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    • 专利摘要:
    GLASS WITH THERMAL RADIATION REFLECTOR COATING. The invention relates to a glazing having a coating that reflects thermal radiation, comprising a substrate (1) and at least one coating (2) that reflects thermal radiation on at least one of the surfaces of the substrate (1), wherein the coating (2) comprises, proceeding from the substrate (1), at least a lower dielectric layer (3), a functional layer (4), which contains at least one transparent, electrically conductive oxide, and an upper dielectric layer (5), and wherein at least one darkening layer (10) is arranged below the lower dielectric layer (3), between the lower dielectric layer (3) and the functional layer (4), between the functional layer (4) and the dielectric layer (5), and/or above the upper dielectric layer (5), and wherein the darkening layer (10) contains at least one metal, a metal nitrite, and/or a metal carbide having a melting point greater than than 1900°C and a specific electrical resistivity of less than 500 μohm*cm.
    公开号:BR112015018645B1
    申请号:R112015018645-9
    申请日:2013-12-19
    公开日:2022-01-25
    发明作者:Martin Melcher；Jan Hagen；Julia Vincent
    申请人:Saint-Gobain Glass France；
    IPC主号:
    专利说明:

    [0001] The invention relates to a panel with a thermal radiation reflective coating, a method for its production, and the use of a darkened layer in a panel with such a coating.
    [0002] The interior of a motor vehicle can heat up enormously in summer with high ambient temperatures and intense direct sunlight. When the temperature outside is lower than the temperature inside the vehicle, which is particularly the case in winter, a cold panel acts as a heat sink, which is perceived as unpleasant by the occupants. The high heating performance of the climate control system must also be provided to prevent excessive cooling of the interior through the motor vehicle windows.
    [0003] Thermal radiation reflective coatings (called “low E coatings”) are known. Such a coating reflects a significant part of sunlight, particularly in the infrared range, which, in summer, results in reduced heating of the vehicle interior. 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 from the inside to the outside.
    [0004] 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. Such a panel can be produced through the use of a transmittance-reducing thermal radiation reflective coating. Transmittance-reducing thermal radiation reflective coatings containing functional layers made of niobium, tantalum, nickel, chromium, zirconium, or alloys thereof are known to the person skilled in the art, for example, from US7592068B2, US7923131B2, and WO2004076174A1. Due to the low light transmittance of the coating, layer defects, in particular production-related defects that may be present, have an undesirably high contrast. Even very small defects with a size, for example, of about 100 □ m can be annoyingly noticeable to an observer, particularly when looking through the panel. Such layer defects, for example, can occur where before and/or during a coating process, particles contaminate the surface of the panel to be coated and are released from the surface after coating. Particles may also be released from the surface during subsequent heat treatment of the panel surface.
    [0005] To avoid the disadvantages of transmittance-reducing coatings, it is possible to apply transparent thermal radiation reflective coatings on tinted panels. Such coatings may contain functional layers based on a transparent conductive oxide, such as indium tin oxide, and are known, for example, from EP 2 141 135 A1, WO 2010115558 A1, and WO 2011105991 A1. Panels with very low light transmittance, for example of less than 8%, however, are not easily realized in this way, as glasses with light transmittance of less than 10% are usually not commercially available.
    [0006] Often, after application of the coating, the panels must be subjected to a thermal treatment and a mechanical transformation. Panels for the automotive sector, e.g. side windows and rear windows in the form of single-pane safety glass and roof panel, side windows, and rear windows in the form of composite safety glass are typically curved and often supplied with pre-sets. -tensioning or partial pre-tensioning in this process. The panel's curvature and pre-tension also place particular demands on the cladding.
    [0007] From US 2008/0070045 A1, another panel with a low E coating is known, wherein the functional layer contains a transparent conductive oxide. The coating contains a layer for absorbing thermal radiation, for example made of titanium nitride. The thickness of the absorption layer is not specified.
    [0008] From US 2005/0123772 A1, a low E coating with a functional layer made of silver is known. The coating contains a light-absorbing layer made of titanium nitride. Low E silver based coatings are very susceptible to corrosion and therefore may not be used on environmentally contacting panel surfaces. Its use is typically restricted to composite panel surfaces facing the middle layer. Use on the inner surface of a panel is therefore not possible.
    [0009] The objective of the present invention is to provide a panel with improved thermal radiation reflective coating, wherein the thermal radiation reflective coating reduces the transmittance of the panel in the visible spectral range. The coating must also be corrosion resistant and must not be damaged during panel bending and pre-tensioning. In addition, a method for producing the panel must be provided.
    [0010] The object of the present invention is realized according to the invention by a panel with a thermal radiation reflective coating according to claim 1. Preferred embodiments arise from the subclaims.
    [0011] The panel according to the invention with a thermal radiation reflective coating comprises a substrate and at least one thermal radiation reflective coating on at least one of the surfaces of the substrate, wherein the coating, proceeding from the substrate, comprises at least: - a lower dielectric layer, - a functional layer containing at least one transparent, electrically conductive oxide, and - an upper dielectric layer, and wherein at least one darkened layer is arranged below the lower dielectric layer, between the lower dielectric layer and the functional layer, between the functional layer and the upper dielectric layer, and/or above the upper dielectric layer, and wherein the darkened layer contains at least one metal, one metal nitride, and/or one metal carbide having a higher melting point than 1900 °C and a specific electrical resistivity of less than 500 μohm*cm.
    [0012] The thermal radiation reflective coating according to the invention is a stack of layers, comprising at least the following individual layers in the order indicated, proceeding from the substrate: - a lower dielectric layer, - above the lower dielectric layer, a functional layer that contains at least one transparent, electrically conductive oxide (TCO), and - above the functional layer, a top dielectric layer.
    [0013] The coating, moreover, comprises at least one darkened layer according to the invention.
    [0014] 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 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 from the substrate than the first layer.
    [0015] 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 arranged between the first and second layers, unless this is explicitly excluded.
    [0016] The highest layer of the coating is, in the context of the invention, that layer that 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.
    [0017] The values indicated for the specific electrical resistivity are measured at a temperature of 20°C. The indicated values for refractive indices are measured at a wavelength of 550 nm.
    [0018] The person skilled in the art, for example, can find the indicated values for the melting point and the specific electrical resistivity in tables or explanatory leaflets. Typically, the values given are for a solid. In the case of thin films, the melting point and specific electrical resistivity can deviate from this. The tabulated values for solids nevertheless provide the person skilled in the art with adequate criteria for selecting suitable materials for the darkened layer in accordance with the invention. The values given for melting point and specific electrical resistivity must be understood in this context.
    [0019] 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.
    [0020] The metal, metal nitride, and/or metal carbide according to the invention of the darkened layer has a low specific electrical resistivity and thus a defined electrical conductivity. By means of such a conductive darkening layer, the transmittance in the visible spectral range of the reflective coating of thermal radiation is reduced, in particular by absorption and/or reflection. Of course, the darkened layer can also reduce transmittance in other spectral ranges, for example in the infrared range. The transmittance level can be adjusted by the number and thickness as well as the material of the darkened layers. Thus, even very dark panels can be realized, in particular, if the coating according to the invention is used on the dyed panels. This is a main advantage of the invention.
    [0021] The metal, metal nitride, and/or metal carbide according to the invention of the darkened layer also has a high melting point. Such darkened layers are advantageously resistant to corrosion and oxidation. Consequently, the coated panel can be further subjected to a temperature treatment, a bending process, and/or a pre-tensioning process without the coating being damaged (e.g., by cracks in the darkened layer) or for light transmittance. be increased once more as a result of oxidation of the darkened layer. This is another main advantage of the present invention.
    [0022] The panel according to the invention is preferably provided, in an opening, for example, of a motor vehicle or a building, to separate the interior from the external environment. The coating according to the invention is preferably disposed on the surface of the substrate which is intended to face inwards in the installed position of the panel. This is particularly advantageous with respect to thermal comfort in the interior. The surface that is intended to face inwardly in the installed position of the panel is referred to, in the context of the invention, as the inner surface. 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 entire panel towards the interior. In the case of low outside temperatures, the coating according to the invention can effectively reflect the radiated heat radiation from the inside and thus reduce the action of the cold panel as a heat sink.
    [0023] The internal lateral 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 inside 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.
    [0024] The panel according to the invention has, in an advantageous embodiment, transmittance in the visible spectral range of less than 25%, preferably less than 15%, particularly preferably less than 10%, so more particularly preferably less than 8%, and in particular less than 6%. The invention is particularly advantageous for panels with transmittance of less than 10%. Such panels are difficult to make using only a dyed substrate because such heavily dyed substrates are typically not commercially available. Panels with such low transmittances may be desirable, in particular as a side window, rear window, or roof panel of a motor vehicle or also in buildings.
    [0025] 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%. This value is also known to the person skilled in the art as the TTS value ("total transmitted sun").
    [0026] The sheeting of the coating according to the invention is preferably from 10 ohm/square to 50 ohm/square, particularly preferably from 15 ohm/square to 30 ohm/square.
    [0027] The thermal radiation reflective coating includes, according to the invention, at least one darkened layer. The coating may also include multiple darkened layers, for example two, three, or four darkened layers, which may be desirable for optical or mechanical reasons.
    [0028] In an advantageous embodiment, the coating contains one or two darkened layers according to the invention. This is particularly advantageous with respect to the simple production of the coating.
    [0029] The darkened layer or multiple darkened layers may be arranged, for example, below the lower dielectric layer, between the lower dielectric layer and the functional layer, between the functional layer and the upper dielectric layer, and/or above the layer superior dielectric.
    [0030] In particularly advantageous embodiments, the darkened layer is or the darkened layers are arranged between the lower dielectric layer and the functional layer and/or between the functional layer and the upper dielectric layer. Preferably, in this case, the darkened layers are in direct contact with the functional layer. It has surprisingly been shown that such a thermal radiation reflective coating is particularly well adapted to withstand without damage a temperature treatment, a bending process, and a pre-strain process.
    [0031] The darkened layer preferably has a thickness of from 2 nm to 50 nm, particularly preferably from 5 nm to 40 nm, more particularly preferably from 10 nm to 30 nm. This is particularly advantageous with respect to the transmittance reducing action as well as the corrosion resistance and bendability of the darkened layer.
    [0032] The darkened layer contains, according to the invention, at least one metal, a metal nitride, and/or a metal carbide. Here, in the context of the invention, the term "metals" also includes alloys of two or more metals. Also included are mixed nitrides and mixed carbides of two or more metals as well as alloys, mixed nitrides, or mixed carbides of a metal with silicon and/or aluminum.
    [0033] Metals and metal carbide may contain small amounts related to the production of oxygen. The oxygen content is in this case preferably less than 30% by weight, particularly preferably less than 20% by weight.
    [0034] The metal which is contained in the darkened layer or whose oxides or nitrides are contained in the darkened layer is preferably selected from transition metals, particularly preferably from groups IVB, VB, and VIB of the periodic system. The darkened layer preferably contains at least one metal, metal nitride, or metal carbide from the group consisting of hafnium, niobium, tantalum, molybdenum, tungsten, titanium nitride, zirconium nitride, hafnium nitride, vanadium nitride, niobium nitride, tantalum nitride, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tantalum carbide, molybdenum carbide, and tungsten carbide, or mixtures or alloys thereof. The melting points TS and the specific electrical resistivities p of the indicated materials are summarized in Table 1 (as also H.O. Pierson: Handbook of Refractory Carbides and Nitrides. Wesduasod: Noyes Publications, 1996).
    [0035] The melting point of the metal, metal nitride, and/or metal carbide is preferably greater than 2200°C, particularly preferably greater than 2500°C. This is particularly advantageous with respect to the corrosion and oxidation resistance of the darkened layer.
    [0036] The specific electrical resistivity of the metal, metal nitride, and/or metal carbide is preferably less than 200 μohm*cm. This is particularly advantageous with respect to the transmittance-reducing action of the darkened layer.
    [0037] The darkened layer preferably contains at least one metal, metal nitride, or metal carbide from the group consisting of hafnium, niobium, tantalum, molybdenum, tungsten, titanium nitride, zirconium nitride, hafnium nitride, niobium nitride, nitride of tantalum, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tantalum carbide, molybdenum carbide, and tungsten carbide, or mixtures or alloys thereof, or alloys, mixed nitrides or carbides mixtures thereof with silicon or aluminum. That is, due to the high melting point greater than 2200°C, particularly advantageous for the corrosion resistance of the darkened layer.
    [0038] The darkened layer more particularly preferably contains at least one metal, metal nitride, or metal carbide from the group consisting of tantalum, molybdenum, tungsten, titanium nitride, zirconium nitride, hafnium nitride, tantalum nitride, carbide titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tantalum carbide, molybdenum carbide, and tungsten carbide, or mixtures or alloys thereof, or alloys, mixed nitrides or mixed carbides thereof with silicon or aluminum. That is, due to the high melting point greater than 2500°C, more particularly advantageous for the corrosion resistance of the darkened layer.
    [0039] In principle, nitrides and carbides are preferred for metals or alloys for the darkened layer. Such darkened layers have been shown to be particularly resistant to corrosion and oxidation and resistant to damage.
    [0040] Metal nitride and metal carbide can be stoichiometric, substoichiometric, or supersubstoichiometric with respect to nitrogen or with respect to carbon. Table 1

    [0041] 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 functional layer material is preferably from 1.7 to 2.3. The functional layer preferably contains at least indium tin oxide (ITO). Thus, particularly good results are obtained with respect to the emissivity and bendability of the coating according to the invention.
    [0042] A functional layer based on TCO, in particular ITO, is not susceptible to corrosion and is therefore particularly suited for use on the inner surface of the panel.
    [0043] 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 carried out under a protective gas atmosphere, eg argon. A small amount of oxygen can also be added to the protective gas, for example to improve the homogeneity of the functional layer.
    [0044] Alternatively, the target may preferably contain at least from 75% by weight to 95% by weight of indium and from 5% by weight to 25% by weight of tin. The deposition of the indium tin oxide is then carried out preferably under the addition of oxygen as reaction gas during sputtering.
    [0045] The emissivity of the panel according to the invention can be influenced by the thickness of the functional layer. The thickness of the functional layer is preferably from 40 nm to 200 nm, particularly preferably from 90 nm to 150 nm, and more particularly preferably from 100 nm to 140 nm, for example approximately 120 nm. In this range for the thickness of the functional layer, particularly advantageous values for the emissivity and a particularly advantageous ability of the functional layer to withstand mechanical transformation such as bending or pre-tension without damage are obtained.
    [0046] However, the functional layer may also include other transparent, electrically conductive oxides, for example, fluorine-doped tin oxide (SnO2:F), antimony-doped tin oxide (SnO2:Sb), mixed indium/ zinc (IZO), gallium-doped or aluminum-doped zinc oxide, niobium-doped titanium oxide, cadmium stannate, and/or zinc stannate.
    [0047] The thermal radiation reflective coating is a stack of layers, which, according to the invention, includes at least two dielectric layers, namely a lower dielectric layer and an upper dielectric layer. The lower dielectric layer is arranged below the functional layer; the upper dielectric layer is arranged above the functional layer. The coating according to the invention may, however, also include one or a plurality of additional dielectric layers, which may be arranged below and/or above the functional layer.
    [0048] The dielectric layers may contain, for example, silicon oxide (SiO2), silicon nitride (Si3N4), zinc oxide (ZnO), tin oxide (SnO2), mixed tin oxide zinc (SnZnOx), of zirconium (ZrO2), hafnium oxide (HfO2), tantalum oxide (Ta2O5), tungsten oxide (WO3), niobium oxide (Nb2O5), or titanium oxide (TiO2) and have, for example, thicknesses of 5 nm to 200 nm.
    [0049] The darkened layer or darkened layers, in principle, can be arranged in any position in the layer stack. The darkened layer may be arranged, for example, between the functional layer and the adjacent dielectric layer above and/or below the functional layer. The darkened layer can be arranged, for example, below the lower dielectric layer. The darkened layer can be arranged, for example, above the higher dielectric layer. The darkened layer may also be disposed between two adjacent dielectric layers.
    [0050] In a preferred embodiment of the invention, the lower dielectric layer is an adhesive layer. Adhesive layer results in a durable stable adhesion of the layers deposited above the adhesive layer under the substrate. The adhesive layer also prevents the accumulation of ions diffusing out of the substrate in the area bordering the functional layer, in particular of 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.
    [0051] The adhesive layer preferably contains at least one oxide or one nitride. The adhesive layer particularly preferably contains silicon oxide (SiO2) or silicon nitride (Si3N4). This is particularly advantageous with respect to the adhesion of the layers deposited above the adhesive layer onto the substrate. The silicon oxide can have dopants, for example, fluorine, carbon, nitrogen, boron, phosphorus, and/or aluminum. The silicon oxide or silicon nitride are more particularly preferably aluminum-doped (SiO2:Al, Si3N4:Al), boron-doped (SiO2:B, Si3N4:B), or zirconium-doped (SiO2:Zr, Si3N4 :Zr). This is particularly advantageous with respect to the optical properties of the coating as well as the speed of application of the adhesive layer, for example by sputtering.
    [0052] The silicon oxide or silicon nitride is preferably deposited using magnetically enhanced sputtering with a target that contains at least silicon. The target for deposition of an adhesive layer containing aluminum-doped silicon oxide or 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 mixtures related to production. The target for deposition of an adhesive layer containing boron-doped silicon oxide or silicon nitride preferably contains from 99.9990% by weight to 99.9999% by weight of silicon and from 0.0001% by weight to 0.001% by weight. boron weight as well as production-related mixtures. The target for deposition of an adhesive layer containing silicon oxide or silicon nitride doped with zirconium 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 mixtures related to production. Deposition is preferably carried out under the addition of oxygen as a reaction gas in the case of silicon oxide; under the addition of nitrogen as reaction gas in the case of silicon nitride during sputtering.
    [0053] Doping the adhesive layer can also improve the smoothness of layers applied above the adhesive layer. The high smoothness of the layers is particularly advantageous in the case of use of the panel according to the invention in the motor vehicle sector since, by these means, an unpleasant rough surface feeling 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.
    [0054] However, the adhesive layer may also contain other materials, for example other oxides such as TiO2, Al2O3, Ta2O5, Y2O3, ZrO2, HfO2, WO3, Nb2O5 ZnO, SnO2, and/or ZnSnOx or nitrides such as AlN.
    [0055] The adhesive layer preferably has a thickness of from 10 nm to 150 nm, particularly preferably from 15 nm to 50 nm, for example approximately 30 nm. This is particularly advantageous with respect to the adhesion of the coating according to the invention and the prevention of diffusion of ions from the substrate into the functional layer.
    [0056] In a preferred embodiment of the invention, the top dielectric layer is a barrier layer to regulate oxygen diffusion during a temperature treatment of the panel. Thus, through the barrier layer, the oxygen content of the functional layer can be influenced and adjusted, which has a definite influence on the properties of the functional layer. Both an excessively low oxygen content and an excessively high oxygen content result in excessively high sheet strength and thus excessively high emissivity. In addition, an excessively low oxygen content results in a sharp, often undesirable color print. An excessively high oxygen content of the functional layer results in the fact that the functional layer is damaged during bending, which is evidenced in particular as cracks within the functional layer.
    [0057] The thickness of the barrier layer is preferably from 5 nm to 50 nm, particularly preferably from 7 nm to 40 nm, more particularly preferably from 10 nm to 30 nm. Thus, particularly good results with respect to sheet strength and bendability are obtained. Furthermore, a barrier layer of these thicknesses advantageously protects the coating against corrosion from a humid atmosphere.
    [0058] The refractive index of the barrier layer material is preferably greater than or equal to the refractive index of the functional layer material. The refractive index of the barrier layer material is particularly preferably from 1.7 to 2.3. Thus, advantageous optical properties of the coating are obtained, in particular an aesthetic color impression during light reflection.
    [0059] The barrier layer preferably contains at least one oxide and/or nitride. The oxide and/or nitride may be stoichiometric or non-stoichiometric. The barrier layer particularly preferably contains at least silicon nitride (Si3N4). This is particularly advantageous with respect to the influence of the barrier layer on the oxidation of the functional layer and on the optical properties of the panel. Silicon nitride may have dopants, for example titanium, zirconium, boron, hafnium, and/or aluminum. The silicon nitride is more particularly preferably aluminum-doped (Si3N4:Al) or zirconium-doped (Si3N4:Zr) or boron-doped (Si3N4:B). This is particularly advantageous with respect to optical properties, bendability, smoothness, and emissivity of the coating as well as the speed of application of the barrier layer, for example by sputtering.
    [0060] The silicon nitride is preferably deposited using magnetically enhanced sputtering with a target that contains at least silicon. The target for deposition of a barrier 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 mixtures related to the production. The target for deposition of a barrier layer containing boron-doped silicon nitride preferably contains from 99.9990% by weight to 99.9999% by weight of silicon and from 0.0001% by weight to 0.001% by weight boron as well as production-related mixtures. The target for deposition of a barrier 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 mixtures related to the production. The deposition of the silicon nitride is preferably done under the addition of nitrogen as reaction gas during sputtering.
    [0061] During a temperature treatment after application of the coating according to the invention, the silicon nitride can be partially oxidized. A barrier layer deposited as Si3N4 then contains, after temperature treatment, SixNyOz, with the oxygen content typically from 0 atomic % to 35 atomic %.
    [0062] However, the barrier layer may alternatively also contain, for example, at least WO3, Nb2O5, Bi2O3, TiO2, and/or AlN.
    [0063] In a preferred embodiment of the invention, a dielectric anti-reflective layer is arranged above the upper dielectric layer. The anti-reflective layer reduces reflections in the visible spectral range of the panel according to the invention and causes a neutral color impression of reflected and transmitted light. The anti-reflective layer also improves the corrosion resistance of the functional layer. The anti-reflective layer material preferably has a refractive index that is less than the refractive index of the functional layer material. The refractive index of the anti-reflective layer material is preferably less than or equal to 1.8.
    [0064] The anti-reflective layer preferably contains at least one oxide. The anti-reflective layer particularly preferably contains silicon dioxide (SiO 2 ). This is particularly advantageous with respect to the optical properties of the panel and the corrosion resistance of the functional layer. The silicon dioxide can have dopants, for example, fluorine, carbon, nitrogen, boron, phosphorus, and/or aluminum. The silicon oxide is more particularly preferably aluminum-doped (SiO2:Al), boron-doped (SiO2:B), or zirconium-doped (SiO2:Zr).
    [0065] However, the anti-reflective layer can also contain other materials, for example, other oxides such as Al2O3.
    [0066] The anti-reflective layer preferably has a thickness of from 20 nm to 150 nm, particularly preferably from 40 nm to 100 nm. This is particularly advantageous with respect to the low reflection and high transmittance of visible light as well as the adjustment of a selected color impression of the panel and the corrosion resistance of the functional layer.
    [0067] In a particularly advantageous embodiment, the thermal radiation reflective coating on the substrate comprises at least: - an adhesive layer as the lower dielectric layer, - above the adhesive layer, a functional layer, - above the functional layer, a barrier layer to regulate oxygen diffusion as the top dielectric layer, and - above the barrier layer, an anti-reflective layer.
    [0068] The darkened layer or multiple darkened layers are preferably arranged below the adhesive layer (i.e. between the substrate and the adhesive layer), between the adhesive layer and the functional layer, between the functional layer and the barrier layer, and/or between the barrier layer and the anti-reflective layer.
    [0069] Above the top dielectric layer (and optionally above the anti-reflective layer), a cover layer can be arranged. The cover layer is preferably the topmost layer of the coating according to the invention. 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 titanium oxide (TiO2), zirconium oxide (ZrO2), hafnium oxide (HfO2), niobium oxide (Nb2O5), tantalum oxide (Ta2O5 ), chromium oxide (Cr2O3), tungsten oxide (WO3), and/or cerium oxide (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 regarding scratch resistance are obtained. The darkened layer may also be disposed between the top dielectric layer and the cover layer or between the anti-reflective layer and the cover layer.
    [0070] Below the lower dielectric layer, an additional dielectric adhesion promoting layer can also be arranged, preferably with a thickness of 2 nm to 15 nm. For example, the adhesive layer may contain SiO2, and the additional adhesion promoting layer may contain at least one oxide such as TiO2, Al2O3, Ta2O5, Y2O3, ZnO, and/or ZnSnOx, or a nitride such as Si3N4 or AlN. Advantageously, the adhesion of the coating according to the invention can be further improved by the adhesion promoting layer. In addition, the adhesion promoting layer enables improved adjustment of color values and transmittance or reflection.
    [0071] The substrate preferably contains 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.
    [0072] In an advantageous embodiment of the invention, the substrate is dyed and/or colored. By combining a dyed or colored substrate with the coating according to the invention, improved thermal radiation reflective panels with reduced transmittance in the visible spectral range, in particular, can be realized. Such panels may be used, for example, in the automotive sector as one of the side windows, rear windows, or roof panels and may be desirable for aesthetic or thermal reasons. Compared to clear substrates with transmittance-reducing thermal radiation reflective coatings (eg based on chromium), any layer defect present is less annoyingly noticeable in the panels according to the invention. Furthermore, transmittance through a dyed substrate is further reduced by the coating according to the invention, such that panels with very low light transmittance can be realized. The substrate preferably has transmittance in the visible spectral range of less than 40%, particularly preferably less than 20%, and more particularly preferably less than 15%, for example approximately 10%. The substrate, however, in principle, can also have higher transmittance, eg greater than or equal to 70%. Thus, light dyeing can be obtained by means of the coating according to the invention.
    [0073] In a particularly advantageous embodiment, the substrate has transmittance in the visible spectral range of less than 15%, and the panel with thermal radiation reflective coating has transmittance of less than 10%. In a more particularly advantageous embodiment, the substrate has a transmittance in the visible spectral range of less than 10%, and the panel with a thermal radiation reflective coating has a transmittance of less than 7%, in particular less than 6%. . Thus, particularly dark panels can be realized.
    [0074] The substrate thickness can vary widely and thus be ideally adapted to the requirements of the individual case. Preferably, panels with standard thicknesses of 1.0mm to 25mm and more preferably 1.4mm to 4.9mm are used. Substrate size can vary widely and is determined by use in accordance with the invention. The substrate has, for example, in automotive engineering and the architectural sector, usual areas from 200 cm2 to 20 m2.
    [0075] The substrate can be flat or also light or enormously curved in one or a plurality of spatial directions. Flat panels occur, for example, in glazing in the architectural sector or in glazing of large areas of buses, trains, or tractors. Curved panels occur, for example, in glazing in the motor vehicle sector, with typical radii of curvature in the range of approximately 10 cm to approximately 40 m. Curvature radii do not have to be constant across the entire panel; enormously curved and less enormously curved regions can be present in a panel. It is a particular advantage of the invention that a flat substrate can be provided with the coating according to the invention and that the coating is not damaged during a downstream bending process which is typically carried out at elevated temperatures, for example 500°C. at 700°C. In principle, the coating can of course also be applied to a curved substrate. The three-dimensional shape of the substrate preferably has no shadow zone such that the substrate, for example, can be sputter coated.
    [0076] The coating according to the invention can be applied to the surface of the substrate over its entire area. However, the substrate surface can also have regions free of coating. 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.
    [0077] The substrate can also be provided on both surfaces with a thermal radiation reflective coating according to the invention in each case.
    [0078] In an advantageous embodiment of the invention, the substrate is joined to a cover panel via at least one intermediate thermoplastic layer to form a composite panel. The cover panel is preferably intended to face the external environment in the installed position of the composite panel, while the substrate faces inwards. The coating according to the invention is preferably disposed on the surface of the substrate facing away from the cover panel.
    [0079] The cover panel preferably contains 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 cover panel preferably has a thickness of from 1.0 mm to 25 mm and particularly preferably from 1.4 mm to 4.9 mm.
    [0080] 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 from 0.3 mm to 0.9 mm.
    [0081] The composite panel has, in an advantageous embodiment, transmittance in the visible spectral range of less than 25%, preferably less than 15%, particularly preferably less than 10%, more particularly preferably less than 8%, and in particular less than 6%. The substrate, cover panel, and/or thermoplastic intermediate layer are preferably dyed and/or colored. The cover panel preferably has transmittance in the visible spectral range of less than 40%; the intermediate thermoplastic layer preferably has a transmittance of 20% to 70%.
    [0082] In a particularly advantageous embodiment, the coating according to the invention is applied to the inwardly facing surface of the substrate, with the substrate constituting the panel of an inwardly facing composite panel. A sun protection coating is further applied to the surface of the substrate facing the cover panel, to the surface of the cover panel facing the substrate, or to a carrier film in the thermoplastic intermediate layer. The sun protection coating is 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 that are separated from each other by dielectric layers with thicknesses from 10 nm to 100 nm. The sun protection coating reflects fractions of incident sunlight outside the visible spectral range, in particular the infrared spectral range. Through the sun protection coating, the heating of the interior by direct sunlight is reduced. Furthermore, the sun protection coating reduces the heating of the composite panel elements arranged behind the sun protection coating and thus the thermal radiation emitted by the composite panel. By combining the sun protection coating with the coating according to the invention for the reflection of thermal radiation, the thermal comfort in the interior is advantageously further improved.
    [0083] The substrate, for example, can also be joined to another panel through spacers to form an insulating glazing unit. The substrate can also be joined to more than one other panel by intermediate thermoplastic layers and/or spacers.
    [0084] The invention further includes a method for producing a panel with a thermal radiation reflective coating, wherein at least: (a) a lower dielectric layer, (b) a functional layer containing at least one transparent, electrically conductive oxide ( TCO), and (c) an upper dielectric layer, are applied in succession on a substrate and wherein, in addition, before process step (a), between process steps (a) and (b), between process steps (b) and (c), and/or after process step (c), at least one darkened layer that contains at least one metal, a metal nitride, and/or a metal carbide with a melting point greater than 1900°C and a specific electrical resistivity of less than 500 μohm*cm is applied.
    [0085] Preferably, an anti-reflective layer is applied after the top dielectric layer. A cover layer can be applied after the top dielectric layer and, optionally, the anti-reflective layer.
    [0086] In principle, a darkened layer can be applied before and/or after each layer. One or even a plurality of darkened layers can be applied.
    [0087] 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 substrate coating. Sputtering is done in a protective gas atmosphere, for example, argon, or in a reactive gas atmosphere, for example, by the addition of oxygen, a hydrocarbon (for example, methane), or nitrogen.
    [0088] 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 plasma enhanced chemical vapor (PECVD), or by wet chemical methods.
    [0089] 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 the temperature treatment. Thus, in particular, the reflective properties with respect to thermal radiation as well as the optical properties of the panel are significantly improved. The darkened layer according to the invention is not damaged during the temperature treatment. In particular, the darkened layer is not oxidized during temperature treatment to a degree that results in an increase in light transmittance.
    [0090] 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.
    [0091] Of course, other temperature treatment steps can take place before or after the bending process. A temperature treatment, alternatively, can also be performed using laser radiation.
    [0092] In an advantageous embodiment, after temperature treatment and, optionally, after bending, the substrate can be supplied with pre-strain or partially pre-strained. For this, the substrate is suitably cooled in a manner known per se. A prestressed substrate typically has surface compressive stresses of at least 69 MPa. A partially prestressed substrate typically has surface compressive stresses of 24 MPa to 52 MPa. A pre-stretched substrate is suitable as single pane safety glass, for example as a side window or rear window of a motor vehicle.
    [0093] In an advantageous embodiment of the invention, after the temperature treatment and, optionally, after the bending process and/or the pre-tensioning process, the substrate is joined by means of at least one thermoplastic layer intermediate to a cover panel to form a composite panel. The substrate is preferably arranged in the composite such that the surface provided with the coating according to the invention faces away from the intermediate thermoplastic layer and the cover panel.
    [0094] The invention further includes the use of the panel according to the invention with thermal radiation reflective coating as a panel or as a component of a panel, in particular as a component of an insulating glazing unit or a composite panel, in buildings, in particular in access or window areas, as a fire door, as a component incorporated into furniture and devices, in particular electronic devices with a cooling or heating function, for example, as an oven door or an oven door refrigerator, or in transportation means for traveling on land, air, or water, in particular on trains, boats, and motor vehicles, for example, as a rear window, side window, and/or roof panel.
    [0095] The invention further includes the use of a darkened layer according to the invention in a thermal radiation reflective coating or in a panel with thermal radiation reflective coating according to the invention to reduce transmittance in the spectral range visible.
    [0096] The invention is explained in detail in the following with reference to the drawings and exemplary embodiments. Drawings are schematic representations and not actual scale. The drawings in no way restrict the invention.
    [0097] They represent: Fig. 1 a cross-section through an embodiment of the panel according to the invention with thermal radiation reflective coating, Fig. 2 is a cross-section through another embodiment of the panel according to the invention with thermal radiation reflective coating, Fig. 3 is a cross-section through another embodiment of the panel according to the invention with thermal radiation reflective coating, Fig. 4 is a cross-section through another embodiment of the panel according to the invention with thermal radiation reflective coating, Fig. 5 is a cross-section through a composite panel including a panel according to the invention, Fig. 6 is a detailed flowchart of an embodiment of the method according to the invention.
    [0098] Fig. 1 represents a cross-section through an embodiment of the panel according to the invention with substrate 1 and thermal radiation reflective coating 2 (also called low-E coating). Substrate 1 contains soda-lime glass and is 2.9 mm thick. Coating 2 comprises a lower dielectric layer 3, a functional layer 4, a darkening layer 10, and an upper functional layer 5. The layers are arranged in the indicated order with increasing distance from the substrate 1.
    [0099] Functional layer 4 is made of indium tin oxide (ITO) and has a thickness of approximately 100 nm. The lower dielectric layer 3 and the upper dielectric layer 5 can be configured in a manner known per se to the person skilled in the art and, for example, can be manufactured from silicon oxide (SiO2) or silicon nitride (Si3N4) and have a thickness of approximately 100 nm.
    [0100] The darkened layer 10 is made of titanium nitride (TiNx) and has a thickness of approximately 20 nm. The darkened layer 10 effects a reduction in the transmittance of coating 2 in the visible spectral range.
    [0101] The darkened layer 10, alternatively, can also be arranged between the lower dielectric layer 3 and the functional layer 4, or between the substrate 1 and the lower dielectric layer 3. The coating 2, alternatively, can also have a plurality of darkened layers 10.
    [0102] By means of the darkened layer 10, the light transmittance of the coating 2 is reduced. If substrate 1 is dyed, the light transmittance through coating 2 is further reduced. Consequently, it is possible to realize very dark panels, for example, with transmittance in the visible spectral range of less than 10%. Panels with such low transmittance are difficult to produce from a dyed substrate alone because panels with such heavy dyeing are typically not commercially available. Unlike a coating with a transmittance-reducing functional layer (based, for example, on nickel, chromium, zirconium, tantalum or niobium) on a clear substrate, layer defects related to the production of coating 2 according to the invention on a dyed substrate 1 have a lower contrast. Consequently, layer defects are less annoyingly noticeable to the observer. These are the main advantages of the present invention.
    [0103] Fig. 2 represents a cross-section through another embodiment of the panel according to the invention with the substrate 1 and the thermal radiation reflective coating 2. The substrate 1 is configured as in Fig. 1. Coating 2 comprises a lower dielectric layer 3, a darkening layer 10, a functional layer 4, an upper functional layer 5, and an anti-reflective layer 6. The layers are arranged in the indicated order with increasing distance from the substrate 1.
    [0104] The lower dielectric layer 3 is an adhesive layer made of aluminum-doped silicon dioxide (SiO2:Al) and has a thickness of approximately 30 nm. Functional layer 4 is made of indium tin oxide (ITO) and has a thickness of approximately 120 nm. The upper dielectric layer 5 is a barrier layer to regulate the diffusion of oxygen during a temperature treatment of the panel. Barrier layer 5 is made of aluminum-doped silicon nitride (Si3N4:Al) and has a thickness of approximately 10 nm. The anti-reflective layer 6 is made of aluminum-doped silicon dioxide (SiO2:Al) and has a thickness of approximately 40 nm.
    [0105] The darkened layer 10 between the lower dielectric layer 3 and the functional layer 4 is made of titanium nitride (TiNx) and has a thickness of approximately 20 nm. The darkened layer 10 effects a reduction in the transmittance of coating 2 in the visible spectral range.
    [0106] The darkened layer 10, alternatively, can also be applied in a different position, for example, between the functional layer 4 and the upper dielectric layer 5, between the upper dielectric layer 5 and the anti-reflective layer 6, or between the substrate 1 and the lower dielectric layer 3. The coating 2, alternatively, may also have a plurality of darkened layers 10.
    [0107] Fig. 3 represents a cross-section through another embodiment of the panel according to the invention with the substrate 1 and the thermal radiation reflective coating 2. The coating 2 comprises, as in Fig. 2, a lower dielectric layer 3 (adhesive layer), a functional layer 4, an upper dielectric layer 5 (barrier layer), and an anti-reflective layer 6. Layers 3, 4, 5, and 6 are configured as in Fig. 2. The coating 2 further includes a cover layer 7 above the anti-reflective layer 6. The cover layer 7 contains, for example, Ta2O5 or TiO2 and has a thickness of 10 nm. The cover layer advantageously protects the coating 2 against mechanical damage, in particular against scratches.
    [0108] The coating 2 further includes three darkened layer 10. The first darkened layer 10 is arranged between the substrate 1 and the lower dielectric layer 3. The second darkened layer 10 is arranged between the lower dielectric layer 3 and the functional layer 4. The third darkened layer 10 is arranged between the functional layer 4 and the upper dielectric layer 5. The darkened layers 10 are made of TiNx and have thicknesses between 10 nm and 15 nm. By means of three darkening layers 10 according to the invention 10, the light transmittance is more enormously reduced than by a single darkening layer 10, without losing the advantageous optical properties as a result of an excessively thick darkening layer 10.
    [0109] Fig. 4 represents a cross-section through a panel according to the invention with thermal radiation reflective coating 2. The panel is intended as a side window of a motor vehicle. Substrate 1 has a thickness of 3.15 mm. Substrate 1 is made of stained soda-lime glass and has a transmittance of approximately 14% in the visible spectral range. The panel is thermally pre-tensioned and curved, as is customary for side windows in the automotive sector.
    [0110] The coating 2 is applied on the inner surface of the substrate 1. In this aspect, the advantageous effect of the coating 2 on the thermal comfort inside the vehicle is particularly pronounced. Coating 2 reflects part of the incident sunlight through the panel, in particular in the infrared range. The thermal radiation emitted from the hot panel towards the vehicle interior is, moreover, at least partially suppressed as a result of the low emissivity of the coating 2. Thus, the interior is heated less strongly in summer. In winter, the thermal radiation emanating from the interior is reflected. Consequently, the cold panel acts less strongly as an uncomfortable heatsink. In addition, the required heating performance of the climate control system can be reduced, which results in significant energy savings.
    [0111] Coating 2 is preferably applied over flat substrate 1 prior to bending substrate 1. Coating a flat substrate is technically significantly simpler than coating a curved substrate. Substrate 1 is then typically heated to a temperature of from 500°C to 700°C, for example 640°C. On the one hand, the temperature treatment is necessary to bend the substrate 1. On the other hand, the emissivity of the coating 2 is regularly improved by the temperature treatment. The upper dielectric layer 5 implemented as a barrier layer influences the degree of oxidation of the functional layer 4 during temperature treatment. The oxygen content of the functional layer 4 is low enough after the temperature treatment that the coating 2 can be subjected to a bending process. Excessively high oxygen content would result in damage to functional layer 4 during bending. On the other hand, the oxygen content of functional layer 4 is high enough after temperature treatment for low emissivity.
    [0112] Coating 2 is configured as in Fig. 2. Light transmittance through the panel is further reduced by the darkening layer 10. The panel with coating 2 thus has transmittance in the visible spectral range of less than 10%. Such dark side (rear) windows may be desirable for thermal and/or aesthetic reasons. The darkened layer 10 according to the invention is suitable because of its corrosion and oxidation resistance to withstand the temperature treatment and bending process without damage.
    [0113] Fig. 5 represents a cross-section through a panel according to the invention with thermal radiation reflective coating 2 as part of a composite panel. The substrate 1 is joined to a cover panel 8 via an intermediate thermoplastic layer 9. The composite panel is intended as a roof panel for a motor vehicle. The composite panel is curved as is customary 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 surface of the substrate 1, which faces the opposite side of 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 are 2.1 mm thick. Intermediate thermoplastic layer 9 contains polyvinyl butyral (PVB) and has a thickness of 0.76 mm.
    [0114] Substrate 1, cover panel 8, and intermediate thermoplastic layer 9 are dyed. Through coating 2, light transmittance is further reduced. Thus, very dark composite panels can be realized.
    [0115] Fig. 6 represents a flowchart of an exemplary embodiment of the method according to the invention for producing a panel with a thermal radiation reflective coating 2. EXAMPLES
    [0116] Panels with thermal radiation reflective coating 2 were produced according to the invention. The exact layer sequence with the materials used and layer thicknesses of Examples 1 to 8 are shown in Table 2 and Table 3. Substrate 1 was made from stained soda-lime glass and had transmittance in the visible spectral range of 25%. The darkened layers 10 contained titanium nitride. Titanium nitride has (on a solid basis) a melting point of 2950°C and a specific electrical resistivity of 20 μohm*cm. The examples differ in terms of the number and thickness as well as the position of the darkened layers 10.
    [0117] In all examples, substrate 1 was initially flat and was supplied with coating 2 according to the invention by means of sputtering. Substrate 1 with coating 2 was then subjected to a 10 minute temperature treatment at 640°C, bent in the process, and provided with a radius of curvature of approximately 30 cm. Table 2
    Table 3

    [0118] The observations on the test panels are summarized in Table 6. RSquare is the sheet strength of coating 2. TL indicates the transmittance of the panels to visible light. RL indicates the reflectivity of the panels to visible light. AL indicates the absorption of the panels for visible light. The optical condition of the coating is influenced, in particular, by cloudiness (“fog”) as well as cracking.
    [0119] By means of the coatings 2 according to the invention with the darkened layers 10, the transmittance of the panel is further reduced. Temperature treatment during panel bending results in a reduction in sheet strength and thus reduced emissivity. The darkened layer 10 is not oxidized, which would result in a significant increase in TL transmittance. The bending process also does not result in coating damage such that the optical condition of the layer is good in all cases. COMPARATIVE EXAMPLES
    [0120] The Comparative Examples differ from the examples according to the invention by the thermal radiation reflective coating 2. The coating comprised, as in the examples, the lower dielectric layer 3, the functional layer 4, the upper dielectric layer 5, and the anti-reflective 6. However, the coatings did not include any darkened layer 10 according to the invention. Instead, each coating had two layers manufactured from a material that did not meet the requirements according to the invention for the darkened layer (as per Table 5, in which the melting points TS and the corresponding p-specific electrical conductivities are summarized).
    [0121] The exact layer sequences with the materials used and layer thicknesses of Comparative Examples 1 to 3 are shown in Table 4. The observations on the test panels are summarized in Table 6. Table 4
    Table 5
    Table 6

    [0122] The darkened layers not according to the invention manufactured from NiCr, Ti, or NiCrN are damaged by temperature treatment with the bending process such that the optical condition of the coating was in all cases unacceptable to customers in the automotive sector. . Furthermore, in particular the absorber layers made of Ti are not sufficiently resistant to oxidation, so that they have, after temperature treatment, significantly increased TL transmittance.
    [0123] From Table 6, it is furthermore discernable that, in particular, the transmittance may be influenced by the thickness of the darkened layers 10. This produces the preferred ranges for the thickness of the darkened layer 10.
    [0124] By means of the darkened layers 10 according to the invention, a reduction in the transmittance of the reflective coating of thermal radiation is obtained. The darkened layers 10 are sufficiently resistant to corrosion and oxidation to withstand a temperature treatment and bending process without damage. This result was unexpected and surprising to the person skilled in the art.
    [0125] Reference Character List: (1) substrate (2) thermal radiation reflective coating (3) lower dielectric layer (4) functional layer (5) upper dielectric layer (6) anti-reflective layer (7) cover layer ( 8) cover panel (9) intermediate thermoplastic layer (10) darkened layer
    权利要求:
    Claims (16)
    [0001]
    1. Panel with a thermal radiation reflective coating, characterized in that it comprises a substrate (1) and at least one thermal radiation reflective coating (2) on at least one of the surfaces of the substrate (1), wherein the reflective coating of thermal radiation (2), proceeding from the substrate (1), comprises: - a lower dielectric layer (3) having a thickness of 5 nm to 200 nm and comprising silicon oxide, silicon nitride, zinc oxide, tin oxide , mixed oxide of foreign zinc, zirconium oxide, hafnium oxide, tantalum oxide, tungsten oxide, niobium oxide or titanium oxide, - a functional layer (4) having a thickness of 100 to 150 nm and comprising oxide of indium tin - a darkened layer (10) having a thickness of 10 to 30 nm and comprising a metal nitride having a melting point greater than 1900°C and a specific electrical resistivity of less than 500 μohm*cm, and - a layer superior dielectric (5) having a thickness ra from 5 nm to 200 nm and comprising silicon oxide, silicon nitride, zinc oxide, tin oxide, mixed zinc foreign oxide, zirconium oxide, hafnium oxide, tantalum oxide, tungsten oxide, niobium oxide or titanium oxide, and wherein at least one darkened layer (10) is disposed between the lower dielectric layer (3) and the functional layer (4) in direct contact with the functional layer, or between the functional layer (4) and the upper dielectric layer (5) in direct contact with the functional layer, or between both the lower dielectric layer (3) and the functional layer (4) in direct contact with the functional layer and between the functional layer (4) and the upper dielectric (5) in direct contact with the functional layer.
    [0002]
    2. Panel according to claim 1, characterized in that it has transmittance in the visible spectral range of less than 25%.
    [0003]
    3. Panel according to claim 1, characterized in that the substrate (1) has transmittance in the visible spectral range of less than 15% and the panel with the thermal radiation reflective coating (2) has transmittance of less than than 10%.
    [0004]
    4. Panel according to claim 1, characterized in that the thickness of the darkened layer (10) is from 5 nm to 20 nm.
    [0005]
    5. Panel according to claim 1, characterized in that the metallic nitride of the darkened layer (10) is selected from groups IV B, V B, and VI B of the periodic system.
    [0006]
    6. Panel according to claim 1, characterized in that the melting point of metal nitride is greater than 2200°C.
    [0007]
    7. Panel according to claim 1, characterized in that the upper dielectric layer (5) comprises silicon oxide or silicon nitride.
    [0008]
    8. Panel according to claim 1, characterized in that the lower dielectric layer (3) comprises silicon oxide or silicon nitride.
    [0009]
    9. Panel according to claim 1, characterized in that the thermal radiation reflective coating (2) further comprises an anti-reflective layer (6), which is arranged above the upper dielectric layer (5).
    [0010]
    10. Panel according to claim 1, characterized in that the thermal radiation reflective coating (2) comprises as its uppermost layer a covering layer (7), which comprises at least one oxide.
    [0011]
    11. Panel according to claim 1, characterized in that the substrate (1) is joined to a cover panel (8) by means of at least one intermediate thermoplastic layer (9) to form a composite panel and in which the coating (2) is arranged on the surface of the substrate (1) facing away from the cover panel (8).
    [0012]
    12. Panel according to claim 1, characterized in that it is used as a panel or a component of a panel in a building or in a means of transport to travel on land, in the air or in the water.
    [0013]
    13. Panel according to claim 1, characterized in that: the lower dielectric layer comprises silicon oxide; the darkened layer comprises a titanium nitride; and the top dielectric layer comprises silicon oxide.
    [0014]
    14. Panel according to claim 1, characterized in that the coating (2) further comprises a second darkened layer between the functional layer and the upper dielectric, wherein the second darkened layer has a thickness of 2 to 50 nm and comprises at least one metal, a metal nitride, a metal carbide, or a mixture thereof, with a melting point greater than 1900 °C and a specific electrical resistivity of less than 500 μohm * cm.
    [0015]
    15. Method for producing a panel, as defined in claim 1, with a thermal radiation reflective coating (2), characterized in that it comprises applying in succession at least: (a) a lower dielectric layer (3) having a thickness from 5 nm to 200 nm and comprising silicon oxide, silicon nitride, zinc oxide, tin oxide, mixed zinc foreign oxide, zirconium oxide, hafnium oxide, tantalum oxide, tungsten oxide, niobium oxide or titanium oxide, (b) a functional layer (4) having a thickness of 100 to 150 nm and comprising indium tin oxide; (c) a darkened layer (10) having a thickness of 10 to 30 nm and comprising a metal nitride having a melting point greater than 1900°C and a specific electrical resistivity of less than 500 μohm*cm (d) a layer higher dielectric (5) having a thickness of 5 nm to 200 nm and comprising silicon oxide, silicon nitride, zinc oxide, tin oxide, mixed oxide of foreign zinc, zirconium oxide, hafnium oxide, tantalum oxide, tungsten oxide, niobium oxide or titanium oxide.
    [0016]
    16. Method according to claim 15, characterized in that the substrate (1) with the coating (2) is heated to a temperature of at least 200°C.
    类似技术:
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    同族专利:
    公开号 | 公开日
    CN104995150B|2018-11-23|
    PT2958872T|2017-06-07|
    EP2958872B1|2017-03-01|
    US20160002100A1|2016-01-07|
    MX2015010760A|2015-11-30|
    PL2958872T3|2017-09-29|
    BR112015018645A2|2017-07-18|
    US10287207B2|2019-05-14|
    EA201591539A1|2016-01-29|
    CA2901778A1|2014-08-28|
    KR101728620B1|2017-04-19|
    ES2626911T3|2017-07-26|
    WO2014127867A1|2014-08-28|
    EA028403B1|2017-11-30|
    JP2016513056A|2016-05-12|
    KR20150107845A|2015-09-23|
    MX360105B|2018-10-23|
    CA2901778C|2019-06-18|
    EP2958872A1|2015-12-30|
    CN104995150A|2015-10-21|
    JP6181210B2|2017-08-16|
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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]|
    2021-06-01| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-12-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-25| 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:
    申请号 | 申请日 | 专利标题
    EP13155969|2013-02-20|
    EP13155969.2|2013-02-20|
    PCT/EP2013/077351|WO2014127867A1|2013-02-20|2013-12-19|Pane having a coating that reflects thermal radiation|
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