Glazing having an improved sun protection coating

Abstract

The invention relates to a coated substrate comprising a substrate (1) having a functional multilayer coating (2) provided thereon over the surface, in particular a sun protection coating and / or heat protection coating, wherein the functional multilayer coating (2) has a three-layer combination (3) with the sequence TiCx (3a) / TiN (3b) / AlN (3c), wherein the three-layer combination (3) is arranged between a first and a second dielectric (4a, 4b) and, starting from the substrate (1), the layer sequence A) first dielectric (4a) / TiCx (3a) / TiN (3b) / AlN (3c) / second dielectric (4b) or B) first dielectric (4a) / AlN (3c) / TiN (3b) / TiCx (3a) / second dielectric (4b) is formed. The invention also relates to a laminated pane (100, 200, 300) comprising at least one such coated substrate, and to a method for the production thereof and to the use thereof, in particular in or as roof panes or side panes of a vehicle, or in or as window panes of a building.

Description

[0001] Glazing with improved solar protection coating

[0002] The invention relates to glazing with an improved solar and heat protection coating, as well as a process for its production and its use.

[0003] Solar control coatings for roof windows in the automotive sector with very low TL transmission between 0.5% and 12%, good aging resistance, and low total transmitted thermal radiation (TTS) are often manufactured using a combination of two highly tinted glass panes laminated together to form a composite pane and a low-E coating on the interior surface of the inner pane based on transparent conductive oxides (TCO), such as indium tin oxide (ITO) or antimony tin oxide. The tinted glass of the panes absorbs solar energy, and the properties of the TCO (low-E coating) reduce the re-emission of thermal energy into the vehicle interior.In addition to the requirement for heavily tinted glass panes, the use of TCO coatings is also problematic, as they have a relatively low specific conductivity and require comparatively thick layers of a cost-intensive material. Furthermore, the commonly used TCO, indium tin oxide, poses the risk of supply chain disruption due to limited available reserves, which is a highly relevant issue for industrial mass production.

[0004] The possibilities for achieving the lowest possible TTS (total transmitted thermal radiation) values ​​with an absorbent glass with a low-E coating are limited. The high absorption leads to a high heat input into the glass, and the heat transfer can only be partially compensated by reducing emissivity.

[0005] To achieve lower TTS values ​​in laminated panes, a tinted outer pane can be replaced with a clear pane. A silver-based IR-reflective coating is applied to side II, the interior-facing surface of this outer pane. This coating drastically reduces heat transfer into the laminated pane and thus leads to a significantly lower TTS value. To achieve the desired low TTS value without a tinted outer pane, a colored thermoplastic interlayer, such as a colored PVB film, can be used.

[0006] Such functional IR-reflective silver coatings, TCO coatings, and electrically conductive coatings are highly susceptible to corrosion and must therefore be hermetically sealed and protected from moisture and chemical degradation. For this purpose, such a functional coating is stripped along a peripheral frame-shaped area of ​​the laminated pane. Stripping is typically performed in a complex and time-consuming process step using mechanical abrasion, for example, grinding with a grinding wheel. Another, equally complex method is the application of a reactive black print to the edge area. The uncoated area is hermetically sealed inside the laminated pane by the thermoplastic interlayer or an acrylic adhesive acting as a vapor barrier.The vapor diffusion barrier protects the corrosion-sensitive functional coating from moisture and atmospheric oxygen. Applying functional silver or TCO coatings to the exposed surfaces of a laminated pane is virtually impossible.

[0007] FR 3 127 490 A1 discloses material comprising a substrate coated with a functional coating comprising at least one titanium nitride-based functional layer and at least two dielectric coatings, each dielectric coating comprising at least one dielectric layer such that each functional layer is arranged between two dielectric coatings, the dielectric coating located directly beneath a functional layer comprising a dielectric layer in contact with the functional layer and selected from an aluminum nitride-based layer and / or a zinc oxide-based layer.

[0008] US 5 112 675 A discloses a heat-absorbing glazing intended for automobiles consisting of clear or tinted glass coated with a layer of titanium carbide and an ITO top layer applied by cathodic sputtering.

[0009] The object of the invention is to provide a substrate, in particular glazing, with an improved solar and heat protection coating that exhibits high chemical and mechanical stability and offers good solar and heat protection efficiency, especially at low transmission values. Furthermore, the coating should be simple, sustainable, and cost-effective to produce.

[0010] These and further objects are achieved according to the proposal of the invention by a coated substrate according to independent claim 1 and a composite pane according to claim 10. Advantageous embodiments of the invention emerge from the subclaims. According to the invention, a coated substrate comprising a substrate with a functional multi-layer coating arranged flat thereon, in particular a solar and / or heat protection coating, is provided, wherein the functional multi-layer coating comprises a three-layer combination of the sequence titanium carbide (TiCx) / titanium nitride (TiN) / aluminum nitride (AIN), wherein the three-layer combination is arranged between a first and a second dielectric and, starting from the substrate, the layer sequence

[0011] A) first dielectric / TiCx / TiN / AIN / second dielectric or

[0012] B) first dielectric / AIN / TiN / TiCx / second dielectric is formed.

[0013] The three-layer combination can also be called a three-layer stack.

[0014] According to the invention, a coated substrate is provided that possesses outstanding functional, optical, energetic, and chemical properties, particularly for applications in the automotive sector, for example, while being simple and cost-effective to produce. Furthermore, the raw materials required for the functional multilayer coating are sustainable, free, and widely available, so there is no fear of disruptions in supply chains. Expensive and less readily available coating materials such as silver or indium tin oxide (ITO) can be replaced without any loss of quality.

[0015] The central element of the functional multi-layer coating according to the invention is the three-layer combination of AlN / TiN / TiCx. This three-layer combination can also be called a three-layer stack and offers a surprising number of advantageous properties. Firstly, the combination of TiN and TiCx can adjust the overall color, reflectivity, and transmittance of the coating, particularly in systems that are required to have low transmittance of, for example, 2% to 20%, such as roof or side windows in vehicles. Furthermore, layers of TiCx and TiN arranged one above the other can exhibit high conductivity, as they have the same crystal II structure and can grow epitaxially on top of each other. TiCx and AlN form a nucleation and growth layer for the TiN layer, as well as a protective oxygen diffusion barrier layer.This allows the titanium nitride layer to be thinner than would be possible on its own. Furthermore, the coating comprising the three-layer stack of AlN / TiN / TiCx can be used not only as an IR-reflective layer, but also as an electrically conductive layer, for example, as a heating layer for a vehicle composite window. The three-layer combination and the coating as a whole are constructed from particularly robust, mechanically and chemically stable layer materials. Advantageously, the coating according to the invention eliminates the need for complex edge-side stripping, as is necessary, for example, with silver layers to prevent corrosion and degradation of the layer. This also contributes in particular to reducing the complexity and costs of the manufacturing process.

[0016] The three-layer stack of AlN / TiN / TiCx is a functional, low-emissivity, IR-reflective multilayer combination that forms the core element of the substrate coating. This three-layer combination, used in the coating on substrates or in combination with laminated panes, achieves low emissivity of < 35%, very low transmission, and, ultimately, an outstanding TTS value of < 20% (total transmitted thermal radiation) (TTS, measured according to ISO 13837). This is achieved without compromising the optical appearance, for example, with regard to reflectivity or reflection colors. Undesirable color shifts in reflection and transmission can be avoided.

[0017] According to the invention, the three-layer AlN / TiN / TiCx stack is sandwiched between a first and a second dielectric, each comprising at least one dielectric layer. The first dielectric, i.e., at least one dielectric layer, is arranged on the surface of the substrate and can also be referred to as the base layer. This improves adhesion to the substrate and also serves as a diffusion barrier layer. The second dielectric, i.e., at least one dielectric layer, serves as a diffusion barrier and protective layer for the functional three-layer combination. Furthermore, all dielectric layers serve to adapt the optical appearance.

[0018] In a preferred embodiment, the titanium nitride (TiN) layer of the three-layer combination has a layer thickness in the range of 10 nm to 60 nm, preferably from 20 nm to 50 nm, particularly preferably from 25 to 45 nm. Titanium nitride as a material is hard and oxidation-stable and, for a ceramic material, has very good electrical and thermal conductivity. Thin TiN layers can be produced, for example, by means of reactive sputtering and then have an attractive blue transmission color and display high IR reflectivity and low emissivity. In a further preferred embodiment, the aluminum nitride (AIN) layer of the three-layer combination has a layer thickness in the range of 1 nm to 15 nm, preferably from 2 nm to 10 nm, particularly preferably from 3 nm to 9 nm.

[0019] In a further preferred embodiment, the titanium carbide (TiCx) layer of the three-layer combination has a layer thickness in the range from 1 nm to 30 nm, preferably from 1 nm to 20 nm, particularly preferably from 1 nm to 15 nm, most particularly preferably from 4 nm to 15 nm.

[0020] A further preferred embodiment of the substrate according to the invention provides that the first dielectric and / or the second dielectric are formed as a single dielectric layer or in multiple layers. In other words, the first dielectric and the second dielectric can be formed independently of one another as single-layered or multi-layered, i.e., as two or more dielectric layers arranged flatly one above the other. These dielectric layers can be formed from the same or different dielectric materials and / or in the same or different layer thicknesses.

[0021] The first dielectric and / or the second dielectric can contain or consist of a material selected from silicon nitride (Sis1^ ), silicon oxynitride (SiOxNy), silicon zirconium nitride, silicon carbide, silicon oxide, metal oxide, metal nitride, metal carbide or a combination thereof. In the case of metal oxides, metal nitrides and metal carbides, the metal can be, for example, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten. To produce the base layer, i.e. the first dielectric layer, known vapor deposition methods such as physical vapor deposition (PVD), in particular sputtering, preferably magnetron sputtering, chemical vapor deposition (CVD) or atomic layer deposition (ALD) can be used.

[0022] In a preferred embodiment, it is provided that the first dielectric and / or the second dielectric preferably contains or is formed from silicon nitride (SisN^), silicon oxynitride (SiOxNy) or silicon zirconium nitride. For the production of dielectric layers, known vapor deposition methods such as PVD, in particular sputtering, preferably magnetron sputtering, CVD or ALD, can be used, for example.

[0023] In another preferred embodiment of the invention, the first dielectric and / or the second dielectric has a high refractive index of greater than 1.6, preferably greater than 1.9.

[0024] It is also possible to use dielectric materials for the first dielectric and / or the second dielectric which have a lower refractive index between 1.6 and 1.3, but a high refractive index is preferred.

[0025] In the context of the present invention, refractive indices are generally given relative to a wavelength of 550 nm. Methods for determining refractive indices are known to those skilled in the art. The refractive indices specified in the context of the invention can be determined, for example, by ellipsometry, for which commercially available ellipsometers can be used.

[0026] In preferred embodiments, the substrate is a transparent or colored substrate made of glass, glass ceramic or a transparent plastic.

[0027] In a preferred embodiment of the coated substrate according to the invention, the functional multilayer coating is electrically conductive and heatable by applying current and voltage. In other words, the functional multilayer coating is functionally connected to a current and voltage source and corresponding connections and / or lines. For example, a voltage in the range of 42 V to 48 V or even 300 V to 400 V can be used, which is typically available in electric vehicles. This is particularly advantageous for defrosting or removing moisture from fogged windows, especially when the coated substrate is used, for example, for rear or side windows in vehicles.Since a voltage of 300 V to 400 V or even up to 500 V is available in such vehicles directly via the primary battery, i.e., via the on-board electrical system, a costly DC / DC converter is advantageously not required. Furthermore, a functional connection for communication with a control unit such as a vehicle's on-board computer can still be established in a visually unobtrusive or wireless manner using conventional methods.

[0028] The invention also relates to a composite pane, in particular for a vehicle or a building, comprising an outer pane with an outer surface and an interior surface, and an inner pane with an outer surface and an interior surface, which are connected to one another by a thermoplastic intermediate layer, wherein the outer pane and / or the inner pane is designed as a coated substrate according to the invention comprising a substrate with a functional multi-layer coating, in particular with at least one sun protection and / or heat protection coating, as described above in various configurations and embodiments.

[0029] The composite pane is intended to separate an interior space, in particular the interior of a vehicle or a building, from the outside environment in a window opening. The composite pane is a laminate and comprises a first and a second pane, which are referred to as the outer pane and the inner pane in the context of the invention and are connected to one another via a thermoplastic intermediate layer. In the context of the invention, the inner pane refers to the pane which faces the interior space in the installed position. The outer pane refers to the pane which faces the outside environment in the installed position. In the context of the invention, the interior-side surface (or inner side or inner surface) is understood to be the surface of the panes which faces the interior space in the installed position.For the purposes of the invention, the outside surface (or outside or outer surface) is understood to mean the surface of the panes which, in the installed position, faces the external environment.

[0030] The surfaces of the panes are typically designated as follows: The outside of the outer pane is designated as Side I. The inside of the outer pane is designated as Side II. The outside of the inner pane is designated as Side III. The inside of the inner pane is designated as Side IV.

[0031] The outer pane and the inner pane are preferably formed independently of one another from glass or plastic, preferably soda-lime glass, alkali aluminosilicate glass, polycarbonate, or polymethacrylate. In a particularly preferred embodiment, the outer pane and the inner pane are made of glass.

[0032] Suitable glass sheets include glass sheets known under the trade names Planiclear and Planilux (each clear glass), VG 10, VG20, VG40 or TSANx, TSA3+, TSA4+ from Saint-Gobain, with the VG series being grey-tinted glasses and the TSA series being green-tinted glasses.

[0033] The outer pane and / or the inner pane preferably have, independently of one another, a thickness of 0.1 to 4 mm, preferably of 1 to 4 mm, particularly preferably of 1.6 mm to about 2.1 mm.

[0034] The interior surface of the outer pane and the exterior surface of the inner pane face each other and are connected to each other by means of the thermoplastic intermediate layer.

[0035] The thermoplastic intermediate layer is formed by one or more thermoplastic films, whereby in the resulting composite pane, the individual films in the resulting intermediate layer may no longer be distinguishable from one another. The thermoplastic films preferably contain polyvinyl butyral (PVB), ethylene-vinyl acetate (EVA), polyurethane (PU), and / or mixtures thereof and / or copolymers thereof, particularly preferably polyvinyl butyral. The films are preferably based on the aforementioned materials, but may contain additional components, for example, plasticizers, colorants, IR or UV absorbers. The thermoplastic films can be clear, transparent, or colored or tinted PVB films.

[0036] The individual polymer films of the interlayer, in particular the PVB films, preferably have a thickness of approximately 0.2 mm to 1 mm, for example, 0.38 mm, 0.76 mm, or 0.81 mm. Further properties of the laminated glass pane can be influenced by the thickness of the films. For example, thicker PVB films result in improved sound absorption, especially if they contain an acoustically effective core, increased burglary resistance of the laminated glass pane, and also increased protection against ultraviolet radiation (UV protection). For the purposes of the present invention, "transparent" means that the overall transmission of the laminated glass pane complies with legal requirements (for example, the European Union Directive ECE-R43) and preferably has a visible light transmittance of more than 50% and in particular more than 60%, for example more than 70%.Accordingly, "opaque" means a light transmission of less than 10%, preferably less than 5%.

[0037] In a preferred embodiment of the composite pane according to the invention, the functional multilayer coating is applied to the interior-facing surface of the outer pane and / or to the interior-facing surface of the inner pane. The functional multilayer coating comprising the three-layer combination AIN / TiN / TiCx can thus advantageously replace a previously conventional IR-reflective TCO or silver layer as a sun protection coating on the interior-facing surface of the outer pane and / or a conventional low-E coating (heat protection coating) on ​​the interior-facing surface of the inner pane. Furthermore, in a preferred embodiment, the functional multilayer coating is applied to both the interior-facing surface of the outer pane and the interior-facing surface of the inner pane.The functional multi-layer coating according to the invention is so robust and stable that it can also be applied to the inside of the inner pane without any problems.

[0038] In one embodiment of the composite pane according to the invention, the functional multilayer coating is formed on the interior-side surface of the outer pane, and a conventional low-E coating is formed on the interior-side surface of the inner pane. The functional multilayer coating comprising the three-layer combination AIN / TiN / TiCx can thus advantageously replace a previously conventional IR-reflective TCO or silver layer as a sun protection coating on the interior-side surface of the outer pane. A conventional low-E coating as a heat-ray-reflecting coating of the composite pane on the inside of the inner pane preferably comprises a functional layer containing a transparent conductive oxide (TCO), preferably indium tin oxide (ITO), or tin oxide (SnO2), which is arranged between dielectric layers.The dielectric layers can be formed, in particular, from dielectric oxides or nitrides, such as ZnO, SnZnO, AlN, TiO2, SiO2, or SiAgN. Such conventional low-E coatings are known, for example, from WO2013 / 127563 A1 or WO2019 / 110172 A1. The invention further relates to a method for producing a coated substrate according to the invention, as well as to a composite pane containing at least one such coated substrate according to the invention, as described above in various embodiments and configurations, at least comprising the steps.

[0039] A) Providing at least one substrate,

[0040] B) applying a first dielectric comprising at least one dielectric layer to the substrate,

[0041] C) Applying a three-layer combination of TiCx / TiN / AIN to the first dielectric applied in step B

[0042] D) Applying a second dielectric comprising at least one dielectric layer to the three-layer combination, wherein in step C) starting from the substrate and a layer sequence TiCx / TiN / AIN or AIN / TiN / TiCx is formed.

[0043] In a preferred embodiment of the method, in step C), the titanium nitride (TiN) layer is created using high-power pulsed magnetron sputtering (HiPIMS). This allows for the creation of particularly conductive layers, which is advantageous for IR reflectivity. Furthermore, particularly hard and tough layers with particularly good adhesion are produced.

[0044] In one embodiment of the process according to the invention, the process comprises, after step D), a heat treatment (annealing), preferably at a temperature of 300°C to 800°C.

[0045] The invention also encompasses the use of a coated substrate according to the invention and a composite pane according to the invention, as described above in various configurations and combinations, in buildings or as a vehicle pane in means of transport for land, air, or water traffic, in particular as a window pane in motor vehicles, in particular as a roof pane, rear window, or side window. Use as a roof pane is particularly preferred.

[0046] Within the scope of the present invention, preferred embodiments which are mentioned for individual features can also be freely combined with one another, provided that they are not contradictory or are mentioned and described exclusively as alternatives to one another. This also applies to features which are mentioned only in relation to the coated substrate or the composite pane or to the method of production. The invention is presented in more detail below with reference to the examples and figures. It should be noted that different aspects are described which can each be used individually or in combination. This means that any aspect can be used with different embodiments of the invention, unless explicitly presented as a pure alternative.

[0047] The drawings are simplified, schematic representations and not to scale. The drawings do not limit the invention in any way.

[0048] They show:

[0049] Fig. 1 shows a schematic cross section through a first embodiment of a substrate according to the invention with the functional multi-layer coating;

[0050] Fig. 2 shows the transmission spectrum of the coated substrate from Example 1;

[0051] Fig. 3 the reflection spectrum of the coated substrate from Example 1;

[0052] Fig. 4 shows a schematic cross section through an embodiment of a composite pane according to the invention with two functional multi-layer coatings;

[0053] Fig. 5 shows a schematic cross section through another embodiment of a composite pane according to the invention with a functional multi-layer coating and a conventional low-E coating.

[0054] Fig. 6 the computer-simulated transmission spectrum of the composite pane from Example 2;

[0055] Fig. 7 the computer-simulated reflection spectrum of the composite pane from Example 2;

[0056] Fig. 8 the computer-simulated transmission spectrum of the composite pane from Example 3;

[0057] Fig. 9 the computer-simulated reflection spectrum of the composite pane from Example 3;

[0058] Fig. 10 the computer-simulated transmission spectrum of the composite pane from Example 4;

[0059] Fig. 11 the computer-simulated reflection spectrum of the composite pane from Example 4;

[0060] Fig. 12 the computer-simulated transmission spectrum of the composite pane from Example 5;

[0061] Fig. 13 the computer-simulated reflection spectrum of the composite pane from Example 5;

[0062] Fig. 14 the computer-simulated transmission spectrum of the composite pane from Example 6;

[0063] Fig. 15 the computer-simulated reflection spectrum of the composite pane from Example 6

[0064] Fig. 16 shows a schematic cross section through an embodiment of a composite pane 300 according to the invention with a functional multi-layer coating.

[0065] Fig. 1 shows a schematic cross-section through an embodiment of a coated substrate according to the invention, comprising a substrate 1 with a functional multi-layer coating 2 arranged thereon, comprising the three-layer combination 3 of a TiCx layer 3a, a TiN layer 3b and an AlN layer 3c as well as a first dielectric 4a and a second dielectric 4b. The first dielectric 4a and the second dielectric 4b surround the three-layer combination 3 in a sandwich-like manner. The first dielectric 4a is arranged on the surface of the substrate 1 and the second dielectric 4b is arranged on the AlN layer 3c. The first dielectric 4a and the second dielectric 4b are schematically shown as a single layer, but in other embodiments they can also be multi-layered, with several layers of dielectric material arranged flat one above the other.In another embodiment, the sequence of layers in the three-layer combination 3 starting from the substrate 1 can also be formed in the sequence AIN-TiN-TiCx.

[0066] Example 1 and Table 1 show an exemplary embodiment of the design of a coated substrate according to the invention shown in Fig. 1.

[0067] Example 1

[0068] Table 1 : Optical properties and emissivity of a tempered inventive

[0069] Substrate

[0070] Table 1 shows the structure and optical properties of the glass substrate coated according to the invention (PLC = Planiclear from Saint Gobain) after heat treatment (annealing) for 8 minutes at 640 °C.

[0071] It means

[0072] TL is the integrated light transmittance according to DIN 5033-7:2014-10 (illuminant A) measured with an angle of incidence of 0° and an observation angle of 2° over a wavelength range from 380 nm to 780 nm; a*TL and b*TL are the values ​​of the transmission color in the L*a*b* color space determined according to DIN 5033-7:2014-10 and DIN 6174, with the view directed towards the surface of the substrate 1 coated with the functional multi-layer coating 2, measured with an angle of incidence of 0° and an observation angle of 2° (illuminant D65) over a wavelength range from 380 nm to 780 nm;

[0073] RLg is the integrated reflectance according to DIN 5033-7:2014-10, whereby the measurement refers to the uncoated surface of the substrate 1, with an angle of incidence of 8° and an observation angle of 10° (illuminant A) over a wavelength range from 380 nm to 780 nm; a*RLg and b*RLg are the values ​​of the reflection color in the L*a*b* color space determined according to DIN 5033-7:2014-10 and DIN 6174, whereby the measurement refers to the uncoated surface of the substrate 1, measured with an angle of incidence of 8° and an observation angle of 10° (illuminant D65) over a wavelength range from 380 nm to 780 nm;

[0074] RLc is the integrated reflectance according to DIN 5033-7:2014-10, whereby the measurement refers to the surface of the substrate 1 coated with the functional multi-layer coating 2 with an angle of incidence of 8° and an observation angle of 10° (illuminant A) over a wavelength range from 380 nm to 780 nm; a*RLc and b*RLc are the values ​​of the reflection color of the surface of the substrate 1 coated with the functional multi-layer coating 2 in the L*a*b* color space determined according to DIN 5033-7:2014-10 and DIN 6174, measured with an angle of incidence of 8° and an observation angle of 10° (illuminant D65) over a wavelength range from 380 nm to 780 nm; s is the normal emissivity at 283 K according to DIN EN 16012:2015-05 based on a measurement of the surface of the substrate 1 coated with the functional multilayer coating 2.

[0075] Unless otherwise stated, the standards indicated are always the standards in the version valid on the date of filing.

[0076] The transmission and reflection spectra associated with the embodiment according to Example 1 are shown in Fig. 2 and Fig. 3, wherein the simulated values ​​(TL sim, RLc sim, RLg sim) and the measured values ​​(TL ex, RLc ex, RLg ex) are indicated in each case. From the transmission and reflection spectra shown in Fig. 2 and Fig. 3, it can be seen that the deviation of the simulated spectra from the measured spectra is very small. Fig. 4 shows a schematic cross-section through an embodiment of a composite pane 100 according to the invention with two functional multi-layer coatings 2. The composite pane 100 comprises an outer pane 1a and an inner pane 1b, which are connected to one another via a thermoplastic intermediate layer 5. The composite pane 100 can be provided, for example, as the roof pane of a passenger car, wherein the outer pane 1a faces the outside environment and the inner pane 1b faces the vehicle interior.The outer pane 1a has an outer surface I and an inner surface II. The inner pane 1b has an outer surface III and an inner surface IV. The outer surfaces I and III face the outside environment, the inner surfaces II and IV face the vehicle interior. The inner surface II of the outer pane 1a and the outer surface III of the inner pane 1b face one another. In the embodiment shown in Fig. 4, the outer pane 1a is designed as a coated substrate according to the invention with a multi-layer coating 2 arranged on the inner surface II of the outer pane 1a, and the inner pane 1b is designed as a coated substrate according to the invention with a multi-layer coating 2-1 arranged on the inner surface IV of the inner pane 1b.

[0077] Fig. 5 shows a schematic cross-section through an embodiment of a composite pane 200 according to the invention with a functional multi-layer coating 2 and a conventional low-E coating 6. The composite pane 200 comprises an outer pane 1a and an inner pane 1b, which are connected to one another via a thermoplastic intermediate layer 5. The composite pane 200 can be provided, for example, as a roof pane of a passenger car, wherein the outer pane 1a faces the external environment and the inner pane 1b faces the vehicle interior. The outer pane 1a has an outer surface I and an inner surface II. The inner pane 1b has an outer surface III and an inner surface IV. The outer surfaces I and III face the external environment, the inner surfaces II and IV face the vehicle interior. The inner surface II of the outer pane 1a and the outer surface III of the inner pane 1b face one another. In the embodiment shown in Fig.In the embodiment shown in Figure 5, the outer pane 1a is designed as a coated substrate according to the invention with a multi-layer coating 2 arranged on the inner surface II of the outer pane 1a and the inner pane 1b is designed as a substrate with a conventional low-E coating 6 arranged on the inner surface IV of the inner pane 1b.

[0078] For the following examples, the (layer) stack structure of the functional

[0079] Coatings (layers and layer thicknesses) are given in Tables 2 to 6, and the optical properties of the finished composite panes are given in Table 7. All optical, aesthetic, and energetic properties of the composite panes according to the invention in Examples 2 to 6 were measured in the laminated and tempered state, or calculated by computer simulation for a laminated and tempered composite pane.

[0080] In Examples 2 to 4, the functional multilayer coating 2 according to the invention, in particular a sun protection coating, comprising the three-layer stack 3 of a TiCx layer 3a, a TiN layer 3b and an AIN layer 3c arranged between a first dielectric 4a and a second dielectric 4b, was applied to the inner side II of a clear outer pane 1a (example Planiclear, PLC from Saint Gobain). To achieve the desired low transmission TL, a tinted PVB film was used for the thermoplastic intermediate layer 5 and laminated to the composite pane 100 with another clear inner pane 1b (for example Planiclear, PLC from Saint Gobain), which carries on the inner side IV a functional multilayer coating 2-1 comprising the three-layer stack 3-1 of a TiCx layer 3a-1, a TiN layer 3b-1 and an AIN layer 3c-1 arranged between a first dielectric 4a-1 and a second dielectric 4b-1.

[0081] Example 2

[0082] Table 2: Structure of a composite pane 100 according to the invention with a blue-coloured PVB

[0083] Intermediate layer and 2% TL. In this embodiment of the invention, two clear glass panes 1a, 1b were laminated to form the composite pane 100 with a blue-tinted PVB film as a thermoplastic intermediate layer 5 optimized for a transmission of 2%. The functional multilayer coating 2 applied to the inner surface II of the outer pane 1a, comprising the three-layer combination 3 in the TiCx / TiN / AIN stack arranged between a first dielectric 4a and a second dielectric 4b, acts in particular as a sun protection coating and leads to reduced heating of a vehicle interior and the inner pane 1b due to the reflection of infrared radiation.In addition, with the functional multilayer coating 2, in addition to good TTS values ​​and emissivities (thermal comfort) that are improved compared to previously known systems, good optical and aesthetic properties, in particular aesthetic transmission and reflection colors, of the composite pane 100 are achieved (Table 7). In this embodiment, a further functional multilayer coating 2-1, comprising the three-layer combination TiCx 3a-1 / TiN 3b-1 / AIN 3c-1 arranged between a first dielectric 4a-1 and a second dielectric 4b-2, is formed on the inner surface IV of the inner pane 1b and arranged as a low-E / heat protection coating. In this preferred embodiment, the composite pane 100 not only has good emission of approximately 25%, but also a particularly low total transmitted thermal radiation of TTS of approximately 15%.The heat-insulating coating on the inner side IV of the inner pane 1b reduces, on the one hand, the emission of heat radiation through the composite pane 100 into the vehicle interior, particularly at high outside temperatures. On the other hand, the heat-insulating coating can reduce the emission of heat radiation from the vehicle interior at low outside temperatures. In addition, the heat-insulating coating can reduce the transmission of visible light into the vehicle interior, so that no tinted panes, or only tinted panes to a lesser extent, need be used if such reduced transmission is desired, for example, in roof windows. These are major advantages of the composite pane according to the invention, since the interior climate of the vehicle interior is significantly improved and the need for air conditioning is reduced.The functional multilayer coatings 2, 2-1 are advantageously particularly robust and resistant, eliminating the need for complex edge stripping, particularly to prevent corrosion. This significantly simplifies the process. Furthermore, the materials used for the functional multilayer coatings 2, 2-1 are particularly inexpensive and widely available. Any disruption to the supply chain can therefore be avoided.

[0084] The transmission and reflection spectra corresponding to Example 2 are shown in Fig. 6 and Fig. 7.

[0085] Example 3

[0086] Table 3: Structure of a composite pane 100 according to the invention with a grey-coloured PVB

[0087] Intermediate layer and 4% TL. The structure of this composite pane 100 is analogous to that in Example 2, wherein the blue-tinted PVB film for the thermoplastic intermediate layer 5 was replaced by a more readily available gray-tinted PVB film and the materials and / or layer thicknesses of the individual layers of the functional multilayer coating 2-1 were changed. In comparison (Table 7), this resulted in a less neutral transmission color. In this embodiment, however, the composite pane 100 also exhibits good energetic behavior with a good emissivity of approximately 25% and a particularly low total transmitted thermal radiation of TTS of approximately 15%. This results in the previously described advantages of, on the one hand, reduced radiation of thermal radiation through the composite pane 100 into the vehicle interior, particularly at high outside temperatures, and, on the other hand, reduced radiation of thermal radiation from the vehicle interior at low outside temperatures.The transmission and reflection spectra corresponding to Example 3 are shown in Fig. 8 and Fig. 9.

[0088] Example 4 Table 4: Example structure of a composite pane 100 according to the invention with a blue colored PVB interlayer 5 and 2% TL.

[0089] In this embodiment of the invention, two clear glass panes 1a, 1b were laminated with a blue-tinted thermoplastic intermediate layer 5 made of PVB optimized for a transmission of 2% to form the composite pane 100. The composite pane 100, with the structure shown in Table 4, is characterized by low internal reflection and an aesthetic transmission color, combined with good emissivity and a particularly low total transmitted thermal radiation of approximately 13% (Table 7). The transmission and reflection spectra associated with Example 4 are shown in Fig. 10 and Fig. 11. Example 5

[0090] Table 5: Structure of an embodiment of a composite pane 200 according to the invention with a functional multi-layer coating 2 on the outer pane 1a and a conventional low-E coating 6 on the inner pane 1b.

[0091] In this embodiment of the invention, the functional multilayer coating 2 on the inner side II of the outer pane 1a is constructed in a layer sequence and layer thickness analogous to that in Example 2. However, in this example, a gray-tinted glass was used as the inner pane 1b, and a clear PVB film was used as the intermediate layer 5. In contrast to Example 2, a conventional low-E coating 6 is applied to the inner side IV of this colored inner pane 1b, comprising a comparatively thick layer based on indium tin oxide, which is sandwiched between two dielectric layers 8a, 8b, 8c, 8d. An emissivity s of approximately 33% and good thermal radiation, and in the color values ​​for transmission as well as internal and external reflection, a total transmitted thermal radiation TTS of still approximately 18%, were achieved (Table 7).

[0092] The transmission and reflection spectra corresponding to Example 5 are shown in Fig. 12 and Fig. 13. Example 6

[0093] Table 6: Structure of an embodiment of a composite pane 200 according to the invention with a functional multi-layer coating 2 on the outer pane 1a and a conventional low-E coating 6 on the inner pane 1b

[0094] The functional multilayer coating 2 on the inner side II of the outer pane 1a is constructed in a layer sequence and layer thickness analogous to that in Example 4. However, in this example, a gray-tinted glass is used as the inner pane 1b, and a clear PVB film is used as the intermediate layer 5. In contrast to Example 4 (as in Example 5), a conventional low-E coating 6 is applied to the inner side IV of this colored inner pane 1b, comprising a comparatively thick layer based on indium tin oxide, which is sandwiched between two dielectric layers 8a, 8b, 8c, 8d.It can be seen that this composite pane 200 with the functional multilayer coating 2 applied to surface II of the outer pane 1a, comprising the three-layer combination 3 with an emissivity of 33% and a TTS of approximately 15%, exhibits good thermal and, in terms of color values ​​for transmission, as well as internal and external reflection, also good optical quality (Table 7). However, the conventional low-E coating 6 is thicker than the functional multilayer coating 2 and, due to the expensive indium tin oxide 7, also more costly. In addition, the indium tin oxide layer-based low-E coating 6, particularly for use as a composite pane 200 in vehicles, must be laboriously removed from the edges by decoating, as this coating is susceptible to corrosion.This can be completely eliminated with a functional multilayer coating 2, which is also based on significantly more cost-effective raw materials, since the materials of the three-layer stack 3 used as the core element are robust, thermally and chemically stable. Therefore, the manufacturing process is also significantly simplified. This also applies to the design in Example 5.

[0095] The transmission and reflection spectra corresponding to Example 6 are shown in Fig. 14 and Fig. 15.

[0096] Table 7 Optical and thermal properties and behavior of the layer stacks laminated to form composite panes from Examples 2 to 6.

[0097] They mean:

[0098] TL is the integrated light transmittance according to DIN 5033-7:2014-10 (illuminant A) measured with an angle of incidence of 0° and an observation angle of 2° over a wavelength range from 380 nm to 780 nm; a*TL and b*TL are the values ​​of the transmission colour in the L*a*b* colour space determined according to DIN 5033-7:2014-10 and DIN 6174, with the view directed onto the coated surface B of the inner pane 1b, measured with an angle of incidence of 0° and an observation angle of 2° (illuminant D65) over a wavelength range from 380 nm to 780 nm;

[0099] RLin is the integrated reflectance according to DIN 5033-7:2014-10, whereby the measurement refers to the coated surface B of the inner pane 1b, with an angle of incidence of 8° and an observation angle of 10° (illuminant A) over a wavelength range from 380 nm to 780 nm; a*RLin and b*RLin are the values ​​of the reflection colour in the L*a*b* colour space determined according to DIN 5033-7:2014-10 and DIN 6174, whereby the measurement refers to the coated surface B of the inner pane 1b, with an angle of incidence of 8° and an observation angle of 10° (illuminant D65) over a wavelength range from 380 nm to 780 nm;

[0100] RLout is the integrated reflectance according to DIN 5033-7:2014-10, whereby the measurement refers to the uncoated surface A of the outer pane 1a, with an angle of incidence of 8° and an observation angle of 10° (illuminant A) over a wavelength range from 380 nm to 780 nm; a*RLout and b*RLout are the values ​​of the reflection color in the L*a*b* color space determined according to DIN 5033-7:2014-10 and DIN 6174, whereby the measurement refers to the uncoated surface A of the outer pane 1a, with an angle of incidence of 8° and an observation angle of 10° (illuminant D65) over a wavelength range from 380 nm to 780 nm; s is the normal emissivity at 283 K according to DIN EN 16012:2015-05, whereby the measurement refers to the coated surface B of the inner pane 1 b and TTS is the total solar energy transmission according to ISO 9050:2003-08.

[0101] Fig. 16 shows a schematic cross-section through an embodiment of a composite pane 300 according to the invention with a functional multi-layer coating 2. The composite pane 300 comprises an outer pane 1a and an inner pane 1b, which are connected to one another via a thermoplastic intermediate layer 5. The composite pane 300 can be provided, for example, as a window pane or component of a window pane in a building, wherein the outer pane 1a faces the outside environment and the inner pane 1b faces the interior. The outer pane 1a has an outer surface I and an inner surface II. The inner pane 1b has an outer surface III and an inner surface IV. The outer surfaces I and III face the outside environment, the inner surfaces II and IV face the vehicle interior. The inner surface II of the outer pane 1a and the outer surface III of the inner pane 1b face one another. In the embodiment shown in Fig.In the embodiment shown in Figure 16, the outer pane 1a is formed as a coated substrate according to the invention with a multilayer coating 2 arranged on the inner surface II of the outer pane 1a, and neither the outer surface III nor the inner surface IV of the inner pane 1b are coated. Example 7.

[0102] Table 8: Structure of an embodiment of a composite pane 300 according to the invention with a functional multi-layer coating 2 on the outer pane 1a

[0103] In this embodiment of the invention, two clear glass panes 1a, 1b were laminated with a clear PVB film as a thermoplastic intermediate layer 5 to form the composite pane 300. A functional multilayer coating 2 comprising the three-layer combination 3 in the stack of TiCx / TiN / AlN arranged between a first dielectric 4a and a second dielectric 4b is applied to the inner surface II of the outer pane 1a.

[0104] Example 8

[0105] Table 9: Structure of an embodiment of a composite pane 300 according to the invention with a functional multilayer coating 2 on the outer pane 1a In this embodiment of the invention, two clear glass panes 1a, 1b were laminated with a clear PVB film as a thermoplastic intermediate layer 5 to form the composite pane 300. A functional multilayer coating 2 comprising the three-layer combination 3 in the stack of TiCx / TiN / AlN arranged between a first dielectric 4a and a second dielectric 4b is applied to the inner surface II of the outer pane 1a.

[0106] Tables 10 and 11 show the optical and thermal properties and behavior of the layer stacks laminated to form composite panes with a structure as in Examples 7 and 8. Table 11 shows the values ​​after heat treatment (annealing) for 8 minutes at 640 °C, and Table 10 lists the values ​​for corresponding unannealed composite panes. The layer thickness of the thermoplastic intermediate layer is 0.76 mm in the unannealed embodiment and 1.52 mm in the annealed embodiment.

[0107] Table 10 Optical and thermal properties and behavior of the layer stacks laminated to composite panes from Examples 7 and 8, which were not subjected to heat treatment (unannealed embodiment).

[0108] They mean:

[0109] TLi is the integrated light transmittance according to DIN 5033-7:2014-10 (illuminant A) measured with an angle of incidence of 0° and an observation angle of 2° over a wavelength range from 380 nm to 780 nm;

[0110] RLouti is the integrated reflectance according to DIN 5033-7:2014-10, whereby the measurement refers to the uncoated surface A of the outer pane 1a, with an angle of incidence of 8° and an observation angle of 10° (illuminant A) over a wavelength range from 380 nm to 780 nm; L*RLouti is the luminance determined according to DIN 5033-7:2014-10 and DIN 6174, whereby the measurement refers to the uncoated surface A of the outer pane 1a; a*RLouti and b*RLouti are the values ​​of the reflection color in the L*a*b* color space determined according to DIN 5033-7:2014-10 and DIN 6174, whereby the measurement refers to the uncoated surface A of the outer pane 1a, with an angle of incidence of 8° and an angle of observation of 10° (illuminant D65) over a wavelength range from 380 nm to 780 nm; gi is the Solar Control Value measured according to ISO 9050 AM 1.5, which corresponds to the percentage of solar energy that passes through the glass into a room.

[0111] Table 11 Optical and thermal properties and behavior of the layer stacks laminated to composite panes from Examples 7 and 8, which were subjected to a heat treatment (annealed embodiment).

[0112] They mean:

[0113] Tl_2 is the integrated light transmittance according to DIN 5033-7:2014-10 (illuminant A) measured with an angle of incidence of 0° and an observation angle of 2° over a wavelength range from 380 nm to 780 nm;

[0114] RLout2 is the integrated reflectance according to DIN 5033-7:2014-10, whereby the measurement refers to the uncoated surface A of the outer pane 1a, with an angle of incidence of 8° and an observation angle of 10° (illuminant A) over a wavelength range from 380 nm to 780 nm;

[0115] L*RLout2 is the luminance determined according to DIN 5033-7:2014-10 and DIN 6174, whereby the measurement refers to the uncoated surface A of the outer pane 1a; a*RLout2 and b*RLout2 are the values ​​of the reflection color in the L*a*b* color space determined according to DIN 5033-7:2014-10 and DIN 6174, whereby the measurement refers to the uncoated surface A of the outer pane 1a, with an angle of incidence of 8° and an angle of observation of 10° (illuminant D65) over a wavelength range from 380 nm to 780 nm; g2 is the Solar Control Value measured according to ISO 9050 AM 1.5, which corresponds to the percentage of solar energy that passes through the glass into a room.

[0116] Delta E (AE) can be used to determine whether a color difference is perceived by an observer. AE is a measure of the distance between two colors and indicates whether the difference between two colors can be perceived by an observer. It is therefore a relative measure with reference to the peculiarities of human color perception. An AE always refers to two colors that are to be compared. AE is calculated by calculating the Euclidean distance between the a*, b* and L* values ​​of the two colors to be compared. The symbols a* and b* are values ​​of the L*a*b* color space, a color model that describes all perceivable colors. L* indicates the brightness value (luminance) and can have values ​​between 0 and 100, a* indicates the chromaticity and color intensity between green and red, while b* indicates the chromaticity and color intensity between blue and yellow.The more negative or positive the values ​​of b* and a* are, the more intense the hue. Values ​​close to 0 for a* and b* indicate a rather dull, or neutral, hue.

[0117] The formula for calculating AE between the color of the unannealed embodiment and the color of the annealed embodiment in Examples 7 and 8 is as follows:

[0118] This results in an AE of 4.1 for example 7 and an AE of 1.7 for example 8.

[0119] For an observer, no color difference is perceptible between two colors if AE is less than 2. An AE of more than 5 is clearly visible to an observer. Colors with an AE of more than 5 are therefore perceived by the observer as different colors.

[0120] Consequently, in the case of the composite pane from Example 8, the observer cannot perceive any color difference between the unannealed embodiment and the tempered embodiment. In the case of the composite pane from Example 7, however, the observer perceives a slight color difference between the unannealed embodiment and the tempered embodiment. In the case of composite panes with a coating on the inner surface of the outer pane consisting of a TiN layer arranged between two dielectric layers (in particular SiA / N layers), the color difference AE between the color of the unannealed embodiment and the color of the tempered embodiment is significantly greater and amounts to, for example, 10, so that the observer perceives two different colors.

[0121] List of reference symbols

[0122] 1 substrate

[0123] 1a outer pane

[0124] 1b inner pane

[0125] 100, 200, 300 composite pane

[0126] 2, 2-1 functional multi-layer coating

[0127] 3, 3-1 three-layer combination (three-layer stack)

[0128] 3a,3a-1 TiCx layer

[0129] 3b,3b-1 TiN layer

[0130] 3c, 3c-1 AIN layer

[0131] 4a, 4a-1 first dielectric

[0132] 4b, 4b-1 second dielectric

[0133] 5 thermoplastic intermediate layer

[0134] 6 conventional low-E coating

[0135] 7 TCO (Transparent Conductive Oxide) layer

[0136] 8a dielectric layer

[0137] 8b dielectric layer

[0138] 8c dielectric layer

[0139] 8d dielectric layer

[0140] I outside surface of the outer pane

[0141] II Interior surface of the outer pane

[0142] III Outer surface of the inner pane

[0143] IV Interior surface of the inner pane

[0144] A uncoated surface of the outer pane

[0145] B coated surface of the inner pane

Claims

Patent claims 1 . Coated substrate, comprising a substrate (1) with a functional multi-layer coating (2) arranged thereon, in particular a sun and / or heat protection coating, characterized in that the functional multi-layer coating (2) comprises a three-layer combination (3) of the sequence TiCx (3a) / TiN (3b) / AIN (3c), wherein the three-layer combination (3) is arranged between a first dielectric (4a) and a second dielectric (4b) and starting from the substrate (1) the layer sequence A) first dielectric (4a) / TiCx (3a) / TiN (3b) / AIN (3c) / second dielectric (4b) or B) first dielectric (4a) / AIN (3c) / TiN (3b) / TiCx (3a) / second dielectric (4b).

2. Coated substrate according to claim 1, characterized in that the titanium nitride (TiN) layer (3b) of the three-layer combination (3) has a layer thickness in the range from 10 nm to 60 nm, preferably from 20 nm to 50 nm, particularly preferably from 25 to 45 nm.

3. Coated substrate according to claim 1 or 2, characterized in that the aluminum nitride (AIN) layer (3c) of the three-layer combination (3) has a layer thickness in the range from 1 nm to 15 nm, preferably from 2 nm to 10 nm, particularly preferably from 3 nm to 9 nm.

4. Coated substrate according to one of claims 1 to 3, characterized in that the titanium carbide (TiCx) layer (3a) of the three-layer combination (3) has a layer thickness in the range from 1 nm to 30 nm, preferably from 1 nm to 20 nm, particularly preferably from 1 nm to 15 nm, most particularly preferably from 4 nm to 15 nm.

5. Coated substrate according to one of claims 1 to 4, characterized in that the first dielectric (4a) and / or the second dielectric (4b) is formed as a single dielectric layer or multi-layered.

6. Coated substrate according to one of claims 1 to 5, characterized in that the first dielectric (4a) and / or the second dielectric (4b) contains or is formed from silicon nitride (SiAl^), silicon oxynitride (SiOxNy) or silicon zirconium nitride.

7. Coated substrate according to one of claims 1 to 6, characterized in that the first dielectric (4a) and / or the second dielectric (4b) has a refractive index of greater than 1.6, preferably greater than 1.

9.

8. Coated substrate according to one of claims 1 to 7, characterized in that the substrate (1) is made of glass, glass ceramic or a transparent plastic.

9. Coated substrate according to one of claims 1 to 8, characterized in that the functional multi-layer coating (2) is electrically conductive and heatable by applying a voltage.

10. Composite pane (100, 200, 300), in particular for a vehicle or a building, comprising an outer pane (1a) with an outer surface (I) and an inner surface (II) and an inner pane (1b) with an outer surface (III) and an inner surface (IV), which are connected to one another by a thermoplastic intermediate layer (5), characterized in that the outer pane (1a) and / or the inner pane (1b) is formed as a coated substrate according to one of claims 1 to 9.

11. Composite pane (100, 200, 300) according to claim 10, characterized in that the functional multi-layer coating (2) is formed on the interior-side surface (II) of the outer pane (1a) and / or on the interior-side surface (IV) of the inner pane (1b).

12. A method for producing a coated substrate according to any one of claims 1 to 9 or a composite pane (100, 200, 300) according to any one of claims 10 or 11, comprising the steps A) Providing at least one substrate (1), B) applying a first dielectric (4a) comprising at least one dielectric layer to the substrate (1), C) Applying a three-layer combination (3) of TiCx (3a) / TiN (3b) / AIN (3c) to the first dielectric (4a) applied in step B, D) applying a second dielectric (4b) comprising at least one dielectric layer to the three-layer combination (3), wherein in step C) starting from the substrate (1) and the first dielectric (4a) arranged thereon, a layer sequence TiCx (3a) / TiN (3b) / AIN (3c) or AIN (3c) / TiN (3b) / TiCx (3a).

13. The method according to claim 12, characterized in that in step C) the titanium nitride (TiN) layer (1b) is produced by high-power pulse magnetron sputtering (HiPIMS).

14. The method according to claim 12 or 13, characterized in that after step D) a heat treatment is carried out, preferably at a temperature of 300°C to 800°C.

15. Use of a coated substrate according to one of claims 1 to 9 or a composite pane (100, 200, 300) according to one of claims 10 or 11 in buildings or in a vehicle pane or as a vehicle pane, in particular as a roof pane, rear window or side window of a vehicle.

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