “precursor of a polymeric component” preferably refers to monomers or monomer mixtures as well as oligomers and mixtures thereof, which can each combine to form the corresponding unbranched or branched polymer, preferably by chemical reaction, more preferably chain polymerization, polyaddition and / or polycondensation.

[0036] The term “reactive functional group” is preferably understood to mean a functional group which can participate in the formation of the corresponding unbranched or branched polymer by chemical reaction, more preferably chain polymerization, polyaddition and / or polycondensation.

[0037] Monomers or monomer mixtures within the meaning of the invention are preferably low-molecular-weight, reactive molecules or mixtures of reactive molecules that can each combine to form the corresponding unbranched or branched polymer by chemical reaction, more preferably chain polymerization, polyaddition, and / or polycondensation, thereby forming a constitutional repeating unit of the polymer. A reactive molecule, for example, a monomer, oligomer, and optionally a polymer, preferably has at least one reactive functional group.

[0038] The term “oligomer” is preferably understood to mean a substance which is composed of preferably 2 to 9 constitutional repeating units which may be the same or different from one another and which may combine to form an unbranched or branched polymer, preferably by chemical reaction, more preferably chain polymerization, polyaddition and / or polycondensation.

[0039] The term “cured polymeric component” preferably refers to a polymeric substance or a mixture of polymeric substances which has a solid state under standard conditions (temperature: 25°C, pressure: 1013 mbar) and is preferably not plastically deformable.

[0040] In step c), the film is preferably introduced into the mold cavity in such a way that the adhesion promoter layer faces the cavity formed by the mold cavity, in particular that the adhesion promoter layer directly adjoins the cavity formed by the mold cavity.

[0041] In step d), components of the polyurethane-forming mixture are preferably mixed together at the mixing head. The mixture provided in step d) is preferably flowable. The mixture can be a solvent-containing and polyurethane-containing composition. The components preferably comprise at least one polyol and one isocyanate.

[0042] The mixture provided in step d) is formed in particular from a polyol and an isocyanate and preferably contains further chemical additives.

[0043] In other words, the polyurethane-forming mixture can be a solvent-containing and polyurethane-containing composition and in particular comprise several components, selected individually or in combination from polyol, isocyanate, catalyst, release agent, and additive. Preferably, a chemical reaction starts when the mixture is provided in step d). The chemical reaction is preferably an exothermic reaction. Furthermore, the chemical reaction is preferably a crosslinking reaction, in which molecular polymer chains are preferably formed. Crosslinks are preferably formed between the polymer chains. Polyurethane is preferably formed during the crosslinking reaction. Preferably, step d) takes place immediately before step e), i.e., the components forming the mixture are mixed with one another immediately before injection into the mold cavity.

[0044] In particular, the chemical reaction begins by mixing the two polyurethane-forming components, polyol and isocyanate. Preferably, a crosslinking reaction occurs, forming the molecular polymer chains. The crosslinking reaction is preferably exothermic. Preferably, the polyol and isocyanate components remain separate before the mixing process and are only combined immediately before injection into the mold cavity according to step e). This prevents a premature chemical reaction. This advantageously allows the rheological flow properties of the mixture to be maintained for injection into the mold cavity in step e).

[0045] The mixture is preferably thin-bodied when injected into the mold cavity in step e). Preferably, the viscosity at the start of injection into the mold cavity according to step e) is in a range between 100 mPas and 300 mPas, preferably 120 mPas and 200 mPas, at a mixture temperature of 40°C to 100°C, preferably at a mixture temperature of 50°C to 75°C, particularly preferably at a mixture temperature of 60°C to 70°C.

[0046] Preferably, the viscosity of the mixture and / or the resulting polyurethane layer increases as the chemical crosslinking reaction progresses until the end of the chemical reaction. Preferably, the mixture and / or the resulting polyurethane layer cures as the chemical crosslinking reaction progresses. Preferably, a fully cured polyurethane layer is formed at the end of the chemical reaction.

[0047] The mixture provided in step d) preferably comprises reactive groups. Particularly preferably, the mixture provided in step d) comprises at least two reactive groups, preferably three or more reactive groups.

[0048] Preferably, the respective components of the mixture each have at least two reactive groups, preferably three or more reactive groups. In particular, the polyol preferably has at least two reactive groups, preferably three or more reactive groups. Furthermore, the isocyanate preferably has at least two reactive groups, preferably three or more reactive groups.

[0049] The reactive groups may preferably be free reactive groups and / or capped reactive groups which release the corresponding reactive group at a temperature in the range of 30°C to 180°C.

[0050] The presence of three or more reactive groups preferably enables the formation of cross-links to form the polyurethane layer.

[0051] Preferably, in step e), the adhesion promoter layer is directly flooded and / or poured over with the mixture. The adhesion promoter layer can be flooded and / or poured over only in certain areas. Preferably, in step e), the film is completely flooded and / or poured over with the mixture on the side bordered by the adhesion promoter layer.

[0052] The term "flooding" in the context of this application can mean overflooding, underflooding, flooding, and / or flooding around. Thus, different orientations of the film in the mold cavity are possible. In this case, the film is covered by the mixture, at least in part, on the side bordered by the adhesion promoter layer. For linguistic simplification, the term "flooding" is used in particular below. The above-mentioned meanings can be interpreted as meanings.

[0053] The polyurethane layer is preferably applied to the adhesion promoter layer in step e) by at least partially flooding and / or pouring over the film on its side delimited by the adhesion promoter layer with at least one solvent-containing, preferably flowable, polyurethane-containing composition and subsequent curing.

[0054] The term “flowable polyurethane-containing composition” is preferably understood to mean a polyurethane-containing composition which preferably has a dynamic viscosity in a range from 2 mPas to 1500 mPas, preferably from 10 mPas to 1000 mPas, more preferably from 10 mPas to 500 mPas, at a temperature of 25°C, preferably determined according to the method described in DIN EN ISO 3219:1994-10, for example using a HAAKE Viscotester® VT550, more preferably using a cylinder measuring device NV and a measuring cup NV.

[0055] As described above, the at least one solvent-containing, preferably flowable, polyurethane-containing composition preferably also comprises free, reactive groups, preferably free isocyanate groups or free groups reactive towards isocyanate groups, and / or corresponding capped, reactive groups which release the corresponding reactive group again at a temperature in a range from 30°C to 180°C.

[0056] During the curing, preferably complete curing, of the adhesion promoter layer, which is at least partially not yet completely cured, and / or the polyurethane layer applied thereon, free isocyanate groups contained in the adhesion promoter layer can therefore, for example, react with free groups reactive towards isocyanate groups of the solvent-containing, preferably flowable, polyurethane-containing composition used to produce the polyurethane layer.

[0057] As a result, the adhesion of the polyurethane layer to the adhesion promoter layer after curing according to the method according to the invention, preferably according to step h), is preferably significantly improved.

[0058] More preferably, the at least one solvent-containing, preferably flowable, polyurethane-containing composition is selected from the group consisting of polyurethane-containing dispersions, polyurethane-containing resins, polyurethane solutions, compositions of polyurethane precursors (2K-PLIR systems) and mixtures thereof, which preferably also have free, reactive groups, preferably isocyanate groups or groups reactive towards isocyanate groups and / or in each case corresponding capped, reactive groups which release the corresponding reactive group again at a temperature in a range from 30°C to 180°C.

[0059] For example, the at least one solvent-containing, preferably flowable, polyurethane-containing composition as described above can be applied to the adhesion promoter layer as compositions of polyurethane precursors (2K-PLIR systems), in particular as a mixture of at least one of the aforementioned compounds having two or more isocyanate groups and at least one of the aforementioned compounds having two or more groups reactive towards isocyanate groups, wherein preferably either the at least one compound having two or more isocyanate groups or the at least one compound having two or more groups reactive towards isocyanate groups is used in molar excess.

[0060] For example, polyurethane-containing dispersions, polyurethane-containing resins and / or polyurethane solutions comprise the aforementioned prepolymers with free groups reactive towards isocyanate groups, which may be crosslinked or uncrosslinked, the aforementioned prepolymers with capped groups reactive towards isocyanate groups, which may be crosslinked or uncrosslinked, or mixtures thereof and / or the aforementioned isocyanate prepolymers, which may be crosslinked or uncrosslinked, the aforementioned capped isocyanate prepolymers, which may be crosslinked or uncrosslinked, or mixtures thereof.

[0061] More preferably, the at least one solvent-containing, preferably flowable, polyurethane-containing composition used to produce the polyurethane layer comprises at least one organic solvent, for example ethyl acetate, 2-butanone, acetone, toluene, xylenes or mixtures thereof.

[0062] Further preferably, at least one solvent-containing, preferably flowable, polyurethane-containing composition used to produce the polyurethane layer, which comprises the aforementioned isocyanate prepolymers, is anhydrous. The aforementioned capped isocyanate prepolymers, however, can be present as an aqueous dispersion. Further preferably, at least one solvent-containing, preferably flowable, polyurethane-containing composition used to produce the polyurethane layer, which comprises the aforementioned prepolymers with free groups reactive toward isocyanate groups, which may be crosslinked or uncrosslinked, the aforementioned prepolymers with capped groups reactive toward isocyanate groups, which may be crosslinked or uncrosslinked, or mixtures thereof, water and / or at least one organic solvent, for example ethyl acetate, 2-butanone, acetone, toluene, xylenes, or mixtures thereof.

[0063] When using 2K PLIR systems, the polyurethane precursors, for example, polyol-containing and isocyanate-containing components, are preferably stored separately and only brought together in the mixing head when required. The reaction heat generated during the reaction of the polyurethane precursors preferably leads to heating to a temperature of 60°C to 180°C, preferably 80°C to 120°C.

[0064] The surfaces or walls of the mold cavity may also preferably have a temperature in a range from 40°C to 160°C, preferably in a range from 80°C to 120°C.

[0065] Preferably, in one embodiment, the polyurethane layer can be applied to the at least one adhesion promoter layer in step e) by open flooding or flooding in a casting tool.

[0066] In open flooding, the surface tension of the at least one solvent-based, preferably flowable, polyurethane-containing composition used to produce the polyurethane layer is preferably utilized in the outer edge region of the component to be flooded. The polyurethane layer is flooded onto the component without a mold that defines the contours of the tool. Curing is preferably achieved by appropriate storage of the flooded component, preferably for a period of 2 s to 60 s, at a temperature in the range of 20°C to 100°C.

[0067] When flooding in a casting tool, the entire process takes place in a closed tool, which defines the area to be flooded as a cavity.

[0068] The filling of the at least one solvent-containing, preferably flowable, polyurethane-containing composition used to produce the polyurethane layer is preferably carried out via a mixing head, preferably at a pressure of less than 10 bar.

[0069] A first curing phase can be initiated by applying heat to the mold, for example at a temperature of 60°C to 160°C, preferably for a period of 60 s to 600 s.

[0070] After removing the casting tool, the component is preferably stored for approximately 24 hours before further use for residual curing.

[0071] During the curing, preferably complete curing, of the adhesion promoter layer, which is at least partially not yet completely cured, and the polyurethane layer applied thereon, free isocyanate groups contained in the adhesion promoter layer can, for example, react with free groups reactive towards isocyanate groups of the solvent-containing, preferably flowable, polyurethane-containing composition used to produce the polyurethane layer.

[0072] Preferably, a layer is referred to as “cured” in the sense of the present invention when the polymer components capable of crosslinking, preferably binders, for example free isocyanate

[0073] Groups and / or free isocyanate-reactive

[0074] Groups of the respective layer have more than 95% networking.

[0075] Preferably, before and / or during and / or after the application of the polyurethane layer in step e), the polyurethane layer can be modified and / or structured, preferably by inserting / placing particles onto the adhesion promoter layer after step c) and / or by using tool structures during the application in step e) and / or by subsequently processing the polyurethane layer by means of process steps selected individually or in combination from laser processing, overprinting, hot stamping, cold stamping, blind stamping, mechanical processing.

[0076] In particular, by means of laser processing and / or mechanical processing and / or the use of tool structures, it is possible to create exposed relief structures in the polyurethane layer with a minimum line width and / or a minimum laserable dot diameter of 5 pm to 150 pm, preferably 10 pm to 100 pm. This allows the finest details, particularly for motifs and / or alphanumeric information, to be produced. It is also possible to combine such fine structures with coarser, macroscopic structures, either in a laterally adjacent combination or as an overlay of a coarse structure with a fine structure.This can be achieved in particular by combining several of the above-mentioned process steps, for example to produce coarse structures with dimensions of the individual structural elements of 0.5 mm to 50 mm in combination with laser processing and / or mechanical processing adjacent thereto and / or superimposed thereon with a minimum line thickness and / or a minimum laserable spot diameter of 5 pm to 150 pm, preferably 10 pm to 100 pm. However, it is also possible for coarse structures and fine structures to be present together as a tool structure and thus molded into the polyurethane layer. The depth of the relief structures can be between 1 pm and the maximum wall thickness of the polyurethane layer, in particular between 1 pm and 30 mm, preferably between 1 pm and 15 mm.

[0077] Preferably, a modification of the polyurethane layer and / or the adhesion promoter layer can take place in register with design features and / or motifs already present in the transfer layer and / or in the decorative layer. For example, a surface structure can be arranged in register with a wood grain, in particular of the decorative layer, and / or a tactile and / or visually perceptible structure can be arranged in register with a motif, in particular of the decorative layer. The aforementioned structures can, for example, be produced individually or multiple times by means of process steps or in combination selected from the use of tool structures during application in step e), laser processing, overprinting, overembossing, and mechanical processing.

[0078] Accurate registration refers to the positioning accuracy of two or more layers, elements, areas and / or layers relative to one another. The registration accuracy should be within a specified tolerance and as small as possible. At the same time, the registration accuracy of several layers, elements, areas and / or layers relative to one another is an important feature for increasing process reliability and / or product quality, as well as protection against counterfeiting. Accurate positioning can be achieved in particular using sensory, preferably optically detectable, register marks. These register marks can either represent special separate layers, elements, areas and / or layers or can themselves be part of the layers, elements, areas and / or layers to be positioned.A polyurethane layer produced by the process according to the invention preferably has transparent or reduced light-transmitting properties.

[0079] Preferably, the method comprises the further following step or step f) comprises the further following sub-step: g) removing the film-coated article from the mold cavity.

[0080] The process according to the invention advantageously allows components to be produced without the use of thermoplastic materials and without the use of an injection molding process with the required production unit. This reduces both investment costs and operating costs. Furthermore, switching between the separate production units for the injection molding process and the polyurethane flooding process is eliminated. This makes the process according to the invention simple and fast compared to the prior art. This allows film-coated articles to be manufactured particularly cost-effectively.

[0081] Furthermore, thermoplastic materials shrink upon cooling. This makes special geometries impossible to achieve with thermoplastic materials. In particular, with thermoplastic materials there is a risk that shrinkage will cause geometric distortions and / or sink marks and / or shrinkage cavities. The term “shrinkage cavities” refers to gas-free cavities inside a molded part. In addition, thermoplastic materials have a high viscosity. Therefore, thermoplastic materials cannot precisely follow complex geometries during injection. In contrast, polyurethane is not thermoplastic, but a reaction product with an initially very low viscosity. Therefore, polyurethane can mold complex geometries. The process according to the invention can therefore advantageously be used particularly flexibly with regard to special geometric specifications. Film-coated articles with complex geometries can be produced.These geometries can, for example, include abrupt or continuous cross-sectional changes, in particular tapers, corners, edges, points, and / or arches. In particular, the film-coated articles can have particularly thick walls and / or abrupt changes in wall thickness. Compared to injection molding with thermoplastic materials, very little and / or very few geometric distortions and / or sink marks and / or cavities occur. The film-coated articles according to the invention therefore advantageously exhibit high optical quality.

[0082] Furthermore, the use of both thermoplastic materials and polyurethane in the production of a specific component can lead to tooling and / or process-related difficulties due to the different shrinkage properties of the different materials. Such difficulties can be avoided by using only polyurethane.

[0083] Advantageously, lower temperatures are required to form the polyurethane layer than when using thermoplastic materials in the injection molding process. Furthermore, the mixture introduced into the mold cavity in step e) is advantageously heated by an exothermic reaction. Depending on the current temporal phase of the exothermic reaction, it is advantageous to temper the mixture, in particular to heat it up or cool it down, so that the exothermic reaction takes place at a roughly constant process temperature. At the beginning of the exothermic reaction, the mixture is therefore heated or cooled by the then prevailing mold temperature, which is higher than the mixture temperature.As the exothermic reaction progresses, with increasing thermal energy released, the largely constant mold temperature leads to a cooling of the mixture, which is heated by the reaction, because the mold temperature is then temporarily below the mixture temperature influenced by the exothermic reaction. The mold temperature remains largely constant during the exothermic reaction.

[0084] Advantageously, lower cavity pressures are still required than in the injection molding process of thermoplastic materials.

[0085] The decoration process using a transfer film, i.e., a lacquer transfer technology, enables a significantly greater design variety compared to other decoration processes such as wet painting, allowing the creation of individual images, technical designs, tactile surfaces, and many other design variations. Decoration using transfer film makes it possible to dispense with one or more subsequent process steps following decoration, such as separate overprinting or lasering of lettering, symbols, etc. This, in turn, advantageously saves decoration costs. A transfer film could incorporate all of these decorative elements, such as decorative printing, negative decorations such as lettering or symbols, etc., already in the layer structure of the transfer layer.

[0086] Further advantageous embodiments of the invention are described in the subclaims.

[0087] According to a further advantageous embodiment of the invention, the film is a label or a print-mold-design sheet (PMD sheet) or an insert.

[0088] The embodiments of the invention as a label, as a PMD sheet, and as an insert are typically products made of or with a carrier layer. The carrier layer can also be called backing material. The carrier layer can consist, for example, of materials selected individually or in combination from ABS, PC, PC-ABS, PMMA, TPE (TPE = thermoplastic elastomer). A decoration and / or information can then be applied to the carrier layer in one or more layers on the front and / or back using processes such as printing, casting, spraying, or laser processes.

[0089] The carrier layer of a label is usually a sheet material. The decoration and / or information can be applied to the carrier layer, for example, by direct printing using screen printing, flexographic printing, gravure printing, or digital printing, as well as by a lamination process and / or the application of a transfer film. A label is usually a two-dimensional printed sheet that is bonded to the plastic material, for example, during injection molding. The layer thickness of the label is preferably between 20 μm and 1000 μm, preferably between 100 μm and 750 μm.

[0090] In PMD technology, the carrier layer is usually available as a sheet material. The application of the decoration and / or information to the carrier layer is carried out in particular by direct printing using screen printing, flexographic printing, gravure printing, or digital printing. Transparent backing materials are preferably used in the PMD process. Due to this fact, it is also possible, among other things, to coat the sheet on the front and back. The coated carrier layer is preferably pre-formed in a forming process, subsequently trimmed and / or lasered along the outer contours to obtain a clean contour and then combined with a plastic material, in particular back-injected, for example in an injection mold. The layer thickness of the PMD sheet is preferably between 20 μm and 1000 μm, more preferably from 100 μm to 750 μm. In insert molding technology, the carrier layer is preferably available as roll material.The decoration and / or information is applied to the backing material (carrier layer) primarily by applying a transfer film and / or by direct printing using screen printing, flexographic printing, gravure printing, or digital printing. The coated carrier layer is fed from a roll into a deep-drawing tool and preformed in a forming process. It is then separated into individual panels. The outer contours are then trimmed and / or lasered to achieve a clean outline. The label is then bonded, in particular back-injected, to a plastic material in an injection mold. The layer thickness of the label is preferably between 20 μm and 1000 μm, preferably between 100 μm and 750 μm.

[0091] The carrier layer is preferably formed from a material selected from the group consisting of polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polycarbonate (PC), acrylonitrile butadiene styrene polycarbonate (ABS-PC), polypropylene (PP) and mixtures thereof.

[0092] If the film is designed as a label, PMD sheet, or insert, the carrier layer can also serve as a protective layer. The carrier layer can form a protective layer on the reverse side of the film-coated article, i.e., a protective layer on the side of the film-coated article facing away from the polyurethane layer.

[0093] According to a further advantageous embodiment of the invention, the adhesion promoter layer is preferably applied directly or indirectly to the decorative layer over the entire surface and / or in certain regions by means of a printing method selected individually or in combination from screen printing, flexographic printing, gravure printing, or inkjet printing. Particularly preferably, the adhesion promoter layer is applied directly or indirectly to the decorative layer over the entire surface and / or in certain regions by means of gravure printing.

[0094] According to a further advantageous embodiment of the invention, the adhesion promoter layer comprises at least one binder selected from the group consisting of polyurethane resins, polyurethane dispersions, acrylic resins, methacrylic resins, phenolic resins, epoxy resins, polyureas, melamine resins, aminoplasts, polyester resins, alkyd resins, polyamide resins, vinyl ester resins and mixtures thereof, preferably polyurethane resins, polyurethane dispersions, phenolic resins, epoxy resins, polyureas, melamine resins, aminoplasts, polyester resins, alkyd resins, polyamide resins and mixtures thereof.

[0095] More preferably, the adhesion promoter layer is not yet fully cured, at least in some areas, and the adhesion promoter layer comprises the at least one binder which has free isocyanate groups and / or free groups reactive towards isocyanate groups, preferably amino groups and / or hydroxyl groups, and / or correspondingly capped analogues thereof, in a proportion of at least 15 wt.% (wt.% = weight percent), preferably from a range of 20 wt.% to 90 wt.%, in each case based on the total weight of the layer.

[0096] The following concrete example can be cited: The adhesion promoter layer is, for example, a mixture of acrylic resin with free OH and / or acid groups and at least one suitable crosslinking agent with a reactive group, for example, a polyfunctional aziridine (PFA) or polyisocyanate. This adhesion promoter layer may be in an incompletely cured state and may undergo a chemical reaction under the reactive conditions during flooding with, for example, polyol or polyisocyanates.

[0097] According to a further advantageous embodiment of the invention, the adhesion promoter layer is designed in such a way that a chemical bond with the polyurethane to be deposited can be established through the adhesion promoter layer.

[0098] In other words, the adhesion promoter layer can be designed in such a way that the adhesion promoter layer reacts chemically with the polyurethane to be deposited.

[0099] The adhesion promoter layer can therefore be designed in such a way that at least one chemical bond with the polyurethane to be deposited can be formed through the adhesion promoter layer.

[0100] In particular, the adhesion promoter layer is designed in such a way that the adhesion promoter layer bonds essentially or exclusively to the polyurethane to be deposited by means of chemical bonds.

[0101] Preferably, the adhesion promoter layer is designed such that at least one covalent bond and / or at least one ionic bond with the polyurethane to be deposited can be formed through the adhesion promoter layer.

[0102] Preferably, the adhesion promoter layer is designed such that the adhesion promoter layer bonds to the polyurethane to be deposited essentially or exclusively by means of covalent bonds and ionic bonds.

[0103] Particularly preferably, the adhesion promoter layer is designed such that it bonds to the polyurethane to be deposited essentially or exclusively by means of covalent bonds. The adhesion promoter layer preferably comprises free, reactive groups and / or capped, reactive groups that release the corresponding reactive group at a temperature in the range of 30°C to 180°C. The term "free, reactive group" preferably refers to a functional group that can form a covalent bond during a polymerization reaction.

[0104] Suitable reactive groups are preferably isocyanate groups (-NCO) and / or groups reactive toward isocyanate groups, preferably amino groups (-NH2) and / or hydroxyl groups (-OH). Capped reactive groups, which can also be referred to as blocked reactive groups, are preferably addition compounds of blocking agents and the aforementioned reactive groups, which release the corresponding reactive group at a temperature in the range from 30°C to 180°C, preferably at a temperature in the range from 40°C to 160°C, more preferably at a temperature in the range from 60°C to 140°C.

[0105] Capped, reactive groups are preferably capped isocyanate groups which release the corresponding reactive group, preferably isocyanate group, at a temperature in the range of 30°C to 180°C.

[0106] For example, the adhesion promoter layer can contain free, reactive isocyanate groups. Free, reactive isocyanate groups can react in the presence of water, for example, atmospheric moisture, to form a carbamic acid, which can undergo further polymerization reactions. According to a further advantageous embodiment of the invention, the adhesion promoter layer is not yet fully cured, at least in some areas.

[0107] A layer is referred to as "not yet fully cured" within the meaning of the present invention if at most 90%, preferably at most 95%, of the functional groups capable of crosslinking of polymers or polymer mixtures, preferably binders or binder mixtures, contained in the layer which is at least partially not yet fully cured, exhibit crosslinking.

[0108] The adhesion promoter layer, which is at least partially not yet fully cured, is preferably cured together with the polyurethane layer applied thereon, preferably completely cured. The polyurethane layer is preferably bonded to the adhesion promoter layer by a material bond. The composite of the film and the polyurethane layer is preferably dimensionally stable.

[0109] More preferably, the adhesion promoter layer does not have any free, ethylenically unsaturated groups.

[0110] During curing, preferably complete curing, of the adhesion promoter layer, which is at least partially not yet fully cured, and / or the polyurethane layer applied thereto, free isocyanate groups contained in the adhesion promoter layer can, for example, react with free isocyanate-reactive groups of the solvent-containing, preferably flowable, polyurethane-containing composition used to produce the polyurethane layer. If the adhesion promoter layer, which is at least partially not yet fully cured, contains free isocyanate-reactive groups, these groups can react accordingly with free isocyanate groups of the solvent-containing, preferably flowable, polyurethane-containing composition used to produce the polyurethane layer.

[0111] As a result, the adhesion of the polyurethane layer to the adhesion promoter layer after curing in step h) described further below for the process according to the invention is preferably significantly improved.

[0112] If the adhesion promoter layer, which is at least partially not yet fully cured, contains, for example, capped reactive groups, these groups release the corresponding reactive groups again in the process according to the invention, preferably in step e), preferably at a temperature in the range from 30°C to 180°C. Subsequently, released isocyanate groups, for example, contained in the adhesion promoter layer, can also react with free, isocyanate-reactive groups of the solvent-containing, preferably flowable, polyurethane-containing composition used to produce the polyurethane layer.

[0113] As a result, the adhesion of the polyurethane layer to the adhesion promoter layer is preferably significantly improved, wherein the storage stability of a film or transfer film according to the invention can preferably also be increased by the presence of capped, reactive groups, for example capped isocyanate groups, in the adhesion promoter layer which is at least partially not yet completely cured.

[0114] Preferably, the polyurethane layer adheres to the primer layer after curing with an adhesive force, determined according to the method described in DIN EN ISO 4624: 2016-08, preferably with a PosiTest® AT series adhesion tester from DeFelsko Corporation (Ogdensburg, NY, USA) using a 20 mm test punch, from a range of 2.5 MPa to 5 MPa, in particular from 2.5 MPa to 10 MPa.

[0115] Therefore, after curing, the polyurethane layer cannot be removed from a film-coated article according to the invention without damaging the film or the transfer layer of the transfer film.

[0116] Furthermore, in particular by applying the polyurethane layer in step e) of the process according to the invention by at least partially flooding and / or pouring over the film on its side delimited by the adhesion promoter layer which is at least partially not yet completely cured, a simple process for producing the polyurethane layer is provided by the mixture with a solvent-containing, preferably flowable, polyurethane-containing composition.

[0117] The flooding and / or pouring preferably allows the use of a large number of different solvent-containing, preferably flowable, polyurethane-containing compositions, which can be specifically tailored, for example, to the composition of the adhesion promoter layer which is at least partially not yet fully cured and / or to the properties to be fulfilled by the polyurethane layer, for example with regard to optical properties, mechanical properties and / or chemical resistance.

[0118] As explained above, the adhesion promoter layer, which is at least partially not yet fully cured, preferably comprises free, reactive groups and / or capped, reactive groups that release the corresponding reactive group at a temperature in the range from 30°C to 180°C. Methods for determining the content of free amino groups, hydroxyl groups, and / or isocyanate groups in raw materials for the production of plastics are known in the art.

[0119] Suitable methods for determining the content of free hydroxyl groups are described, for example, in ASTM E1899-16 (“Standard Test Method for Hydroxyl Groups Using Reaction with p-Toluenesulfonyl Isocyanate (TSI) and Potentiometric Titration with Tetrabutylammonium Hydroxide”, 2016, ASTM International, West Conshohocken, PA, USA), ASTM D4273-11 (“Standard Test Method for Polyurethane Raw Materials: Determination of Primary Hydroxyl Content of Polyether Polyols”, 2011, ASTM International, West Conshohocken, PA, USA), DIN 53240-3:2016-03 (“Binders for paints and varnishes - Determination of hydroxyl number - Part 3: Rapid method”, issue date: 2016-03), ISO 14900:2017-03 (“Plastics - Polyols for use in the production of polyurethane - Determination of hydroxyl number”, Issue date: 2017-03) or ASTM D4274-16 (“Standard Test Methods for Testing Polyurethane Raw Materials: Determination of Hydroxyl Numbers of Polyols”, 2016, ASTM International, West Conshohocken, PA, USA).

[0120] Suitable methods for determining the content of free isocyanate groups are described, for example, in DIN EN ISO 14896:2009-07 (“Plastics - Polyurethane raw materials - Determination of isocyanate content”, issue date 2009-07) or ASTM D2572-97(2010) (“Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers”, 2010, ASTM International, West Conshohocken, PA, USA).

[0121] A suitable method for determining the content of free amino groups is described, for example, in ASTM D2074-07(2013) (“Standard Test Methods for Total, Primary, Secondary, and Tertiary Amine Values ​​of Fatty Amines by Alternative Indicator Method”, 2013, ASTM International, West Conshohocken, PA, USA).

[0122] Preferably, free, reactive groups, preferably free isocyanate groups and / or free groups reactive towards isocyanate groups, preferably amino groups and / or hydroxy groups, or correspondingly capped analogues of the adhesion promoter layer, which is at least partially not yet fully cured, are bound to monomers, prepolymers and / or mixtures thereof contained in the layer.

[0123] More preferably, free, reactive groups, preferably free isocyanate groups and / or free groups reactive towards isocyanate groups, preferably amino groups and / or hydroxyl groups, and / or correspondingly capped analogues thereof of the adhesion promoter layer, which is at least partially not yet fully cured, are bound to binders, crosslinking agents and / or mixtures thereof contained in the adhesion promoter layer.

[0124] The adhesion promoter layer, which is at least partially not yet fully cured, preferably comprises at least one binder which has free isocyanate groups and / or free groups reactive towards isocyanate groups, preferably amino groups and / or hydroxyl groups, and / or correspondingly capped analogues thereof.

[0125] Suitable binders are preferably selected from the group consisting of polyurethane resins, polyurethane dispersions, phenolic resins, epoxy resins, polyureas, melamine resins, aminoplasts, polyester resins, alkyd resins, polyamide resins, and mixtures thereof, more preferably polyurethane resins, polyurethane dispersions, phenolic resins, polyureas, melamine resins, aminoplasts, polyester resins, alkyd resins, polyamide resins, and mixtures thereof. More preferably, the at least one binder present in the adhesion promoter layer, which is at least partially not yet fully cured, contains no free, ethylenically unsaturated groups.

[0126] In a preferred embodiment, the adhesion promoter layer, which is at least partially not yet fully cured, comprises or consists of at least one aqueous, uncrosslinked or crosslinked polyurethane dispersion, which preferably has free groups reactive towards isocyanate groups, more preferably amino groups and / or hydroxyl groups, or at least one uncrosslinked or crosslinked polyurethane resin, which preferably has isocyanate groups and / or capped analogues thereof or groups reactive towards isocyanate groups, more preferably amino groups and / or hydroxyl groups, and / or correspondingly capped analogues thereof.

[0127] Capped reactive groups can also be referred to as capped analogues of the aforementioned free groups reactive towards isocyanate groups or capped analogues of the aforementioned isocyanate groups.

[0128] Suitable compounds with capped, reactive groups are known in the art and include, for example, isocyanate groups that have been blocked (capped) by the addition of organic compounds with acidic H atoms, so-called blocking agents.

[0129] Suitable blocking agents with acidic hydrogen atoms include, for example, dialkyl malonates with alkyl groups, which may be identical or different from one another and have 1 to 4 carbon atoms, alkyl acetoacetates with an alkyl group having 1 to 4 carbon atoms, phenol derivatives, secondary amines, lactams, pyrazoles, oximes, or mixtures thereof. Examples of suitable dialkyl malonates are dimethyl malonate, diethyl malonate, diisopropyl malonate, di-tert-butyl malonate, and mixtures thereof.

[0130] Examples of suitable alkyl acetoacetates are methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate and mixtures thereof.

[0131] Examples of suitable phenol derivatives are phenol, cresols, nonylphenols and mixtures thereof.

[0132] Examples of suitable secondary amines are N-isopropyl-N-methylamine, N-isopropyl-N-ethylamine, N-tert-butyl-N-methylamine, N-tert-butyl-N-isopropylamine, N,N-diisopropylamine, N-tert-butyl-N-benzylamine (BEBA), N,N-dicyclohexylamine and mixtures thereof.

[0133] An example of a suitable lactam is s-caprolactam. An example of a suitable pyrazole is 3,5-dimethylpyrazole (DMP).

[0134] Examples of suitable oximes are aromatic aldoximes, aliphatic, cycloaliphatic, or aromatic ketoximes, and mixtures thereof. Examples of suitable aromatic aldoximes are benzaldoxime, tolylaldoxime, terephthaldialdoxime, isophthaldialdoxime, and mixtures thereof. Suitable ketoximes include, for example, acetone oxime, methyl ethyl ketoxime, methyl propyl ketoxime, 2-butanone oxime, methyl isobutyl ketoxime, 3-methyl-2-butanone oxime, diisobutyl ketoxime, 2-pentanone oxime, 3-pentanone oxime, 4-methyl-2-pentanone oxime, 2-heptanone oxime, 3-heptanone oxime, ethylhexyl ketoxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, and mixtures thereof. Preferably, the aforementioned compounds with capped, reactive groups can be used together with at least one catalyst. All known compounds that can catalyze isocyanate reactions can be used as catalysts.Examples include titanates such as tetrabutyl titanate and tetrapropyl titanate, tin carboxylates such as dibutyltin dilaulate (DBTL), dibutyltin diacetate, tin octoate; tin oxides such as dibutyltin oxide, and dioctyltin oxide; organoaluminum compounds such as.

[0135] Aluminum trisacetylacetonate, aluminum trisethylacetoacetate; chelating compounds such as titanium tetraacetylacetonate; amine compounds such as triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1,8-diazabicyclo-(5,4,0)undec-7-ene (DBU), 1,4-diazabicyclo[2,2,2]octane, N,N-dimethylpiperazine, 1,8-diazabicyclo[5,4,0]undec-7-ene, dimorpholinodimethyl ether, dimorpholinodiethyl ether (DMDEE), or mixtures thereof. The presence of one of the aforementioned catalysts preferably leads to a reduction in the temperature required to release the corresponding reactive group from the corresponding capped analogue.

[0136] The term "prepolymer" preferably refers to reactive oligomers, which are preferably used to produce binders contained in the adhesion promoter layer, preferably polyurethane polymers. Prepolymers can, for example, have at least two identical groups, preferably at least two free isocyanate groups and / or at least two free groups reactive toward isocyanate groups, for example, amino and / or hydroxy groups, and / or correspondingly capped analogues thereof.

[0137] The adhesion promoter layer, which is at least partially not yet fully cured, can be produced, for example, by reacting at least one compound having two or more isocyanate groups with at least one compound having two or more groups reactive towards isocyanate groups, for example hydroxyl groups and / or amino groups, wherein preferably either the at least one compound having two or more isocyanate groups or the at least one compound having two or more groups reactive towards isocyanate groups is used in excess.

[0138] Suitable compounds having two or more isocyanate groups are known and include, for example, monomeric isocyanates having two or more isocyanate groups, isocyanate adducts, isocyanate prepolymers having two or more isocyanate groups or mixtures thereof.

[0139] Monomeric isocyanates with two or more isocyanate groups are, for example, aliphatic isocyanates with two or more isocyanate groups, cycloaliphatic isocyanates with two or more isocyanate groups, aromatic isocyanates with two or more isocyanate groups, adducts thereof, or mixtures thereof, for example 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene diisocyanate (NDI), 4,4'-diisocyanatodicyclohexylmethane (H12MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), pentamethylene diisocyanate (PDI), 1 ,3-Phenylene diisocyanate, 1,4-Phenylene diisocyanate, adducts thereof or mixtures thereof.

[0140] Isocyanate adducts are commercially available and are preferably formed by dimerization or trimerization of one of the aforementioned aliphatic diisocyanates, cycloaliphatic diisocyanates or aromatic diisocyanates.

[0141] For example, the trimer of 1,6-hexamethylene diisocyanate (HDI), also known as HDI biuret, is commercially available from Covestro AG (Leverkusen, Germany) under the trade name Desmodur® N. Suitable compounds with two or more isocyanate groups include isocyanate prepolymers.

[0142] Isocyanate prepolymers are commercially available and can preferably be obtained by reacting at least one of the aforementioned aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates, adducts thereof or mixtures thereof with at least one diol or polyol, wherein the diisocyanate used is preferably used in a molar excess, based on the number of free OH groups of the diol or polyol used.

[0143] Isocyanate prepolymers therefore preferably have urethane groups and free, reactive isocyanate groups in the polymer chain, which can preferably be at least partially capped.

[0144] Isocyanate prepolymers can also be partially converted to allophanates and / or biurets by increasing the temperature.

[0145] Suitable compounds having two or more hydroxide groups are polyhydric alcohols selected, for example, from the group consisting of alkanediols, alkanetriols, alkanetetraols, polyester polyols, polyether polyols, and mixtures thereof.

[0146] Suitable polyester polyols are preferably reaction products of polyfunctional, preferably difunctional alcohols, optionally together with small amounts of trifunctional alcohols, and polyfunctional, preferably difunctional and / or trifunctional carboxylic acids. Instead of free polycarboxylic acids, the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters with alcohols having preferably 1 to 3 carbon atoms can also be used. Polyols and carboxylic acids known per se for the production of polyesters can be selected.Examples of diols suitable for producing such polyester polyols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, pentanediol, the isomeric hexanediols, octanediol, 1,4-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 1,2,4-butanetriol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, or polybutylene glycol. Aromatic diols can also be used.

[0147] The polycarboxylic acids used can be aliphatic, cycloaliphatic, aromatic, or heterocyclic, or both. They can optionally be substituted, for example, by alkyl groups, alkenyl groups, ether groups, or halogens. Suitable polycarboxylic acids include, for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, or mixtures of two or more thereof. Suitable tricarboxylic acids, which may optionally be present in proportion, include citric acid or trimellitic acid. All of the acids mentioned can be used individually or as mixtures of two or more thereof.

[0148] However, polyester polyols of oleochemical origin can also be used. Such polyester polyols can be prepared, for example, by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 C atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12 C atoms in the alkyl radical. Other suitable polyester polyols are polycarbonate polyols. Polycarbonates can be obtained, for example, by the reaction of diols such as propylene glycol, 1,4-butanediol or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol or mixtures of two or more thereof with diaryl carbonates, for example diphenyl carbonate, or with phosgene. Another group of suitable polyols are polylactones, for example polyesters based on ε-caprolactone.Polyester polyols that contain one or more urethane groups in the molecular chain are also suitable.

[0149] Suitable polyether polyols include, for example, reaction products of low-molecular-weight polyfunctional alcohols with alkylene oxides. The alkylene oxides preferably have 2 to 4 carbon atoms. Suitable examples are the reaction products of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof with aliphatic diols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, the isomeric butanediols, hexanediols, 2,2-dimethyl-1,3-propanediol, 2-methylpropanediol, 1,6-hexanediol, 2,4,4-trimethylhexanediol-1,6, 2,2,4-trimethylhexanediol-1,6, 1,4-cyclohexanedimethanol, or aromatic diols, such as 4,4'-dihydroxydiphenylpropane, bisphenol A, bisphenol F, pyrocatechol, resorcinol, hydroquinone or mixtures of two or more thereof. Furthermore, the reaction products of polyfunctional alcohols, such as glycerol, trimethylolethane or trimethylolpropane, pentaerythritol or sugar alcohols with the alkylene oxides may also be suitable.

[0150] Other suitable polyols are produced by polymerization of tetrahydrofuran.

[0151] Furthermore, the aforementioned polyether polyols or polyester polyols, preferably polyether polyols, can be amino-functionalized, wherein preferably one or more hydroxide groups are replaced by one or more amino groups, primary amino groups and / or secondary amino groups.

[0152] For example, amino-functionalized polyether polyols, which may also be referred to as amino-terminated polyethers, are known to those skilled in the art and can be obtained commercially, for example, under the name JEFFAMINE ® from Huntsman Corporation (The Woodlands, TX, USA).

[0153] Preferably, the adhesion promoter layer, which is at least partially not yet fully cured, can comprise or consist of isocyanate prepolymers, which can be crosslinked or uncrosslinked, capped isocyanate prepolymers, which can be crosslinked or uncrosslinked, or mixtures thereof, wherein the aforementioned isocyanate prepolymers or capped isocyanate prepolymers can contain traces of monomeric diisocyanates and / or adducts thereof, preferably in a proportion of less than 5% by weight, preferably less than 1% by weight, in each case based on the total weight of the prepolymer used.

[0154] Prepolymers with free groups reactive toward isocyanate groups, more preferably amino groups and / or hydroxyl groups, can preferably be obtained by reacting at least one of the aforementioned aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates, adducts thereof, or mixtures thereof with at least one diol, polyol, and / or amino-functionalized polyether polyol, wherein the diols, polyols, and / or amino-functionalized polyether polyols used are preferably employed in a molar excess, based on the number of free isocyanate groups in the diisocyanate used. Prepolymers with free groups reactive toward isocyanate groups thus preferably have urethane groups and free, reactive hydroxyl groups and / or amino groups in the polymer chain, which can preferably be at least partially capped, for example by thermally reversible addition of isocyanate.

[0155] Alternatively, the adhesion promoter layer, which is at least partially not yet fully cured, can comprise or consist of prepolymers with free groups reactive towards isocyanate groups, which can be crosslinked or uncrosslinked, prepolymers with capped groups reactive towards isocyanate groups, which can be crosslinked or uncrosslinked, or mixtures thereof, wherein the aforementioned prepolymers can contain traces of diols, polyols and / or amino-functionalized polyether polyols used, preferably in a proportion of less than 5% by weight, preferably less than 1% by weight, in each case based on the total weight of the prepolymer used.

[0156] More preferably, the aforementioned isocyanate prepolymers, capped isocyanate prepolymers, prepolymers with free groups reactive towards isocyanate groups, and / or prepolymers with capped groups reactive towards isocyanate groups of the adhesion promoter layer which is at least partially not yet completely cured can be crosslinked by using suitable crosslinking agents, for example polyfunctional aziridines (PFA).

[0157] Furthermore, the adhesion promoter layer, which is at least partially not yet fully cured, can comprise at least one co-binder, which is preferably selected from the group consisting of acrylic resins, methacrylic resins, vinyl ester resins, and mixtures thereof, and more preferably contains no free, ethylenically unsaturated groups. More preferably, the adhesion promoter layer, which is at least partially not yet fully cured, comprises the at least one co-binder in a proportion from a range of at most 30 wt.%, more preferably from a range of at most 25 wt.%, preferably from a range of 5 wt.% to 20 wt.%, in each case based on the total weight of the layer.

[0158] Furthermore, the adhesion promoter layer, which is at least partially not yet fully cured, can contain at least one crosslinking agent which preferably has at least two free isocyanate groups and / or at least two free groups reactive towards isocyanate groups, for example amino and / or hydroxy groups.

[0159] Suitable crosslinking agents are known and include organic compounds having two or more free reactive groups, for example aliphatic or alicyclic compounds having two or more free isocyanate groups, aliphatic or alicyclic compounds having two or more free hydroxide groups, aliphatic or alicyclic compounds having two or more free amine groups, in each case appropriately capped analogues thereof or mixtures thereof.

[0160] More preferably, the adhesion promoter layer, which is at least partially not yet fully cured, comprises the at least one crosslinking agent in a proportion from a range of at most 15 wt.%, more preferably of at most 12 wt.%, preferably from a range of 1 wt.% to 10 wt.%, in each case based on the total weight of the layer.

[0161] Preferably, the adhesion promoter layer, which is at least partially not yet fully cured, contains at least one, preferably inorganic, filler in a proportion of at most 15 wt.%, preferably from a range of 0.1 wt.% to 12 wt.%, more preferably from a range of 1 wt.% to 10 wt.%, in each case based on the total weight of the layer.

[0162] Preferably, the adhesion promoter layer, which is at least partially not yet fully cured, contains at least one, preferably organic, additive, for example at least one wetting agent, at least one leveling agent, at least one defoamer, at least one thixotropic agent or a mixture thereof, preferably in a proportion of at most 12 wt.%, preferably from a range of 0.1 wt.% to 10 wt.%, in each case based on the total weight of the layer.

[0163] More preferably, the adhesion promoter layer, which is at least partially not yet fully cured, has a thickness in a range from 0.5 pm to 15 pm, more preferably in a range from 1 pm to 12 pm.

[0164] Preferably, the adhesion promoter layer, which is at least partially not yet fully cured, does not comprise any photoinitiators.

[0165] Photoinitiators are chemical compounds that decompose in a photolysis reaction after absorbing light, forming reactive species that can initiate a reaction, such as polymerization. These reactive species can be radicals, anions, or cations.

[0166] More preferably, the adhesion promoter layer, which is at least partially not yet fully cured, does not comprise any photoinitiators or binders with free, ethylenically unsaturated groups.

[0167] According to a further advantageous embodiment of the invention, the adhesion promoter layer has a layer thickness selected from a range of 0.1 pm to 15 pm, preferably from 0.5 pm to 10 pm, particularly preferably from 1 pm to 4 pm. According to a further advantageous embodiment of the invention, the at least one decorative layer has at least one decorative element.

[0168] The at least one decorative layer can contain one or more lacquer layers with a layer thickness selected from a range of 0.1 μm to 15 μm, preferably from 0.3 μm to 8 μm. This lacquer layer or these lacquer layers can be colored, i.e., pigmented and / or dyed. These additional lacquer layers can be printed as a solid surface or partially or regionally within the decor. The lacquer layers can preferably be applied using gravure printing, screen printing, flexographic printing, and / or inkjet printing.

[0169] Alternatively or additionally, one or more lacquer layers of the decorative layer can be transparent.

[0170] The at least one decorative layer can contain at least one metal layer. The metal layer is preferably applied by metallization using a PVD process or by a CVD process, such as vapor deposition and / or sputtering. The metal layer preferably has a layer thickness selected from a range of 1 nm to 200 nm, preferably from 5 nm to 40 nm. Possible metals include Cr, In, Al, Sn, Ag, and Si. Furthermore, a combination of one or more lacquer layers with at least one metallization is also possible.

[0171] The at least one decorative layer and / or the at least one decorative element can be arranged in regions or over the entire surface. At least a first region of the decorative layer and / or at least one first decorative element can have different configurations. In particular, the design or shape of the at least one first region of the decorative layer and / or of the at least one first decorative element is selected from one or more of the following groups: motif, lettering, letter, number, symbol, geometric figure, visually recognizable design element, pattern, logo, code, and conductor track.

[0172] In the following paragraph, the term “layer” refers to a lacquer layer, a decorative layer or a decorative element:

[0173] If a layer is only applied in certain areas, this can be done as a continuous endless pattern or as a single-image decoration or as a combination of both. Several partially applied layers can (but do not have to) be arranged in register, i.e. in precise position relative to one another. For example, a single-image decoration of one layer can overlap with an endless pattern of another partially applied layer. For example, a single-image decoration of one layer can overlap with an endless pattern of another partially applied layer. For example, an endless pattern of one layer can overlap with an endless pattern of another partially applied layer.

[0174] According to a further advantageous embodiment of the invention, several decorative layers comprise at least one lacquer, individually or in combination or as a mixture selected from a UV-crosslinked lacquer, a thermally crosslinked lacquer, or a thermoplastic lacquer. The decorative layers are each independently unpigmented or pigmented, or colored or uncolored.

[0175] According to a further advantageous embodiment of the invention, the at least one decorative layer containing at least one decorative element is selected from the group consisting of transparent and / or colored lacquer layers, in particular comprising one or more dyes and / or pigments, replication layers with a molded optically active surface structure, reflection layers, in particular opaque reflection layers, transparent reflection layers, metallic reflection layers or dielectric reflection layers, optically variable layers, optically active layers, interference multilayer systems, volume hologram layers, liquid crystal layers, in particular cholesteric liquid crystal layers, electrically conductive layers, antenna layers, electrode layers, magnetic layers, magnetic storage layers, barrier layers and combinations thereof.

[0176] In the present application, a film, layer, or ply with a transmittance greater than 70% is preferably referred to as transparent. With a transmittance between 50% and 70%, the film, layer, or ply is preferably referred to as translucent. With a transmittance of less than 50%, the film, layer, or ply is preferably referred to as opaque. The stated percentage values ​​refer in particular to a transmittance in the wavelength range perceivable by the human eye. The wavelength range perceivable by the human eye is preferably assumed to be the wavelength range from 380 nm to 780 nm.

[0177] According to a further advantageous embodiment of the invention, the polyurethane layer has a wall thickness selected from a range of 0.2 mm to 30 mm, preferably from 0.3 mm to 20 mm, particularly preferably from 0.5 mm to 15 mm. The film-coated article is preferably dimensionally stable.

[0178] The wall thickness of the polyurethane layer can also be referred to as the “layer thickness” of the polyurethane layer or as the “layer thickness” or “thickness” of the polyurethane layer.

[0179] Advantageously, film-coated articles according to the invention can have a wide range of wall thicknesses. In particular, film-coated articles according to the invention can have particularly thin and / or particularly thick wall thicknesses. Advantageously, film-coated articles according to the invention can have both particularly thin and particularly thick wall thicknesses. Such wall thicknesses are very difficult or impossible to achieve using an injection molding process with thermoplastic materials.

[0180] According to a further advantageous embodiment of the invention, the polyurethane layer has a wall thickness that remains constant along the areal extent of the polyurethane layer and / or along the areal extent of the decorative layer.

[0181] The planar extension of the polyurethane layer is preferably parallel to the planar extension of the decorative layer. Furthermore, the extension of the plane formed by the polyurethane layer (or decorative layer) is preferably parallel to the extension of the plane formed by the decorative layer. The longitudinal extension of the polyurethane layer is preferably parallel to the longitudinal extension of the decorative layer. The transverse extension of the polyurethane layer is also preferably parallel to the transverse extension of the decorative layer.

[0182] According to a further advantageous embodiment of the invention, the polyurethane layer has a wall thickness that does not remain constant along the areal extent of the polyurethane layer and / or along the areal extent of the decorative layer. The wall thickness preferably has a first wall thickness at least in a first region and preferably a second wall thickness at least in a second region. The wall thickness can change continuously or in one or more stages. The first wall thickness can differ from the second wall thickness in particular by 5% to 75%, preferably by 10% to 50%. With regard to the first and second regions, reference is made to the above explanation of the term “region”.

[0183] Advantageously, film-coated articles according to the invention can have particularly complex geometries. These geometries can, for example, include abrupt or continuous cross-sectional changes, in particular tapers, corners, edges, points, and / or curves.

[0184] According to a further advantageous embodiment of the invention, the polyurethane layer has at least one continuous change in wall thickness along the areal extent of the polyurethane layer and / or along the areal extent of the decorative layer.

[0185] According to a further advantageous embodiment of the invention, the polyurethane layer has at least one wall thickness change along the planar extent of the polyurethane layer and / or along the planar extent of the decorative layer. A wall thickness change is understood, in particular, to mean a gradual change in the wall thickness. The wall thickness change preferably runs perpendicular to the decorative layer. A wall thickness change is therefore preferably understood to mean an abrupt and / or discrete wall thickness change.

[0186] Advantageously, film-coated articles according to the invention can have abrupt wall thickness changes.

[0187] According to a further advantageous embodiment of the invention, the film-coated article is delimited on a first side by the polyurethane layer and on an opposite second side by the protective layer and / or the carrier layer.

[0188] The film-coated article is therefore preferably protected on its first side by the polyurethane layer.

[0189] If the film is designed as a transfer film, the protective layer of the transfer layer preferably forms the boundary of the film-coated article on the second side of the film-coated article, i.e., on the side of the film-coated article facing away from the polyurethane layer. In this case, the film-coated article is preferably protected by the protective layer of the transfer layer on its second side. If the film is designed as a label, PMD sheet, or insert, the carrier layer can also serve as a protective layer.

[0190] Preferably, the carrier layer in the film-coated article forms the backing layer. More specifically, the carrier layer in the film-coated article forms the protective layer on the second side of the film-coated article, i.e., on the side of the film-coated article facing away from the polyurethane layer. In this case, the film-coated article is preferably protected by the carrier layer of the film on its second side.

[0191] According to a further advantageous embodiment of the invention, the carrier layer has at least one anchoring region for anchoring or fastening, in particular adhesive bonds and / or functional elements, such as conductor tracks, sensors, lights, and / or electronic components. The carrier layer preferably has functional elements, such as conductor tracks, sensors, lights, and / or electronic components. According to a further advantageous embodiment of the invention, the polyurethane layer has a transmission of greater than 50%, preferably greater than 70%, for the wavelength range perceivable by the human eye.

[0192] With a transmission greater than 70%, the polyurethane layer is preferably referred to as transparent. With a transmission between 50% and 70%, the polyurethane layer is preferably referred to as translucent.

[0193] The wavelength range perceivable by the human eye is preferably assumed to be the wavelength range from 380 nm to 780 nm.

[0194] The polyurethane layer is advantageously highly translucent. This high translucency allows for good design representation of decorative layers, mask layers, and / or other optical functional layers located below or behind the polyurethane layer.

[0195] According to a further advantageous embodiment of the invention, the decorative layer embedded in the film-coated article is visible or perceptible to the human eye from both sides of the layer structure, at least partially or completely, and / or measurable by an optical sensor unit.

[0196] The decorative layer embedded in the article is therefore visible to a human observer, in particular, from both sides of the layered structure. More precisely, the decorative layer embedded in the film-coated article is preferably at least partially or completely visible both from the first side of the film-coated article through the polyurethane layer and from the opposite second side of the article through the protective layer and / or the carrier layer. Preferably, therefore, both the polyurethane layer and the protective layer and / or the carrier layer are transparent. In addition, the article is preferably protected on the outside by both the polyurethane layer and the protective layer and / or the carrier layer.

[0197] According to a further advantageous embodiment of the invention, the polyurethane layer adheres to the adhesion promoter layer with an adhesive force selected from a range of 2.5 MPa to 10 MPa, preferably from 2.5 MPa to 5 MPa.

[0198] Preferably, the adhesive force is determined according to the method described in DIN EN ISO 4624: 2016-08, particularly preferably with a PosiTest® AT series adhesion tester from DeFelsko Corporation (Ogdensburg, NY, USA) using a 20 mm test punch.

[0199] Therefore, after curing, the polyurethane layer can preferably not be removed from a film-coated article according to the invention without damaging the film or the transfer layer of the transfer film.

[0200] According to a further advantageous embodiment of the invention, the film-coated article does not comprise an injection-molded thermoplastic, i.e., no injection-molded thermoplastic material.

[0201] According to a further advantageous embodiment of the invention, the mixture is injected into the mold cavity in step e) at a filling pressure selected from a range of 70 bar to 140 bar, preferably from 80 bar to 100 bar. According to a further advantageous embodiment of the invention, the mold cavity forms a negative for the polyurethane layer to be formed. The mold cavity preferably has cavity regions of varying thicknesses to form different wall thicknesses of the polyurethane layer.

[0202] Preferably, the mold cavity has at least one first cavity region for producing the first wall thickness of the polyurethane layer and at least one second cavity region for producing the second wall thickness of the polyurethane layer. The first wall thickness can differ from the second wall thickness, in particular, by 5% to 75%, preferably by 10% to 50%.

[0203] According to a further advantageous embodiment of the invention, the polyurethane layer is formed in the mold cavity as a result of the injection of the mixture according to step e) at a temperature selected from a range of 40°C to 160°C, preferably from 60°C to 140°C, particularly preferably from 80°C to 120°C, and / or at a pressure selected from a range of 3 bar to 100 bar, preferably from 5 bar to 50 bar, particularly preferably from 8 bar to 30 bar.

[0204] Advantageously, lower temperatures are required to form the polyurethane layer than when using thermoplastic materials in the injection molding process.

[0205] Preferably, an exothermic reaction starts in the mixture when the polyurethane-forming mixture is made available at the mixing head in step d). This exothermic reaction preferably heats the mixture introduced into the mold cavity in step e). Depending on the current temporal phase of the exothermic reaction, it is advantageous to temper the mixture, in particular to heat it up or cool it down, so that the exothermic reaction takes place at a roughly constant process temperature. At the start of the exothermic reaction, the mixture is therefore heated up or cooled down by the then prevailing mold temperature, which is higher than the mixture temperature.As the exothermic reaction progresses, with increasing thermal energy released, the largely constant mold temperature leads to a cooling of the mixture, which is heated by the reaction, because the mold temperature is then temporarily below the mixture temperature influenced by the exothermic reaction. The mold temperature remains largely constant during the exothermic reaction.

[0206] The mold cavity is preferably preheated to a temperature selected from a range of 40°C to 160°C, preferably 60°C to 140°C, particularly preferably 80°C to 120°C, prior to injecting the mixture according to step e). The temperature of the mixture at the start of the chemical reaction and / or immediately after mixing the mixture according to step d) and / or immediately upon injection into the mold cavity is preferably lower than the temperature of the mold cavity (mold temperature). Due to the low thermal conductivity of the polyurethane of approximately 0.020 W / Km to 0.040 W / Km, the mixture and / or the forming polyurethane layer preferably assumes the preset temperature of the mold cavity (mold temperature) over time and / or as the reaction progresses.

[0207] The temperature difference for cooling the film-coated article formed in the mold cavity is preferably between 0°C and 100°C, preferably between 0°C and 50°C, particularly preferably between 0°C and 30°C. The temperature difference for cooling the film-coated article formed in the mold cavity is thus advantageously much lower than when injection molding thermoplastic materials. Advantageously, lower pressures are required to form the polyurethane layer than when using thermoplastic materials in the injection molding process.

[0208] According to a further advantageous embodiment of the invention, the method additionally comprises the following step, which is preferably carried out after step e): h) curing the mixture inside and / or outside the mold cavity to form the polyurethane layer.

[0209] The duration of the curing process within the mold cavity is preferably 10 seconds to 120 seconds, particularly preferably 20 seconds to 90 seconds. This is in particular 2 to 10 times the pot life of the mixture, preferably 3 to 7 times the pot life of the mixture. The pot life is the processability or service life of the reactive mixture.

[0210] The duration of the curing process outside the mold cavity, in particular on a holding device having the shape of the film-coated article, is preferably 5 minutes to 90 minutes, particularly preferably 5 minutes to 45 minutes.

[0211] Preferably, the viscosity of the mixture and / or the resulting polyurethane layer increases as the chemical crosslinking reaction progresses. Preferably, the mixture and / or the resulting polyurethane layer cures as the chemical crosslinking reaction progresses. Preferably, a fully cured polyurethane layer is formed at the end of the chemical crosslinking reaction. Preferably, the mixture is fully cured in step h) to form the polyurethane layer.

[0212] The curing according to step h) is preferably carried out at a temperature selected from a range of 20°C to 160°C, preferably from 20°C to 120°C.

[0213] In the case of the adhesion promoter layer being designed that is at least partially not yet fully cured, the adhesion promoter layer, which is at least partially not yet fully cured, is preferably cured together with the mixture applied thereto and / or with the polyurethane layer applied thereto, preferably completely cured. In this case, crosslinks preferably form between the polyurethane layer and the adhesion promoter layer. The polyurethane layer is preferably bonded to the adhesion promoter layer in a material-to-material manner. The composite of the film and the polyurethane layer is preferably dimensionally stable.

[0214] Preferably, the polyurethane layer cannot be removed from the adhesion promoter layer without causing damage.

[0215] According to a further advantageous embodiment of the invention, the method additionally comprises the following step, which is preferably carried out after step e), g) and / or step h): i) Removing the carrier layer of the film.

[0216] This advantageous embodiment therefore preferably relates to the design of the film as a transfer film.

[0217] After performing step i), preferably only the transfer layer of the transfer film remains on the film-coated article. The release layer can be arranged completely or partially on the transfer layer after removal of the carrier layer from the film and / or completely or partially on the carrier layer.

[0218] According to a further advantageous embodiment of the invention, the film in step c) is provided as a roll and / or as a continuous film and / or as a sheet and / or is introduced into the mold cavity by means of film feed device technology.

[0219] Preferably, the process is carried out as an IMD process (IMD = In-Mold Decoration). The film comprising the decorative layer is conveyed as a transfer film with a carrier layer and a transfer layer containing the decorative layer, particularly as a roll, and is introduced into the mold cavity, particularly according to step c).

[0220] Compared to other decoration methods such as varnishing, the lacquer transfer technology decoration process advantageously enables a significantly greater variety of designs. This allows for the creation of individual images, technical designs, tactile surfaces, and many other design variations.

[0221] According to a further advantageous embodiment of the invention, the method has the further following step or step a), c) and / or step f) comprises the further following sub-step: j) cleaning the film and / or the film-coated article, preferably the adhesion promoter layer and / or the polyurethane layer, in particular by means of at least one brush, a blower and / or a suction device. According to a further advantageous embodiment of the invention, the method has the further following step or step f) comprises the further following sub-step: k) printing the film-coated article, preferably the polyurethane layer, in particular in at least a first and / or second area, preferably alone or in combination selected from inkjet printing, gravure printing, screen printing, planographic printing, letterpress and flexographic printing.

[0222] According to a further advantageous embodiment of the invention, the method has the further following step or step c) comprises the further following sub-step: l) Pretreatment of the film, preferably of the adhesion promoter layer, in particular by means of a method alone or in combination selected from corona treatment, flame treatment, plasma treatment.

[0223] According to a further advantageous embodiment of the invention, the method comprises the further following step or step f) comprises the further following sub-step: m) cutting the film-coated article by means of punching or water jet cutting or laser cutting.

[0224] Cutting preferably refers to external cutting.

[0225] Preferably, the method can comprise the following further step, or step f) can comprise the following sub-step: n) dividing the film-coated article into individual panels, in particular in the case of roll goods having multiple panels or in the case of a sheet having multiple panels. According to a further advantageous embodiment of the invention, the film-coated article obtained in step f) is selected from the group consisting of displays, touch fields, panels, bezels, and functional elements, in particular from the following areas: white goods, motor vehicles, aviation, ships, household appliances, telecommunications equipment, consumer goods, documents, security elements, labels, and / or electronic items.

[0226] According to a further advantageous embodiment of the invention, the method does not include thermoplastic injection molding.

[0227] It is also possible for the process steps and substeps to be performed once or multiple times. In particular, process steps and substeps can be repeated. The preferred sequence of process steps comprises at least the order of step a) - step b) - step c) - step d) - step e) - step f), whereby, in particular, further steps or substeps can be inserted between these steps.

[0228] Of course, the above-mentioned material characteristics can also be applied equivalently in a process or the above-mentioned process characteristics can be applied in the product.

[0229] The invention is explained below using several exemplary embodiments with the aid of the accompanying drawings. The exemplary embodiments shown are therefore not to be understood as limiting.

[0230] Fig. 1 shows a plot of the viscosity level of different

[0231] Polyurethane-forming mixtures depending on temperature.

[0232] Fig. 2 shows a schematic structure of a transfer film for

[0233] Implementation of the method. Fig. 3 shows a schematic structure of a first film-coated article.

[0234] Fig. 4 shows a schematic structure of a second film-coated article.

[0235] Fig. 5 shows a flow chart of an exemplary method according to the invention.

[0236] Figure 1 shows a plot of the viscosity of various polyurethane-forming mixtures as a function of temperature. The plot refers to the time before the start of the crosslinking reaction. The plot refers only to the viscosity of the polyurethane-forming mixture before the reaction. The influence of the temperature of the mold cavity (tool temperature) is not taken into account.

[0237] The numerical values ​​for Fig. 1 are shown in the following Table 1. The data comes from Ruehl Puromer GmbH.

[0238] Table 1 : Dependence of the viscosity of various polyurethane-forming mixtures on temperature

[0239] Fig. 2 shows a schematic structure of a transfer film 1 for carrying out the method. The transfer film 1 comprises a carrier layer 10 and a transfer layer 13. The carrier layer 10 comprises a carrier layer 11 and a release layer 12. The transfer layer 13 comprises a protective layer 14, at least one decorative layer 15, and an adhesion promoter layer 16.

[0240] The carrier layer 11 preferably has a layer thickness of between 10 μm and 100 μm, preferably between 23 μm and 75 μm. In the exemplary transfer film 1, the carrier layer 11 has a layer thickness of 75 μm. The release layer 12 preferably has a layer thickness of 0.1 nm to 50 nm. The release layer is arranged on the side of the carrier layer 10 facing the transfer layer 13 and consists of a thin wax layer.

[0241] The protective layer 14 preferably has a layer thickness of between 0.1 μm and 20 μm, preferably between 1 μm and 3 μm. In the exemplary transfer film 1, the protective layer 14 is formed from a protective lacquer and preferably has a layer thickness of 2 μm.

[0242] The at least one decorative layer 15 preferably comprises one or more lacquer layers and / or one or more metal layers. The lacquer layers preferably have a layer thickness between 0.1 μm and 15 μm, preferably between 0.3 μm and 8 μm. The metal layers preferably have a layer thickness between 1 nm and 200 nm, preferably between 5 nm and 40 nm. In the exemplary transfer film 1, the decorative layer comprises a lacquer layer with a layer thickness of 4 μm and a metal layer with a layer thickness of 30 nm.

[0243] The adhesion promoter layer 16 preferably has a layer thickness selected from a range of 0.1 μm to 15 μm, preferably from 0.5 μm to 10 μm, particularly preferably from 1 μm to 4 μm. In the exemplary transfer film 1, the adhesion promoter layer 16 has a layer thickness of 2 μm.

[0244] The adhesion promoter layer, for example, is a mixture of acrylic resin with free OH and / or acid groups and at least one suitable crosslinking agent with a reactive group, such as a polyfunctional aziridine (PFA) or polyisocyanate. This adhesion promoter layer may be in an incompletely cured state and may undergo a chemical reaction under the reactive conditions during flooding with, for example, polyol or polyisocyanates.

[0245] Fig. 3 shows a schematic structure of a first film-coated article. The film-coated article 2 comprises the transfer layer 13 of the transfer film 1 shown in Fig. 1. In addition, the film-coated article 2 comprises a polyurethane layer P applied directly to the adhesion promoter layer 16.

[0246] The polyurethane layer P preferably has a wall thickness selected from a range of 0.2 mm to 30 mm, preferably from 0.3 mm to 13 mm, particularly preferably from 1 mm to 8 mm.

[0247] In the embodiment shown in Fig. 3, the film-coated article 2 has a flat polyurethane layer P. The polyurethane layer P thus has a constant wall thickness. The wall thickness of the polyurethane layer P is, for example, 12 mm. The film-coated article 2 shown is dimensionally stable.

[0248] The mixture preferably contains a polyol, an isocyanate, and other chemical additives as components. For example, "Puroclear 3351 IT" from Ruehl Puromer GmbH is used as a mixture. The polyol "Puroclear 3351 IT" as a single component has a density of 1.09 g / cm³ at a temperature of 20°C. 3 and at a temperature of 25°C a viscosity of 1000 mPas.

[0249] The isocyanate “Puronate 960 / 1” as a single component has a density of 1.13 g / cm at a temperature of 20°C 3 and at a temperature of 25°C a viscosity of 2500 mPas.

[0250] Fig. 4 shows a schematic structure of a second film-coated article. The structure of the second film-coated article corresponds to the structure of the first film-coated article. Unlike the first film-coated article, the polyurethane layer P of the second film-coated article forms various wall thicknesses. The wall thickness of the polyurethane layer P varies between 1 mm and 10 mm.

[0251] Advantageously, a film-coated article 2 according to the invention can mold complex geometries. The film-coated article 2 can form a concrete three-dimensional body. The film-coated article 2 is dimensionally stable.

[0252] Fig. 5 shows a flowchart for an exemplary method according to the invention. The following steps preferably occur sequentially.

[0253] In a step S01, a film according to the invention is provided. The film is configured, for example, as the transfer film 1 shown in Fig. 1 with the carrier layer 10 and the transfer layer 13. The carrier layer 10 comprises the carrier layer 11 and the release layer 12. The transfer layer 13 comprises the protective layer 14, the decorative layer 15, and the adhesion promoter layer 16.

[0254] The adhesion promoter layer 16, for example, is not yet fully cured. The transfer film 1 is provided, for example, as a roll and / or continuous film.

[0255] In step S02, a mold cavity is prepared. The tool forming the mold cavity is preheated, for example, to a temperature preferably in the range between 80°C and 120°C, particularly preferably in the range between 90°C and 110°C. This is referred to as the tool temperature.

[0256] In a step S03, the transfer film 1 is introduced into the mold cavity. The transfer film 1 is preferably introduced into the mold cavity using film feed technology.

[0257] In step S04, a polyurethane-forming mixture is provided at a mixing head. The mixture preferably contains a polyol, an isocyanate, and other chemical additives as components. For example, "Puroclear 3351 IT" from Ruehl Puromer GmbH is used as the mixture. The components are mixed at the mixing head. Mixing the components at the mixing head initiates an exothermic chemical crosslinking reaction.

[0258] The polyol “Puroclear 3351 IT” as a single component has a density of 1.09 g / cm at a temperature of 20°C 3 and at a temperature of 25°C a viscosity of 1000 mPas.

[0259] The isocyanate “Puronate 960 / 1” as a single component has a density of 1.13 g / cm at a temperature of 20°C 3 and at a temperature of 25°C a viscosity of 2500 mPas.

[0260] The Puroclear 3351 IT and the isocyanate and, if necessary, other chemical additives as individual components or already premixed with one of the two main components are brought together in the mixing head, preferably at a raw material temperature of 60°C to 70°C.

[0261] The recommended tool temperature for this PUR mixture should preferably be in the range between 80°C and 90°C.

[0262] The mixture is injected into the mold cavity in step S05, which immediately follows step S04. The mixture is injected into the mold cavity, for example, at a filling pressure of 70 bar to 140 bar. In this exemplary embodiment, the transfer film 1 is completely flooded with the mixture on its side bordered by the adhesion promoter layer 16.

[0263] The temperature of the mixture when injected into the mold cavity is, for example, 60°C to 70°C. The filling pressure of the mixture when injected into the mold cavity is, for example, 70 bar to 140 bar. The viscosity of the mixture when injected into the mold cavity is, for example, up to 100 mPas.

[0264] In this example, the temperature of the mixture during injection into the mold cavity is lower than the temperature of the mold cavity (mold temperature). The duration of the injection, i.e., the filling phase, is approximately 5 seconds to 20 seconds, depending on the existing mold temperature.

[0265] In a step S06, the mixture cures in the mold cavity as a result of the exothermic chemical crosslinking reaction. This forms the polyurethane layer P. In particular, an exothermic chemical crosslinking reaction also occurs between the mixture forming the polyurethane layer and the not yet fully cured adhesion promoter layer 16. Crosslinks preferably form between the mixture forming the polyurethane layer and the adhesion promoter layer 16. The resulting polyurethane layer P is preferably bonded to the adhesion promoter layer 16 by a material bond. Curing creates a composite of the film and the polyurethane layer, which forms a precursor to the film-coated article. The composite of the film and the polyurethane layer is dimensionally stable.

[0266] Immediately after the mixture has been completely injected into the mold cavity, the temperature of the mixture is approximately 100°C. This temperature corresponds to the mold temperature or is slightly higher than the mold temperature. Immediately after the mixture has been completely injected into the mold cavity, the cavity pressure is approximately 50 bar to 150 bar. Immediately after the mixture has been completely injected into the mold cavity, the viscosity of the mixture is up to 100 mPas. The viscosity of the mixture remains unchanged from the viscosity at the start of injection.

[0267] After the mixture has been completely injected into the mold cavity, the so-called holding time is approximately 60 seconds. This is approximately five times the pot life. In this example, the curing time after removal of the component is approximately 30 minutes. This time can be accelerated, for example, by using cooling, resulting in reduced practical curing times of approximately 10 minutes.

[0268] Due to the low thermal conductivity of the polyurethane of approximately 0.020 W / Km to 0.040 W / Km, the mixture and / or the forming polyurethane layer P takes on the preset temperature of the mold cavity (tool temperature) as time progresses, which in this example is 100°C.

[0269] Due to the exothermic chemical crosslinking reaction, no additional heat input is required during curing in this example. After the mixture is completely injected into the mold cavity, the cavity pressure is approximately 50 bar to 150 bar. The cavity pressure decreases over the holding time in the mold due to the increase in viscosity of the PUR mixture.

[0270] As the chemical crosslinking reaction progresses, the viscosity of the mixture and / or the forming polyurethane layer P increases. The mixture and / or the forming polyurethane layer P cures.

[0271] At the end of the chemical crosslinking reaction, the temperature of the mixture in the mold cavity is approximately 100°C (corresponding to the mold temperature). The cavity pressure in the mold cavity at the end of the chemical crosslinking reaction is approximately 50 bar.

[0272] In a step S07, the composite of the film and the polyurethane layer is removed from the mold cavity.

[0273] In a step S08, the carrier layer 10 of the transfer film 1 is removed. In this example, both the carrier layer 11 and the release layer 12 of the carrier layer 10 are completely removed. As a result, only the transfer layer 13 of the transfer film 1 remains on the film-coated article 2. Preferably, the film-coated article 2 is detached from the carrier layer 10 immediately during removal.

[0274] In a step S09, the film-coated article 2 is placed on a holding device outside the tool (i.e., outside the mold cavity). The holding device preferably has the shape of the film-coated article.

[0275] In a step S10, the film-coated article 2 is cooled to a temperature of, for example, 20°C to 25°C (room temperature). The temperature difference for cooling the film-coated article 2, starting from the temperature of the mixture in the mold cavity, is only approximately 80 K. The temperature difference for cooling the film-coated article 2 is thus advantageously much lower than during injection molding of thermoplastic materials. The curing process preferably continues while the film-coated article 2 is cooling and is preferably completed when it reaches room temperature.

[0276] In a step S11, the finished film-coated article 2 is obtained. The finished film-coated article 2 is dimensionally stable.

[0277] After achieving dimensional stability, the following further steps can be carried out:

[0278] - Milling the excess contours of the polyurethane layer P to create a “clean” outer contour.

[0279] - polishing the film-coated article 2, in particular the polyurethane layer P.

[0280] - lasering the polyurethane layer P and / or the protective layer 14 opposite the polyurethane layer P.

[0281] The same sequence of steps S01 to S11, with the exception of step S08 (removal of the carrier layer of the transfer film 1), also applies to film configurations as a label, PMD sheet (print-mold-design sheet), or insert. The composite of the film and the polyurethane layer in steps S06 and S07 can already be referred to as film-coated article 2.

[0282] Advantageously, the process according to the invention eliminates the need to switch between separate production units for injection molding and polyurethane flooding. This makes the process according to the invention simple and fast compared to the prior art. Thus, film-coated articles can be produced particularly cost-effectively. It will be clear to those skilled in the art that the above-mentioned embodiments of the devices, equipment, methods, or process steps can be combined with one another in any way and do not represent any limitations, particularly in terms of their design and combination.

[0283] List of reference symbols 1 Transfer film

[0284] 2 Foil-coated article

[0285] P Polyurethane layer

[0286] 10 carrier layers

[0287] 11 Carrier layer

[0288] 12 release layer

[0289] 13 Transmission situation

[0290] 14 Protective layer

[0291] 15 decorative layer

[0292] 16 Adhesion promoter layer

Claims

Patent claims 1. Film for coating with polyurethane, in particular for flooding with polyurethane, wherein the film comprises at least one adhesion promoter layer (16), wherein the film additionally comprises a protective layer (14) and / or a carrier layer (11), characterized in that the adhesion promoter layer (16) is designed for the adhesion of polyurethane.

2. Film according to claim 1, characterized in that the film comprises at least one decorative layer (15), and that the adhesion promoter layer (16) is arranged on the side of the at least one decorative layer (15) facing away from the protective layer (14) and / or the carrier layer (11).

3. Foil according to claim 1 or 2, characterized in that the foil is a transfer foil (1), wherein the transfer foil (1) comprises a carrier layer (10) and a transfer layer (13) arranged on the carrier layer (10), wherein the transfer layer (13) comprises the at least one decorative layer (15), the protective layer (14) and the adhesion promoter layer (16), and wherein the The carrier layer (10) is arranged on the side of the at least one decorative layer (15) facing away from the adhesion promoter layer (16), and the carrier layer (10) comprises the carrier layer (11).

4. Foil according to claim 3, characterized in that the carrier layer (10) additionally comprises a release layer (12) preferably with a layer thickness of 0.1 nm to 50 nm, wherein the release layer (12) is arranged on the side of the carrier layer (10) facing the transfer layer (13), and wherein the release layer (12) preferably comprises or consists of at least one wax.

5. Film according to claim 1 or 2, characterized in that the film is a label or a print-mold design sheet (PMD sheet) or an insert, and wherein the carrier layer (11) is preferably formed from a material selected from the group consisting of polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polycarbonate (PC), acrylonitrile butadiene styrene polycarbonate (ABS-PC), polypropylene (PP) and mixtures thereof.

6. Film according to one of the preceding claims, characterized in that the adhesion promoter layer (16) is preferably applied directly or indirectly to the decorative layer (15) over the entire surface and / or in certain areas by means of a printing method, selected individually or in combination from screen printing, flexographic printing, gravure printing, inkjet printing.

7. Film according to one of the preceding claims, characterized in that, that the adhesion promoter layer (16) comprises at least one binder selected from the group consisting of polyurethane resins, polyurethane dispersions, acrylic resins, methacrylic resins, phenolic resins, epoxy resins, polyureas, melamine resins, aminoplasts, polyester resins, alkyd resins, polyamide resins, vinyl ester resins and mixtures thereof, preferably polyurethane resins, polyurethane dispersions, phenolic resins, epoxy resins, polyureas, melamine resins, aminoplasts, polyester resins, alkyd resins, polyamide resins and mixtures thereof.

8. Film according to one of the preceding claims, characterized in that the adhesion promoter layer (16) is designed in such a way that a chemical bond with the polyurethane to be deposited can be formed through the adhesion promoter layer (16).

9. Film according to one of the preceding claims, characterized in that the adhesion promoter layer (16) is not yet fully cured at least in some areas.

10. Film according to one of the preceding claims, characterized in that the adhesion promoter layer (16) has a layer thickness selected from a range of 0.1 pm to 15 pm, preferably from 0.5 pm to 10 pm, particularly preferably from 1 pm to 4 pm.

11. Foil according to one of the preceding claims, characterized in that the at least one decorative layer (15) has at least one decorative element.

12. Foil according to one of the preceding claims, characterized in that several decorative layers (15) comprise at least one lacquer, individually or in combination or as a mixture selected from a UV-crosslinked lacquer, a thermally crosslinked lacquer, a thermoplastic lacquer, and that the decorative layers (15) are each independently unpigmented or pigmented or colored or undyed.

13. Foil according to one of the preceding claims, characterized in that the at least one decorative layer (15) containing at least one decorative element is selected from the group consisting of transparent and / or colored lacquer layers, in particular comprising one or more dyes and / or pigments, replica layers with a molded optically active surface structure, reflective layers, in particular opaque reflective layers, transparent reflective layers, metallic reflective layers or dielectric reflective layers, optically variable layers, optically active layers, interference multilayer systems, volume hologram layers, liquid crystal layers, in particular cholesteric liquid crystal layers, electrically conductive layers, antenna layers, electrode layers, magnetic layers, magnetic storage layers, barrier layers and combinations thereof.

14. Foil-coated article comprising a foil according to claim 1, 2, 5 to 13 or the transfer layer (13) of the foil designed as a transfer foil (1) according to claim 3 or 4, and a polyurethane layer (P) cast onto the adhesion promoter layer (16).

15. Foil-coated article according to claim 14, characterized in that that the polyurethane layer (P) has a wall thickness selected from a range of 0.2 mm to 30 mm, preferably from 0.3 mm to 20 mm, particularly preferably from 0.5 mm to 15 mm.

16. Foil-coated article according to claim 14 or 15, characterized in that the polyurethane layer (P) has a wall thickness that remains constant along the planar extent of the polyurethane layer (P) and / or along the planar extent of the decorative layer (15).

17. Foil-coated article according to claim 14 or 15, characterized in that the polyurethane layer (P) has a wall thickness that is not constant along the planar extent of the polyurethane layer (P) and / or along the planar extent of the decorative layer (15), wherein the wall thickness preferably has a first wall thickness at least in a first region and preferably a second wall thickness at least in a second region, wherein the first wall thickness differs from the second wall thickness in particular by 5% to 75%, preferably by 10% to 50%.

18. Foil-coated article according to one of claims 14 to 17, characterized in that the polyurethane layer (P) has at least a continuous change in wall thickness along the planar extent of the polyurethane layer (P) and / or along the planar extent of the decorative layer (15).

19. Foil-coated article according to one of claims 14 to 18, characterized in that, that the polyurethane layer (P) has at least one wall thickness change along the planar extent of the polyurethane layer (P) and / or along the planar extent of the decorative layer (15), wherein the wall thickness change preferably runs perpendicular to the decorative layer (15).

20. Foil-coated article according to one of claims 14 to 19, characterized in that the foil-coated article (2) is limited on a first side by the polyurethane layer (P) and on an opposite second side by the protective layer (14) and / or the carrier layer (11).

21. Foil-coated article according to one of claims 14 to 20, characterized in that the carrier layer (11) has at least one anchoring area for anchoring or fastening, in particular bonding and / or functional elements, such as conductor tracks, sensors, lights and / or electronic components.

22. Foil-coated article according to one of claims 14 to 21, characterized in that the polyurethane layer (P) has a transmission greater than 50%, preferably greater than 70% for the wavelength range perceptible to the human eye.

23. Foil-coated article according to claim 22, characterized in that the decorative layer (15) embedded in the foil-coated article (2) is perceptible to the human eye and / or measurable by an optical sensor unit from both sides of the layer structure, at least partially or completely.

24. Foil-coated article according to one of claims 14 to 23, characterized in that the polyurethane layer (P) adheres to the adhesion promoter layer (16) with an adhesive force selected from a range of 2.5 MPa to 10 MPa, preferably from 2.5 MPa to 5 MPa.

25. Film-coated article according to one of claims 14 to 24, characterized in that the film-coated article (2) does not comprise an injection-molded thermoplastic.

26. Method for producing a film-coated article (2), preferably for producing the film-coated article (2) according to any one of claims 14 to 25, wherein the method comprises the following steps, in particular in the following order: a) providing a film according to any one of claims 1 to 13, b) providing a mold cavity, c) introducing the film into the mold cavity, d) providing a polyurethane-forming mixture at a mixing head, e) injecting the mixture into the mold cavity so that the film is at least partially flooded and / or coated by the mixture on its side bounded by the adhesion promoter layer (16), f) obtaining the film-coated article (2).

27. Method according to claim 26, characterized in that the mixture is injected in step e) into the mold cavity with a filling pressure selected from a range of 70 bar to 140 bar, preferably from 80 bar to 100 bar.

28. Method according to claim 26 or 27, characterized in that the mold cavity forms a negative for the polyurethane layer (P) to be formed, wherein the mold cavity preferably has cavity areas of different thicknesses to form different wall thicknesses of the polyurethane layer (P).

29. Method according to one of claims 26 to 28, characterized in that the polyurethane layer (P) forms in the mold cavity as a result of injecting the mixture according to step e) at a temperature selected from a range of 40°C to 160°C, preferably from 60°C to 140°C, particularly preferably from 80°C to 120°C, and / or at a pressure selected from a range of 3 bar to 100 bar, preferably from 5 bar to 50 bar, particularly preferably from 8 bar to 30 bar.

30. Method according to any one of claims 26 to 29, characterized in that the method additionally comprises the following step, which is preferably carried out after step e): h) hardening the mixture inside and / or outside the mold cavity to form the polyurethane layer (P).

31. Method according to one of claims 26 to 30, characterized in that the method additionally comprises the following step, which is preferably carried out after step e) and / or after step h): i) removal of the carrier layer (10) of the film.

32. Method according to one of claims 26 to 31, characterized in that the film is provided in step c) as roll material and / or as continuous film and / or as a sheet and / or is introduced into the mold cavity by means of film feeder technology.

33. Method according to any one of claims 26 to 32, characterized in that the method comprises the further following step or that step a), c) and / or step f) comprises the further following sub-step: j) cleaning the film and / or the film-coated article (2), preferably the adhesion promoter layer (16) and / or the polyurethane layer (P), in particular by at least one brush, a blower and / or a suction device.

34. Method according to one of claims 26 to 33, characterized in that the method comprises the further following step or that step f) comprises the further following sub-step: k) printing the film-coated article (2), preferably the polyurethane layer (P), in particular in at least a first and / or second area, preferably alone or in combination selected from inkjet printing, gravure printing, screen printing, planographic printing, letterpress printing and flexographic printing.

35. Method according to one of claims 26 to 34, characterized in that the method comprises the further following step or that step c) comprises the further following sub-step: l) Pretreatment of the film, preferably the adhesion promoter layer, in particular by means of a method alone or in combination selected from corona treatment, flame treatment and plasma treatment.

36. Method according to one of claims 26 to 35, characterized in that the method comprises the further following step or that step f) comprises the further following sub-step: m) cutting the foil-coated article (2) by punching or waterjet cutting or laser cutting.

37. Method according to one of claims 26 to 36, characterized in that the foil-coated article (2) obtained in step f) is selected from the group consisting of display, touch field, panel, bezel, functional element, in particular from the following areas: white goods, motor vehicles, aviation, ships, household appliances, telecommunications equipment, consumer goods, documents, security elements, labels and / or electronic articles.

38. Method according to one of claims 26 to 37, characterized in that the method does not include thermoplastic injection molding.

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