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    • 专利摘要:
    glazing with thermal radiation reflective coating. the invention relates to a glazing with a coating that reflects thermal radiation, comprising at least one substrate (1) and at least one coating that reflects thermal radiation (2) at least on the surface inside the substrate (1) , wherein the glazing has a transmission in the visible spectrum range of less than 5%, and -starting from the substrate (1), the coating (2) at least comprises: -an adhesive layer (3) containing at least one material with a refractive index of less than 1.8, - a functional layer (4) containing at least one electrically conductive transparent oxide, - an optically high refractive index layer (5) containing at least one material with a refractive index greater than or equal to 1.8, and - an optically low refractive index layer (6) containing at least one material with a refractive index of less than 1.8.
    公开号:BR112015018648B1
    申请号:R112015018648-3
    申请日:2013-12-19
    公开日:2021-09-08
    发明作者:Jan Hagen；Florian Manz
    申请人:Saint-Gobain Glass France；
    IPC主号:
    专利说明:

    [0001] The invention concerns a panel with thermal radiation reflective coating, a method for its production, and its use.
    [0002] The interior of a motor vehicle can become extremely hot in summer with high ambient temperatures and intense direct sunlight. When the temperature outside is lower than the temperature inside the vehicle, which occurs particularly in winter, a cold panel acts as a heat sink, which is perceived as unpleasant by the occupants. High heating performance of the climate control system must also be provided to prevent excessive interior cooling through motor vehicle windows.
    [0003] Thermal radiation reflecting coatings (called “low-E coatings”) are known. Such a coating reflects a significant portion of sunlight, particularly in the infrared range, which, in summer, results in reduced vehicle interior heating. In addition, the coating reduces the emission of long-wave thermal radiation from a heated panel inside the vehicle when the coating is applied to the surface of a panel facing the interior of the vehicle. Furthermore, in the case of low temperatures outside in winter, such a coating reduces the emission of heat outside from the interior in external environments.
    [0004] A large number of thermal radiation reflective coatings are known to the person skilled in the art. Such coatings may contain functional layers made of niobium, tantalum, nickel, chromium, zirconium, or alloys thereof, as disclosed, for example, in US7592068B2, US7923131B2 and WO2004076174A1. The coatings can also contain functional layers made of silver, as known, for example, from EP 877 006 B1, EP 1 047 644 B1 and EP 1 917 222 B1. Furthermore, coatings with functional layers made of indium tin oxide are also known, for example, from EP2141135A1, WO2010115558A1 and WO2011105991A1.
    [0005] For aesthetic or thermal reasons, it may be desirable for a motor vehicle window panel to have reduced light transmittance. This is often the case, for example, with rear side windows, rear windows, or roof panel. It is customary to use tinted glass for such panels. However, heavily tinted glass has the disadvantage of a high level of reflection on the inside compared to the level of transmittance. While the lower transmittance on the outside ensures a desired increase in privacy, the optical impression to vehicle occupants is degraded. The perception of the external environment is interrupted for the occupants, in particular when the level of reflection from the inside is greater than the level of transmittance. Also, excessively strong reflections have an annoying or irritating effect on occupants. When the inner side surface of the panel is provided with a thermal radiation reflective coating, the reflection cannot be reduced in a simple way by conventional anti-reflective coatings because the two coatings are usually not optically compatible with each other and, consequently, cannot simply be combined.
    [0006] The objective of the present invention is to provide a panel with improved thermal radiation reflector coating as well as a method for its production. The panel should have reduced inside reflection with low light transmittance.
    [0007] The purpose of the present invention is carried out according to the invention by a panel with thermal radiation reflecting coating according to claim 1. The preferred embodiments arise from the subclaims.
    [0008] The panel according to the invention with thermal radiation reflecting coating comprises at least one substrate and at least one thermal radiation reflecting coating at least on the inner side surface of the substrate, wherein the panel has transmittance in the visible spectral range of less than 5% and wherein the coating comprises, proceeding from the substrate, at least: - an adhesive layer containing at least one material with a refractive index of less than 1.8, - a functional layer containing at least a transparent, electrically conductive oxide (TCO), - a layer with an optically high refractive index that contains at least one material with a refractive index greater than or equal to 1.8, and - a layer with an optically low refractive index which contains at least one material with a refractive index of less than 1.8.
    [0009] The panel according to the invention is provided, in an opening, for example, of a motor vehicle or a building, to separate the inside from the external environment. The surface which is intended to face inwardly in the installed position of the panel is referred to, in the context of the invention, as the inner side surface. The coating according to the invention is arranged, according to the invention, on the inner side surface of the substrate. This is particularly advantageous with respect to thermal comfort indoors. The coating according to the invention can, in the case of high external temperatures and sunlight, particularly effectively at least partially reflect the thermal radiation radiated by the panel all towards the interior. In the case of low temperatures outside, the coating according to the invention can effectively reflect the radiated thermal radiation outside the interior and thus reduce the action of the cold panel as a heat sink.
    [0010] The enormous advantage of the invention resides in the combination of a panel with very low light transmittance and the thermal radiation reflecting coating according to the invention. The low light transmittance of the panel is typically achieved by means of a dyed substrate and/or dyed layers joined to the substrate (eg, another panel and a polymeric film on a composite panel). Such a panel itself has a high level of reflection on the inside. The pronounced reflection is often perceived, by individuals located inside the panel, as uncomfortable or even irritating. This is particularly true when the level of reflection from the inside is greater than the level of transmittance, by which means the perception of the external environment is disrupted or impeded. It has surprisingly been shown that the coating according to the invention has, in addition to the reflection action of thermal radiation, a reflection-reducing action. By means of the coating according to the invention, the level of reflection on the inside is advantageously reduced and the ratio of the transmittance level to the level of reflection on the inside is advantageously increased.
    [0011] The thermal radiation reflecting coating according to the invention is a layered structure comprising at least the following layers: - the adhesive layer according to the invention, - above the adhesive layer, the functional layer according to invention, - above the functional layer, the optically high refractive index layer according to the invention, and - above the optically high refractive index layer, the optically low refractive index layer according to the invention.
    [0012] When a first layer is arranged above a second layer, this means, in the context of the invention, that the first layer is arranged further away from the substrate than the second layer. When a first layer is arranged below a second layer, this means, in the context of the invention, that the second layer is arranged further away from the substrate than the first layer.
    [0013] When a first layer is arranged above or below a second layer, this does not necessarily mean, in the context of the invention, that the first and second layers are situated in direct contact with each other. One or a plurality of additional layers may be disposed between the first and second layers, unless this is explicitly excluded.
    [0014] The highest layer of the coating is, in the context of the invention, that layer which is at the greatest distance from the substrate. The lowest layer of the coating is, in the context of the invention, that layer which is at the minimum distance from the substrate.
    [0015] When a layer or another element contains at least one material, this includes, in the context of the invention, the case where the layer is manufactured from the material.
    [0016] Oxides and nitrides, in principle, can be stoichiometric, substoichiometric, or supersubstoichiometric in relation to oxygen content or nitrogen content.
    [0017] The indicated values for the refractive indices are measured at a wavelength of 550 nm.
    [0018] The internal emissivity of the panel according to the invention is preferably less than or equal to 35%, particularly preferably less than or equal to 25%, more particularly preferably less than or equal to 20% . Here, the term “inside emissivity” refers to the measurement that indicates how much thermal radiation the panel emits within an internal space, for example, a building or a motor vehicle, in the installed position compared to an ideal thermal emitter (a black body). In the context of the invention, “emissivity” means the normal emission level at 283 K according to EN 12898.
    [0019] The panel according to the invention preferably has transmittance in the visible spectral range of less than 4%, particularly preferably of less than 3%. With panels with such low transmittance, the level of reflection from the inside is particularly advantageously reduced.
    [0020] The TL/RL ratio of the transmittance level TL inside in the visible spectral range to the level of reflection inside RL in the visible spectral range is preferably greater than or equal to 0.6, so particularly preferably greater than or equal to 0.8, more particularly preferably greater than or equal to 1, and in particular greater than or equal to 1.5. This is particularly advantageous with respect to a pleasant perception of the external environment by an observer on the inside.
    [0021] The inside transmittance level describes, in this case, the fraction of the radiation that penetrates from the outside through the panel to the inside of the radiation in the visible spectral range that impinges the panel. The fraction of the radiation's inside reflection level describes the fraction of the radiation that is reflected back inside the radiation in the visible spectral range that impinges on the inside panel.
    [0022] The value of the panel according to the invention for the total energy input of sunlight is preferably less than 50%, particularly preferably less than 40%, more particularly preferably less than 30%, in particular less than 20%. This value is also known to the person skilled in the art as the TTS ("total transmitted sun") value.
    [0023] The existence of coating sheet according to the invention is preferably from 10 ohm/square to 50 ohm/square, particularly preferably from 15 ohm/square to 30 ohm/square.
    [0024] In an advantageous embodiment of the invention, the panel according to the invention is a composite panel. The substrate is joined to a cover panel by means of at least one intermediate thermoplastic layer. The cover panel is intended to face the external environment in the installed position of the composite panel, while the substrate is facing inwards. The coating according to the invention is disposed on the substrate surface facing away from the cover panel, which is the inner side surface of the composite panel.
    [0025] The substrate and optionally the cover panel preferably contain glass, particularly preferably flat glass, float glass, quartz glass, borosilicate glass, soda-lime glass, or plastics, preferably rigid plastics, in particular polyethylene , polypropylene, polycarbonate, polymethyl methacrylate, polystyrene, polyamide, polyester, polyvinyl chloride, and/or mixtures thereof. The substrate and, optionally, the cover panel preferably have a thickness of 1.0mm to 25mm and particularly preferably 1.4mm to 4.9mm.
    [0026] When the panel according to the invention is a composite panel, the intermediate thermoplastic layer preferably contains thermoplastic plastics, for example, polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyurethane (PU), polyethylene terephthalate (PET), or multiple layers thereof, preferably with thicknesses of 0.3 mm to 0.9 mm.
    [0027] The panel has, according to the invention, transmittance in the visible spectral range of less than or equal to 5%. For this, the substrate is preferably dyed and/or appropriately colored. When the panel is a composite panel, cover panel and/or the intermediate thermoplastic layer can alternatively or additionally also be colored and/or dyed. In the case of a composite panel, the substrate and cover panel preferably have, in each case, transmittance in the visible spectral range of less than 35%, particularly preferably less than 30%. The intermediate thermoplastic layer preferably has transmittance from 20% to 80%, particularly preferably from 20% to 70%, more particularly preferably from 20% to 50%.
    [0028] The functional layer has reflective properties for thermal radiation, in particular infrared radiation, although it is largely transparent in the visible spectral range. According to the invention, the functional layer contains at least one transparent, electrically conductive oxide (TCO). The refractive index of the electrically conductive, transparent oxide is preferably from 1.7 to 2.3. The functional layer preferably contains at least fluorine-doped tin oxide (SnO2:F), antimony-doped tin oxide (SnO2:Sb), and/or indium tin oxide (ITO), particularly preferably indium tin oxide (ITO). Thus, particularly good results are obtained with respect to the emissivity and the bendability of the coating according to the invention.
    [0029] The indium tin oxide is preferably deposited using magnetically enhanced sputtering with a target fabricated from indium tin oxide. The target preferably contains from 75% by weight to 95% by weight of indium oxide and from 5% by weight to 25% by weight of tin oxide as well as production-related mixtures. The deposition of the indium tin oxide is preferably done under a protective gas atmosphere, eg argon. A small amount of oxygen can also be added to the shielding gas, for example, to improve the homogeneity of the functional layer.
    Alternatively, the target may preferably contain at least 75 wt% to 95 wt% indium and 5 wt% to 25 wt% tin. The deposition of the indium tin oxide is then preferably carried out under the addition of oxygen as off-gas during sputtering.
    [0031] However, the functional layer can also include other transparent, electrically conductive oxides, for example, mixed indium/zinc oxide (IZO), gallium-doped or aluminum-doped zinc oxide, niobium-doped titanium oxide, stannate of cadmium, and/or zinc stannate.
    [0032] The thickness of the functional layer is preferably from 50 nm to 150 nm, particularly preferably from 60 nm to 140 nm, and more particularly preferably from 70 nm to 130 nm. In this range for the thickness of the functional layer, on the one hand, advantageous anti-reflective action is obtained and, on the other hand, low emissivity.
    [0033] The optically high refractive index layer performs in particular an adjustment of the reflection color of the panel according to the invention. Furthermore, by means of the optically high refractive index layer, the stability as well as the corrosion and oxidation resistance of the functional layer can be improved. This is particularly advantageous when the panel provided with the coating is to be subjected to a temperature treatment, a bending process, and/or a pre-straining process.
    [0034] The refractive index of the optically high refractive index layer material is preferably from 1.7 to 2.3 and is particularly preferable greater than or equal to the refractive index of the functional layer material. Thus, advantageous optical properties of the coating are obtained, in particular an aesthetic color impression.
    [0035] The optically high refractive index layer preferably contains at least one oxide or nitride, particularly preferably tungsten oxide, niobium oxide, tantalium oxide, zirconium oxide, hafnium oxide, bismuth oxide, bismuth oxide titanium, silicon nitride, zirconium nitride, hafnium nitride, and/or aluminum nitride. The optically high refractive index layer particularly preferably contains silicon nitride (Si3N4). Thus, particularly good results are obtained with respect to coating stability and optical properties. Silicon nitride can have dopants, for example titanium, zirconium, boron, hafnium and/or aluminum. Silicon nitride is most particularly preferably doped with aluminum (Si3N4:Al) or doped with zirconium (Si3N4:Zr) or doped with boron (Si3N4:B). This is particularly advantageous with regard to the optical properties and emissivity of the coating as well as the speed of application of the optically high refractive index layer, for example, by sputtering.
    [0036] Silicon nitride is preferably deposited using magnetically enhanced sputter with a target that contains at least silicon. The target for deposition of a layer containing aluminum doped silicon nitride preferably contains from 80% by weight to 95% by weight of silicon and from 5% by weight to 20% by weight of aluminum as well as production-related mixtures. The target for deposition of a boron-doped silicon nitride containing layer preferably contains from 99.9990 wt% to 99.9999 wt% silicon and from 0.0001 wt% to 0.001 wt% boron as well as production-related mixtures. The target for the deposition of a layer containing zirconium-doped silicon nitride preferably contains from 60% by weight to 90% by weight of silicon and from 10% by weight to 40% by weight of zirconium as well as production-related mixtures. The deposition of silicon nitride is preferably done under the addition of nitrogen as off-gas during sputtering.
    [0037] The thickness of the optically high refractive index layer is preferably less than 20 nm, particularly preferably less than 12 nm, more particularly preferably less than 10 nm and in particular less than 8 nm. The thickness of the optically high refractive index layer should be at least 1 nm, preferably at least 2 nm. In this range for the thickness of the optically high refractive index layer, particularly advantageous anti-reflective properties of the coating according to the invention are obtained. The thickness is preferably from 1 nm to 20 nm, particularly preferably from 2 nm to 12 nm, more particularly preferably from 2 nm to 10 nm, and in particular from 2 nm to 8 nm.
    [0038] During a temperature treatment after application of the coating according to the invention, the silicon nitride can be partially oxidized. A layer deposited as Si3N4 then contains, after temperature treatment, SixNyOz, with the oxygen content typically from 0% atomic to 35% atomic.
    [0039] The adhesive layer results in a durable stable adhesion of the layers deposited above the adhesive layer on the substrate. The adhesive layer further prevents the accumulation of ions diffusing from the substrate in the boundary area to the functional layer, in particular sodium ions if the substrate is made of glass. Such ions can lead to corrosion and poor adhesion of the functional layer. The adhesive layer is therefore particularly advantageous with respect to the stability of the functional layer.
    [0040] The adhesive layer preferably contains at least one material with a refractive index between 1.5 and 1.8. The material of the adhesive layer preferably has a refractive index in the range of the refractive index of the substrate. The adhesive layer can contain, for example, at least one oxide and/or a nitride, preferably at least one oxide. The adhesive layer particularly preferably contains silicon dioxide (SiO2). This is particularly advantageous with respect to adhesion of the layers to the substrate deposited above the adhesive layer. Silicon dioxide can have dopants, for example fluorine, carbon, nitrogen, boron, phosphorus and/or aluminum. Silicon dioxide is most particularly preferably doped with aluminum (SiO2:Al), doped with boron (SiO2:B), or doped with zirconium (SiO2:Zr). This is particularly advantageous with regard to the optical properties of the coating as well as the speed of application of the adhesive layer, for example by sputtering.
    [0041] Silicon dioxide is preferably deposited using magnetically enhanced sputter with a target that contains at least silicon. The target for the deposition of an aluminum-doped silicon dioxide-containing adhesive layer preferably contains from 80% by weight to 95% by weight of silicon and from 5% by weight to 20% by weight of aluminum as well as production-related mixtures . The target for the deposition of a boron-doped silicon dioxide containing adhesive layer preferably contains from 99.9990 wt% to 99.9999 wt% silicon and from 0.0001 wt% to 0.001 wt% boron thus as production-related mixtures. The target for the deposition of a zirconium-doped silicon dioxide-containing adhesive layer preferably contains from 60% by weight to 90% by weight of silicon and from 10% by weight to 40% by weight of zirconium as well as production-related mixtures . The deposition of silicon dioxide is preferably done under the addition of oxygen as off-gas during sputtering.
    [0042] Doping of the adhesive layer can also improve the smoothness of the layers applied above the adhesive layer. The high smoothness of the layers is particularly advantageous in the case of using the panel according to the invention in the motor vehicle sector since, by these means, an unpleasant rough surface feel of the panel is avoided. When the panel according to the invention is a side window panel, it can be moved with low friction with the sealing lips.
    [0043] However, alternatively, the adhesive layer can also contain, for example, aluminum oxide (Al2O3).
    The adhesive layer preferably has a thickness of 10 nm to 150 nm, particularly preferably of 15 nm to 50 nm, for example approximately 30 nm. This is particularly advantageous with regard to adhesion of the coating according to the invention and the prevention of diffusion of ions from the substrate into the functional layer.
    [0045] An additional optically active layer, preferably with a thickness of 5 nm to 40 nm, may also be disposed below the adhesive layer. For example, the adhesive layer can contain SiO2 and the additional optically active layer can contain at least one oxide, such as TiO2, Al2O3, Ta2O5, Y2O3, ZnO, and/or ZnSnOx, or a nitride, such as AlN or Si3N4. By means of the optically active layer, the anti-reflective properties of the coating according to the invention are advantageously further improved. In addition, the optically active layer allows for improved adjustment of color values in transmittance or reflection.
    [0046] The optically low refractive index layer is critical for the anti-reflective action of the coating according to the invention. Furthermore, by means of the optically low refractive index layer, a neutral color impression of reflected and transmitted light is obtained and the corrosion resistance of the functional layer is improved.
    [0047] The optically low refractive index layer, for example, may contain at least an oxide and/or a nitride. The optically low refractive index layer preferably contains at least one oxide, particularly preferably at least silicon oxide (SiO2). This is particularly advantageous with respect to the optical properties of the panel and the corrosion resistance of the functional layer. Silicon dioxide can have dopants, for example fluorine, carbon, nitrogen, boron, phosphorus and/or aluminum. Silicon oxide is more particularly preferably doped with aluminum (SiO2:Al), doped with boron (SiO2:B), or doped with zirconium (SiO2:Zr). Thus, particularly good results are obtained.
    [0048] However, alternatively, the optically low refractive index layer may contain, for example, aluminum oxide (Al2O3).
    [0049] The optically low refractive index layer preferably has a thickness from 40 nm to 130 nm, particularly preferably from 50 nm to 120 nm, more particularly preferably from 60 nm to 110 nm, and in particular from 70 nm to 100 nm. This is particularly advantageous with respect to low reflection and high visible light transmittance as well as the adjustment of a selected color impression of the panel and the corrosion resistance of the functional layer. In this range for the optically low refractive index layer thickness, particularly advantageous anti-reflective properties of the coating according to the invention are obtained.
    [0050] In an advantageous embodiment of the invention, a cover layer is arranged above the optically high refractive index layer. The cover layer protects the coating according to the invention against damage, in particular against scratches. The cover layer preferably contains at least one oxide, particularly preferably at least TiO2, ZrO2, HfO2, Nb2O5, Ta2O5, Cr2O3, WO3 and/or CeO2. The thickness of the cover layer is preferably from 2 nm to 50 nm, particularly preferably from 5 nm to 20 nm. Thus, particularly good results are obtained with respect to scratch resistance.
    [0051] In an advantageous embodiment, no layer with a refractive index greater than the refractive index of the adhesive layer is disposed below the adhesive layer and no layer with a refractive index greater than the refractive index of the layer of optically low refractive index is arranged above the optically low refractive index layer. This is particularly advantageous with respect to the optical properties of the panel and a single-layer structure.
    [0052] The panel according to the invention can be flat or light or enormously curved in one or a plurality of spatial directions. Such curved panels occur, in particular, for glazing in the motor vehicle sector. Typical radii of curvature of curved panels are in the range of approximately 10 cm to approximately 40 m. The coating according to the invention has been shown to be particularly well adapted to withstand a bending process without damage such as cracking.
    [0053] The coating according to the invention can be applied on the surface of the substrate over its entire area. However, the substrate surface may also have free coating regions. The substrate surface, for example, may have a circumferential coating free edge region and/or a coating free region that serves as a data transmission window or a communication window. In the coating-free region, the panel is permeable to electromagnetic radiation and in particular to infrared radiation.
    [0054] When the panel according to the invention is a composite panel, in an advantageous embodiment, a sun protection coating is applied on the surface of the substrate facing the cover panel, on the surface of the cover panel facing onto the substrate, or onto a carrier film in the intermediate thermoplastic layer. The sun protection coating is there advantageously protected against corrosion and mechanical damage. The sun protection coating preferably comprises at least one metallic layer based on silver or a silver-containing alloy with a thickness of 5 nm to 25 nm. Particularly good results are obtained with two or three functional layers which are separated from each other by dielectric layers with thicknesses from 10 nm to 100 nm. The sunshield coating reflects fractions of incident sunlight outside the visible spectral range, in particular the infrared spectral range. Through the solar protection coating, the heating of the interior by direct sunlight is reduced. Furthermore, the solar protection coating reduces the heating of the composite panel elements placed behind the solar protection coating and thus the thermal radiation emitted by the composite panel. By combining the solar protection coating with the coating according to the invention for reflecting thermal radiation, the thermal comfort in the interior is advantageously further improved.
    [0055] The invention further comprises a method for producing a panel according to the invention with thermal radiation reflective coating, wherein at least: (a) an adhesive layer (3) containing at least one material with a refractive index of less than 1.8, (b) a functional layer (4) that contains at least one transparent, electrically conductive oxide (TCO), (c) an optically high refractive index layer (5) that contains at least one material with a refractive index greater than or equal to 1.8, and (d) an optically low refractive index layer (6) which contains at least one material with a refractive index of less than 1.8, are applied in succession to the inner side surface of a substrate.
    The individual layers are deposited by methods known per se, preferably by magnetically enhanced sputtering. This is particularly advantageous with respect to simple, fast, economical, and uniform coating of the substrate. Sputtering is done in a protective gas atmosphere, eg argon, or in a reactive gas atmosphere, eg by the addition of oxygen or nitrogen.
    [0057] However, the individual layers can also be applied by other methods known to the person skilled in the art, for example, by vapor deposition or chemical vapor deposition (CVD), by atomic layer deposition (ALD), by deposition of chemical vapor enhanced by plasma (PECVD), or by wet chemical methods.
    [0058] Preferably after application of the thermal radiation reflective coating, the panel is subjected to a temperature treatment. The substrate with the coating according to the invention is heated to a temperature of at least 200°C, particularly preferably at least 300°C. The crystallinity of the functional layer is, in particular, improved by temperature treatment. In particular, the temperature treatment reduces the sheet strength of the coating, which results in reduced emissivity and improved reflective properties with respect to thermal radiation. Furthermore, the optical properties of the panel are significantly improved.
    [0059] In an advantageous embodiment of the method according to the invention, the temperature treatment takes place within a bending process. The substrate with the coating according to the invention is curved, in the heated state, in one or a plurality of spatial directions. The temperature to which the substrate is heated is preferably from 500°C to 700°C. It is a particular advantage of the coating for reflecting thermal radiation according to the invention that it can be subjected to such a bending process without being damaged. The darkened layer according to the invention is not damaged during the bending process, for example by cracking.
    [0060] Of course, other temperature treatment steps can occur before or after the bending process. A temperature treatment, alternatively, can also be performed using laser radiation.
    [0061] In an advantageous embodiment, after temperature treatment and optionally after bending, the substrate can be provided with pre-tensioned or partially pre-tensioned. For this, the substrate is suitably cooled in a manner known to you. A pre-strained substrate typically has surface compressive stresses of at least 69 MPa. A partially pre-tensioned substrate typically has surface compressive stresses of 24 MPa to 52 MPa. A pre-tensioned substrate is suitable as single-pane safety glass, for example, as a side window or rear window of a motor vehicle.
    [0062] In an advantageous embodiment of the invention, after application of the coating, the substrate is joined by means of at least one intermediate thermoplastic layer to a cover panel to form a composite panel. In principle, the substrate can also be first joined to the cover panel and then provided with the coating.
    [0063] The invention further includes the use of the panel according to the invention with thermal radiation reflective coating in buildings, as a component incorporated in furniture and devices, or in means of transport for travel by land, in air, or in water , in particular on trains, boats, and motor vehicles, for example, as a rear window, side window, and/or roof panel.
    [0064] The invention is explained in detail in the following with reference to drawings and exemplary embodiments. Drawings are schematic representations and not true scale. The drawings in no way restrict the invention.
    [0065] They represent: Fig. 1 a cross section through an embodiment of the panel according to the invention with thermal radiation reflective coating, Fig. 2 a cross section through another embodiment of the panel according to the invention with thermal radiation reflecting coating, Fig. 3 a cross section through another embodiment of the panel according to the invention with thermal radiation reflecting coating, Fig. 4 a diagram of the TL/RL ratio as a function of adhesive layer thickness, Fig. 5 a diagram of the TL/RL ratio as a function of the functional layer thickness, Fig. 6 a diagram of the TL/RL ratio as a function of the optically high refractive index layer thickness, Fig. 7 a diagram of the TL/RL ratio as a function of the thickness of the optically low refractive index layer, and Fig. 8 a detailed flowchart of an embodiment of the method according to the invention.
    [0066] Fig. 1 represents a cross section through an embodiment of the panel according to the invention with the substrate 1 and the thermal radiation reflecting coating 2. The substrate 1 contains, for example, dyed soda-lime glass and has a thickness of 6mm. The coating 2 comprises an adhesive layer 3, a functional layer 4, an optically high refractive index layer 5, and an optically low refractive index layer 6. The layers are arranged in the order indicated with increasing distance from substrate 1.
    [0067] The adhesive layer 3 is manufactured, for example, from silicon oxide doped with aluminum and has a thickness of 30 nm. The functional layer 4 is manufactured, for example, from indium tin oxide (ITO) and has a thickness of 130 nm. The optically high refractive index layer 5 is manufactured, for example, from aluminum-doped silicon nitride and has a thickness of 5 nm. The optically low refractive index layer 6 is manufactured, for example, from aluminum doped silicon oxide and has a thickness of 70 nm auf.
    [0068] The individual layers of coating 2 were deposited using magnetically enhanced sputter. The target for the deposition of the adhesive layer 3 and the optically low refractive index layer 6 contained 92 wt% silicon and 8 wt% aluminium. The deposition was done under the addition of oxygen as off-gas during sputtering. The target for the deposition of the functional layer 4 contained 90% by weight of indium oxide and 10% by weight of tin oxide. The deposition was done under a protective gaseous atmosphere of argon with an oxygen fraction of less than 1%. The target for the deposition of the optically high refractive index layer 5 contained 92 wt% silicon and 8 wt% aluminium. The deposition was carried out under the addition of nitrogen as off-gas during sputtering.
    [0069] Fig. 2 represents a cross section through another embodiment of the panel according to the invention with the substrate 1 and the thermal radiation reflecting coating 2. The coating 2 is configured as in Fig. 1 with the adhesive layer 3, functional layer 4, optically high refractive index layer 5, and optically low refractive index layer 6. A cover layer 7 is disposed above the coating 2. The cover layer contains TiO2 and has a thickness of 10 nm. By means of the covering layer, the coating 2 is advantageously protected against mechanical damage, in particular against scratches.
    [0070] Fig. 3 represents a cross section through a panel according to the invention with thermal radiation reflective coating 2 as a composite panel. The substrate 1 is joined to a cover panel 8 by means of an intermediate thermoplastic layer 9. The composite panel is intended as a roof panel for a motor vehicle. The composite panel is curved as usual for panels in the automotive sector. In the installed position of the composite panel, the cover panel 8 faces the external environment and the substrate 1 faces the interior of the vehicle. The inner side surface of the substrate 1, which faces away from the cover panel 8 and the intermediate thermoplastic layer 9, is provided with the coating 2 according to the invention. Substrate 1 and cover panel 8 are made of soda-lime glass and in each case have a thickness of 2.1 mm. Intermediate thermoplastic layer 9 contains dyed polyvinyl butyral (PVB) and has a thickness of 0.76 mm.
    [0071] The substrate 1, the cover panel 8, and the intermediate thermoplastic layer 9 are dyed. Substrate 1 and cover panel 9 have, for example, in each case transmittance in the visible spectral range of 27%; the intermediate thermoplastic layer 8 has, for example, a transmittance of 23 %. The composite panel has, without cladding 2, transmittance TL from the inside in the visible spectral range of 2.3% and reflection RL from the inside of 4.4% auf. The TL/RL ratio is 0.5 without the coating 2. The thermal radiation reflective coating 2 according to the invention surprisingly improves not only the thermal comfort inside the motor vehicle, but also acts as an anti-reflective coating. The RL reflection from the inside is reduced to 2.0% by coating 2. The TL/RL ratio is increased to 1.1 by coating 2. As a result of coating 2, individuals inside the motor vehicle are able to perceive better the external environment and are less disturbed by reflections.
    [0072] Fig. 4, Fig. 5, Fig. 6, and Fig. 7 show simulation results of the TL/RL ratio from the TL transmittance level in the visible spectral range to the RL reflection level in the visible spectral range. The higher the TL/RL ratio, the less pronounced the nuisance of reflections on the inside and the more pleasant the optical impression of the panel. Fig. 4 shows the TL/RL ratio as a function of the thickness of adhesive layer 3. Fig. 5 shows the TL/RL ratio as a function of the thickness of the functional layer 4. Fig. 6 shows the TL/RL ratio as a function of the thickness of the optically high refractive index layer 5. Fig. 7 presents the TL/RL ratio as a function of the thickness of the optically low refractive index layer 6.
    [0073] The simulations assume the basic layer structure, whose layer sequence is presented with materials and layer thicknesses in Table 1. In each case, one of the layer thicknesses was varied; the remaining layer thicknesses corresponded to the values in Table 1. The aggregate of substrate 1, intermediate thermoplastic layer 8, and cover glass 9 had, without coating 2, TL transmittance of approximately 4.2 %.
    [0074] By way of comparison, the figures show the TL/RL ratio without coating 2. The values are given in each case for two different observation angles α. Angle α is the angle between the observation direction (connection line between the observer and the panel) and the normal surface of the panel. Table 1

    [0075] The absolute values for the TL/RL ratio depend on the transmittance through the panel. A lower transmittance with unchanged reflection results in a lower TL/RL ratio. This means that the same coating 2 on a panel with lower transmittance produces a lower TL/RL ratio than on a panel with higher transmittance. The qualitative dependence of the TL/RL ratio is, however, independent of the transmittance of the panel and can be found in the figures.
    [0076] From Fig. 4, it is discernible that the TL/RL ratio has no evident dependence on the thickness of the adhesive layer 3. The thickness of the adhesive layer 3 thus hardly influences the anti-reflective properties of the coating 2. The thickness of adhesive layer 3, therefore, can be selected on the basis of adhesion promoting properties and barrier action against ion diffusion. It has been shown that particularly good results are obtained with an adhesive layer having a thickness of 10 nm to 150 nm, preferably 15 nm to 50 nm.
    [0077] From Fig. 5, it is discernible that the thickness of the functional layer 4 has a clear influence on the anti-reflective properties of the coating 2 and thus on the TL/RL ratio. The maximum for the TL/RL ratio is obtained at a thickness of approximately 100 nm. In order to improve the reflective action of thermal radiation, a thicker functional layer 4, however, may be desirable. It has been shown that for functional layer 4 thicknesses from 50 nm to 150 nm, preferably from 60 nm to 140 nm, particularly preferably from 70 nm to 130 nm, a good fit between the TL/RL ratio and the reflective action of the radiation thermal is obtained.
    [0078] From Fig. 6 it is discernible that the thickness of the optically high refractive index layer 5 has an evident influence on the anti-reflective properties of the coating 2 and thus on the TL/RL ratio. The TL/RL ratio becomes higher the thinner the optically high refractive index layer 5 is implemented. With a thickness of less than 20 nm, the TL/RL ratio is greater than with uncoated panel 2. Particularly good results are obtained for a layer thickness of optically high refractive index 5 of less than 12 nm, preferably less than 10 nm, particularly preferably less than 8 nm. However, for the optically high refractive index layer 5 to be able to effectively protect the functional layer 4 against corrosion and oxidation, it must have a thickness of at least 1 nm, preferably at least 2 nm.
    [0079] From Fig. 7, it is discernible that the thickness of the optically low refractive index layer 6 has an evident influence on the anti-reflective properties of the coating 2 and thus on the TL/RL ratio. With a thickness of approximately 40 nm to 130 nm, the TL/RL ratio is greater than with the uncoated panel 2. Particularly good results are obtained for a layer thickness of optically low refractive index 6 from 50 nm to 120 nm , preferably from 60 nm to 110 nm, particularly preferably from 70 nm to 100 nm.
    [0080] By means of the coating 2 according to the invention, not only a reflecting action of thermal radiation is obtained, but also an anti-reflective action. When coating 2 is applied over the panel with low light transmittance, it reduces annoying and irritating inside reflections. The anti-reflective action is even more pronounced with the incidence of oblique light. These results were unexpected and surprising to the person skilled in the art.
    [0081] Fig. 8 represents a flowchart of an exemplary embodiment of the method according to the invention for producing a panel with thermal radiation reflective coating 2.
    [0082] List of Reference Characters: (1) substrate (2) thermal radiation reflective coating (3) adhesive layer (4) functional layer (5) optically high refractive index layer (6) optically refractive index layer bottom (7) cover layer (8) cover panel (9) intermediate thermoplastic layer
    权利要求:
    Claims (14)
    [0001]
    1. Panel with thermal radiation reflecting coating separating an interior of the panel from an external environment, wherein the panel comprises at least one substrate (1) and at least one thermal radiation reflecting coating (2) situated on at least one surface inner side of the substrate (1), in which the panel has transmittance in the visible spectral range of less than 5%, and characterized by the fact that the coating (2), proceeding from the substrate (1), comprises at least: - an adhesive layer (3) containing at least one material with a refractive index of less than 1.8, - a functional layer (4) containing at least one transparent, electrically conductive oxide, - an index layer of optically high refraction (5) containing at least one material with a refractive index greater than or equal to 1.8, and - an optically low refractive index layer (6) containing at least one material with an index of refraction of less than 1.8.
    [0002]
    2. Panel according to claim 1, characterized in that it is a composite panel, in which the substrate (1) is joined to a cover panel (8) by means of at least one intermediate thermoplastic layer (9) .
    [0003]
    3. Panel according to claim 1, characterized in that it has transmittance in the visible spectral range of less than 4%.
    [0004]
    4. Panel according to claim 1, characterized in that the adhesive layer (3) contains at least one oxide.
    [0005]
    5. Panel according to claim 1, characterized in that the adhesive layer (3) has a thickness of 10 nm to 150 nm.
    [0006]
    6. Panel according to claim 1, characterized in that the functional layer (4) contains at least fluorine-doped tin oxide, antimony-doped tin oxide, indium tin oxide or a mixture thereof.
    [0007]
    7. Panel according to claim 1, characterized in that the functional layer (4) has a thickness of 50 nm to 150 nm.
    [0008]
    8. Panel according to claim 1, characterized in that the optically high refractive index layer (5) contains at least one oxide or nitride.
    [0009]
    9. Panel according to claim 1, characterized in that the optically high refractive index layer (5) has a thickness of at least 1 nm and less than 20 nm.
    [0010]
    10. Panel according to claim 1, characterized in that the optically low refractive index layer (6) contains at least one oxide.
    [0011]
    11. Panel according to claim 1, characterized in that the optically low refractive index layer (6) has a thickness of 40 nm to 130 nm.
    [0012]
    12. Panel according to claim 1, characterized in that a covering layer (7) containing at least one oxide is arranged above the optically low refractive index layer (6).
    [0013]
    13. Panel according to claim 1, characterized in that the ratio of the transmittance level TL inside the visible spectral range to the reflection level RL inside the visible spectral range TL/RL of the panel is greater than or equal to 0.6.
    [0014]
    14. Panel according to claim 1, characterized in that it is a rear window, side window, and/or roof panel of a train, boat or motor vehicle.
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    ES2873150T3|2021-11-03|
    EA027662B1|2017-08-31|
    JP6012887B2|2016-10-25|
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    US20160002099A1|2016-01-07|
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    MX360106B|2018-10-23|
    BR112015018648A2|2017-07-18|
    US9650291B2|2017-05-16|
    EP2958871A1|2015-12-30|
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    EP2958871B1|2021-03-10|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-05-18| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-08-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-09-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/12/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
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    EP13155970|2013-02-20|
    EP13155970.0|2013-02-20|
    PCT/EP2013/077352|WO2014127868A1|2013-02-20|2013-12-19|Panel with a coating which reflects thermal radiation|
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